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‘THE PHILIPPINE
JOURNAL OF SCIENCE
ALVIN J. COX, M.A., Pu. D.
GENERAL EDITOR
SECTION A
CHEMICAL AND GEOLOGICAL SCIENCES
AND THE INDUSTRIES
EDITED WITH THE COOPERATION OF
W. D. SMITH, Pu. D.; H. D. GIBBS, Pu. D.; W. C. REIBLING, Cu. E.
W. E. PRATT, A. M.; R. R. WILLIAMS, M. S.; D. 8S. PRATT, Pu. D.
R. C. MCGREGOR, A. B.
VOLUME VIII
1913
WITH 54 PLATES, 38 TExT FIGURES, AND 4 MAPS
BUREAU OF PRINTING
1913
2323 25
CONTENTS
No. 1, February, 1913
Gisss, H. D., WiuuiaMs, R. R., and GALAJIKIAN, A. S. Methyl
salicylate IV. The saponification of methyl salicylate, methyl
benzoate, and the methyl ether of methyl salicylate...................-.--
Text figures 1 to 5.
Gipss, H. D., and Pratt, D. S. The mutual influence of hydroxyl
and carboxyl and some related groups in the ortho position.
A study of the absorption spectra of phenol, o-cresol, o-hydroxy-
benzyl alcohol, salicylic acid and its methyl ester, methyl ether
of salicylic acid and its methyl ester, benzyl alcohol, benzyl
acetate, benzyl methyl ether, benzyl chloride, and methyl ben-
zoate eps aks ce sae ae EE SG ce ee SR ace
Text figures 1 to 5.
Pratt, D. S., and Gispps, H. D. The absorption spectra of pheno-
quinone, 2, 5-dianilinoquinone, 2, 5-dianilinoquinoneanil, and 2,
5-dianilinoquinonedianil (azophenine) .............2..2.-----------eeeeceeeeeeeeeeees
Text figures 1 and 2.
Pratt, D. S., and Det Rosario, J. I. Philippine fruits: Their
composition and characteristics: <...<..-...::cc:c.-0c:-ccce-scrovecsaccecessncenaseaceneee
Plates I to XVI.
No. 2, April, 1913
EDDINGFIELD, F. T. Ore deposits of the Philippine Islands................
Plates I to III. Text figures 1 to 4.
REIBLING, W. C. A bonus system for the purchase of Portland
OBSEIEEIVE | ganas eos aes eee ee pee al tao ee Sie ER ee aa ee Be
EDDINGFIELD, F. T. Alteration and enrichment in calcite-quartz-man-
ganese gold deposits in the Philippine Islands...............................
EDDINGFIELD, F. T. Gogo, Entada scandens Bentham, and its effect
OMe rolds and old: Solution sz. -i..2. 22 vecceececce sos cteceee ct sckecacncsecncccscananeent
No. 3, June, 1913
AGCAOILI, FRANCISCO. The composition of various milks and their
adaptability for infant feeding... 2... o.oo cies
Plate I.
Dovey, E. R. The composition of carabao’s milk...
TEMPONGCO, CLODOALDO. Sugar-cane experiments............0.200.200.002-2----
PratTT, D. S., and Gispps, H. D. The two phthaloximes: A study
of their absorption spectra and constitution..........00.0.00220.00.00.0.20----
Plates I and II. Text figures 1 to 6.
Pratt, D. S. The optical efficiency of tinted glasses in relieving
CRE SESS aS ie toe 5 UO ers eo Oe
Plate I.
Page.
33
51
59
81
107
125
135
iv Contents
No. 4, August, 1913
Page.
SADERRA Mas6, MIGUEL, and SMITH, WARREN D. The relation of
seismic disturbances in the Philippines to the geologic structure.. 199
Maps 1 to 3.
SMITH, WARREN D. Contributions to the stratigraphy and fossil
invertebrate fauna of the Philippine Islands.......................--.-2.- 235
Plates I to XX.
No. 5, October, 1913
PRATT, WALLACE E., and SMITH, WARREN D. The geology and
petroleum resources of the southern part of Bondoc Peninsula,
Tayabas Provinee, P.\0.. a ee ae 301
Plates 1 to X. Text figure 1. Map 1.
No. 6, December, 1913
Pratt, D. S., THURLOW, L. W., WILLIAMS, R. R., and Gipss, H. D.
The nipa palm as a commercial source of sugar. A considera-
tion of the principal difficulties encountered in collecting and
preserving -nipa-palm ‘sap... 2 eee 877
PrATT, DAvip S. The absorption spectra of various phthalides and
related compounds ..........2..-.l.2.08 i 399
Text figures 1 to 15.
West, Aucustus P. Analysis and composition of red lead_............... 429
EDITORIAL. Copra spoilage on a large scale.._........--22-220eesceeeeeeeee eee 439
Plate I.
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THE PHILIPPINE
JOURNAL OF SCIENCE
A. CHEMICAL AND GEOLOGICAL SCIENCES
AND THE INDUSTRIES
VoL. VIII FEBRUARY, 1913 No. 1
METHYL SALICYLATE IV.1. THE SAPONIFICATION OF METHYL
SALICYLATE, METHYL BENZOATE, ‘AND THE METHYL
ETHER OF METHYL SALICYLATE
By H. D. Gipss,’ R. R. WILLIAMS,
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
and
A. S. GALAJIKIAN *
(From the Department of Mathematics, University of the Philippines,
Manila, P. I.) ,
Five text figures
In the first paper on this subject it was shown that salicylic
acid could be accurately determined in the presence of its methyl
ester by first adding an excess of sodium hydrogen carbonate
solution, which will unite with the acid to form sodium salicylate,
and then shaking out the ester with a suitable solvent such as
chloroform. The principle of this separation depends upon the
fact that the rate of saponification of the ester by sodium hy-
*I. The separation of salicylic acid from methyl salicylate and the
hydrolysis of the ester, by H. D. Gibbs, This Journal, Sec. A (1908), 3,
101; Journ. Am. Chem. Soc. (1908), 30, 1465; II. Solubility in water at
30°, by H. D. Gibbs, This Journal, Sec. A (1908), 3, 357; III. The colora-
tion of methyl salicylate and some allied compounds in the sunlight, by
H. D. Gibbs, R. R. Williams, and D. S. Pratt, cbid (1912), 7, 79.
*Associate professor of chemistry, College of Medicine and Surgery,
University of the Philippines.
* Assistant professor of mathematics, College of Civil Engineering,
University of the Philippines.
115512 ;
2 The Philippine Journal of Science 1913
drogen carbonate is negligible since the concentration of sodium
hydroxide in the solution is very small.*
Preliminary comparisons of the rate of saponification of the
ester with sodium hydroxide, sodium carbonate, and sodium
hydrogen carbonate showed that the first was fairly rapid, the
second was very slow, and the last had an almost infinitesimal
speed.
Calculations, by means of the formula,®
dC dc
eau (ae )v— 8 (Ge) v
a log C, — log Cy
,
from two different sets of data, gave the values 0.994 and 1.028,
average 1.011, which signified that the reaction between an
excess of methyl salicylate and sodium hydroxide was of the
first order: The velocity constants obtained were very un-
satisfactory and since, at that time, they were not necessary
for the purposes in hand, they were not mentioned and no
explanation was attempted. In this paper much of the pre-
liminary work has been repeated with greater accuracy, the
investigation extended to include methyl! benzoate and the methyl
ether of methyl salicylate, and explanations of the peculiar
phenomena involved are offered.
Methyl salicylate is capable of a variety of reactions, several
of which occur simultaneously in alkaline solution, and affect
the velocity of saponification more or less markedly. Of these,
the following have been noted and studied, and are doubtless
the most important if not the only reactions occurring in alkaline
solution: (1) The splitting of the carboxyl group with for-
mation of carbon dioxide, methyl alcohol, and phenol; (2) the
formation of a colored compound in presence of sunlight and
oxygen ;° (3) the substitution of a metal atom for the hydrogen
of the phenol group with formation of a salt of the methyl ester,
which in water solution is capable of a considerable hydrolysis.
The splitting with formation of carbon dioxide is a reaction
which salicylic acid undergoes very readily at higher temper-
atures,’ but which had not been noted in the case of the methyl
‘The significance of the concentration of sodium salt of methyl salicylate
in the solution will be pointed out later in this paper. This factor is
negligible in the analytical separation.
*Van’t Hoff, Vorlesungen tiber theoretische und physikalische Chemie.
Braunschweig (1901), 1, 194.
* Methyl Salicylate III, loc. cit.
"Meyer u. Jacobson, Org. Chem. (1894), 2, 629.
vi, A,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 8
ester. The formation of the colored compound has a very slight
effect on the rate of saponification even in the light.
The third reaction, that of the formation of a salt of the ester,
has been studied ®* and is responsible for some of the most in-
teresting derivatives of this substance. It has been of special
interest historically because of the analogy of these salts to
those of acetoacetic ether. The same reactivity of the phenol
group is exhibited by the free acid ° and its salts as well as by the
ester. Therefore, the rate of saponification of the ester is also
affected by the formation of basic salicylates C,H, (OM)
COOM.
Lastly must be taken into account the limited solubility of
methyl salicylate which renders the system nonhomogeneous
during saponification unless carried out with low concentrations.
Saponification in nonhomogeneous systems has been studied by
Kremann ” in the case of ethyl benzoate.
The saponification of methyl salicylate with sodium hy-
droxide has been carefully investigated by Goldschmidt and
Scholz in one of their series of papers.1! However, it was seen
that the problem could be attacked from a different standpoint
and some corrections made in their formula as applied to methyl
salicylate. The work of Goldschmidt and Scholz will be taken
up again in the discussion of our own results.
I. CARBON DIOXIDE FORMATION
An experiment was first carried out to determine if carbon
dioxide was formed from methyl] salicylate at low temperature,
and, if so, under what conditions and to what extent.
*Graebe, Ann. Phar. (1866), 139, 184; Schreiner, Ann. d. Chem. (1879),
197, 19; Freer, Am. Chem. Journ. (1892), 14, 411; Nicola, Chem. Cen-
tralbl. (1907), 2, 49.
*Piria, Ann. d. Chem. (1855), 93, 262; Lajoux et Grandval, Compt.
rend. Acad. sci. (1893), 117, 44; Adam, Bull. Soc. chim. (1894), 11, 204;
Kellas, Zeitschr. f. physik. Chem. (1897), 24, 220; Imbert et. Astruc,
Compt. rend. Acad. sci. (1900), 130, 85; Buroni, Gazz. chim. ital. (1902),
32, 311; Ley und Erler, Zeitschr. f. elek. Chem. (1907), 13, 797; de
Coninck, Compt. rend. Acad. sci. (1907), 144, 757, 1118; Goldschmidt
und Scholz, Ber. d. deutschen chem. Ges. (1907) 40, 624; Kailan, Monatsh.
f. Chem. (1907), 28, 115; Thiil und Roemer, Zeitschr. f. physik. Chem.
(1908), 63, 711.
* Monatsh. f. Chem. (1905), 26, 315. See also Reicher, Ann. d. Chem.
(1885), 228, 285.
“ Ber. d. deutschen chem. Ges. (1907), 40, 686. See also Kellas, Zeitschr.
f. phys. Chem. (1909), 66, 81; (1909), 67, 257; and Finlay and Turner,
Journ. Chem. Soc. (1905), 87, 747.
4 The Philippine Journal of Science 1918
Pure sodium hydroxide was prepared by the following method.
Pure metallic sodium freed from oxide, carbonate, and hydro-
carbons so far as possible was introduced into a test tube, the
bottom of which was connected to a mercury pump by a piece
of narrow glass tubing about 3 millimeters internal diameter
and from 0.5 to 1 meter long. A slight constriction was made
in this tube near the test tube. The end of the test tube was
then sealed, and the whole exhausted and warmed to drive off
hydrocarbon vapors. After sealing the narrow tube near the
pump, the sodium was melted and allowed to flow by gravitation
through the constriction, thus filling the tube with pure metallic
sodium, the crust of oxide and carbonate being held back.
Pieces of this tube were broken off and quickly dropped through
the hole of a rubber stopper into a flask of pure water, the at-
mosphere over which had been replaced by hydrogen. A rapid
current of hydrogen was passing through the flask when it was
opened to admit the sodium. After the sodium had dissolved, the
flask was opened and quickly substituted for flask D (fig. 1), the
apparatus in the meantime having been freed from any carbon
dioxide by a soda-lime tube connected at A and sticks of caustic
soda in the flask D. It was found on acidifying, boiling, and car-
rying the gases with a stream of hydrogen into barium hydrox-
ide solution, forced from a bottle into F’, through stopcock G, and ©
thus obtained pure, that no trace of carbon dioxide was evolved
from the sodium hydroxide thus prepared. C and E are con-
densers for holding back vapors of the boiling liquid. Two
experiments were made with such a solution. In the first, about
0.5 gram of sodium as hydroxide was allowed to react for fifteen
hours at room temperature with a small excess of the ester in-
troduced through the funnel B. At the end of this time the
solution was acidified with sulphuric acid, boiled, and the vapors
passed into the barium hydroxide solution. A slight precipitate
of barium carbonate was formed. A second experiment, carried
out in the same manner except that the alkali was allowed to
react with the ester overnight at 50°, produced a much larger
precipitate of barium carbonate. By comparing the volume of
this precipitate with precipitates from measured quantities of
N/50 NaHCO, solution in tubes of approximately the same
diameter, it was estimated to represent 0.3 to 0.5 milligram of
carbon dioxide.
An experiment with 5 grams of the ester and 100 cubic centi-
meters of N/10 sulphuric acid showed that the carboxyl group
vil, A,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV
°
Scale 1=4 Cm
Fic. 1—Apparatus for detecting carbon dioxide formation.
6 The Philippine Journal of Science 1913
is not split by boiling in dilute acid solution. This proves that
the carbon dioxide is a result of the alkaline hydrolysis and
probably from salts, rather than from the ester itself.
A further proof of this statement is found in the following
experiment. A sealed tube containing salicylic acid and N/10
sulphuric acid was heated on a steam bath in the dark for eight
months without the formation of any color and with no appre-
ciable internal pressure. The absence of color is an indication
that no carbon dioxide is split off. If phenol were formed, it
is probable that some color would be produced by the oxidation
of phenol to quinone.’ The extent to which the splitting of car-
bon dioxide takes place in alkaline solution is so small as to render
carbon dioxide formation a negligible factor of the rate of sapon-
ification at ordinary temperatures.
II. THE FORMATION OF SODIUM METHYL SALICYLATE AND ITS
HYDROLYSIS
The influence of sodium methy] salicylate on the rate of sapon-
ification depends upon the degree of hydrolytic dissociation of
the salt in water solution. Goldschmidt has calculated the value
for r in the following equilibrium equation to be 0.001.
Cyaon x (C,H OH-COOCE: _,.
CcH.-ONa-COOCHS
His method was to determine the affinity constant of the phenol
group of the ester and to obtain the hydrolytic constant of the
salt from the relationship
K
Si oa
KSGkir
B E
in which K , K , and K are the affinity constants of water,
W E
the base (diethylamine), and the ester, respectively. It was
thought advisable to determine the hydrolytic constant of sodium
methyl salicylate by a more direct method. If methyl] salicylate
be dissolved in pure aqueous sodium hydroxide, after the first
moment of time, the following substances are present, the con-
“The compounds which cause the red color in phenol, by Gibbs, This
Journal, Sec. A (1908), 3, 361, and The oxidation of phenol, ibid. (1909),
4, 133.
vill, A,1 Gibbs, Williams, Galajikian Methyl Salicylate IV 7
centrations of which may be represented by the symbols opposite
them.
Free base (NaOH) n
Free ester (CcsH:OH-COOCH:) e
Sodium methyl salicylate (C;-H:ONa-COOCH;:) m
Mono-sodium salicylate (C;sH:OH-COONa) s
Di-sodium salicylate (CsH:ONa-COONa) d
Let a = the total concentration of sodium atoms and 7 = the
total concentration of radicals containing the benzene grouping.
Let x = the concentration of sodium titrated as combined when
Congo red is employed as indicator. Then the following rela-
tions are true.
—=r (1)
m
ns
—=r’=0.03 (Goldschmidt) (2)
d
x=s+d (3)
a—x=m+n+d (4)
i=m+e+s4+d. (5)
Equation (1) represents the hydrolytic equilibrium of sodium
methyl salicylate. Equation (2) represents the equilibrium for
di-sodium salicylate, and Goldschmidt’s average experimental
. value of 0.03 is used as the hydrolytic constant. Equations (3),
(4), and (5) follow from the fact that, with most indicators
such as Congo red, the sodium in the phenol position is titrated
as free.
Solving the above five simultaneous equations,
_ 0.03 e (a—i+e)
¥~(e+0.03) (G—x—e)° Wy
a can be determined by previous titration of the sodium hydrox-
ide solution, 7 by the colorimetric method for salicylic acid after
complete saponification, and x by titration at any time when the
system has attained equilibrium, disregarding the progress of
the saponification. For determining e, two methods are applic-
able: The first, by using an excess of the ester in which case e
will be equal to the maximum solubility, about 0.005 molar; and
the second, according to Farmer and Warth," by means of its
partition between water and an immiscible solvent.
_
* Trans. Chem. Soc. London (1901), 79, 863; ibid. (1904), 85, 1713.
8 The Philippine Journal of Science 1913
For our experiments, a sample of ligroine free from benzene
hydrocarbons was used. For determining the partition coeffi-
cient, 500 cubic centimeters of pure water were shaken at 30°
with 25 cubic centimeters of ligroine in which a weighed amount
of ester was dissolved. After two hours’ shaking, the water
was siphoned off and colorimetric determinations were made of
the methyl] salicylate in 10 cubic centimeters of each layer.
Ester Ester ae
: Partition
Experiment No. per ce. of | per cc. of 5
ligroine. water, | Coefficient. |
== je ee ee
IR RS A yl ES Ne eee a ee ee ante: 2s 0. 08962 0. 00064 140.0
Die es ee eS me oe a ee 0. 06300 0. 00048 131.2
Behe a ee erie a a a 0. 07977 0. 00060 132.8 |
“Averare 2252 ee 2026 gi a ee ee ee ee 134.7
Therefore, the concentration of methy! salicylate in the ligroine
will be about 135 times that in the water under the conditions
stated.
In order to determine the hydrolytic constant of sodium methyl
salicylate, experiments were carried out under the same con-
dition as above, except that pure dilute aqueous sodium hydroxide
of known titre was substituted for the water. a, i, and x were
determined by the methods given above; e was taken as 1/135
times the concentration of methyl salicylate in the superincum-
bent ligroine layer. The data obtained follow. 7 was calculated
from equation (6).
No. 1. No. 2.
a= 0.0159 0.0638
= 0.0072 0.0155
— 0.0114 0.0600
e= 0.0005 0.0059
— 0.00066 0.00124
Experiments by the method of maximum solubility were
carried out as follows. About 5 grams (a large excess) of
methyl! salicylate were shaken for about two: hours at 30° with
about 25 cubic centimeters of standard sodium hydroxide with
the following results:
No. 1. No. 2.
a= 0.0993 0.0993
xis 0.0483 0.0481
iS 0.0970 0.0971
e = 0.005 0.005
r= 0.00072 0.00070
vil, 4,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 9
a, x, and i were determined as before, and e taken as 0.005,
the maximum solubility.
While neither method is capable of great accuracy, still the
four values of r computed according to equation (6) confirm
Goldschmidt’s result of 0.001 as substantially correct.
III. THE EFFECT OF NONHOMOGENEITY ON THE RATE OF
SAPONIFICATION
THE SAPONIFICATION OF METHYL BENZOATE
For this purpose the reaction of methyl benzoate with sodium
hydroxide was first studied. This reaction is a bimolecular one
when it takes place in a homogeneous medium. When, however,
the hydrolysis takes place in aqueous solution in which the ester
is but slightly soluble, the reaction proceeds sensibly as a mono-
molecular one. This has already been pointed out by Kremann **
in the case of ethyl benzoate and amyl acetate which he took as
typical representatives of the class of difficultly soluble esters.
He failed to point out the mathematical basis for the observa-
tions, contenting himself with a statement of the uselessness of
such observations as a means of learning the mechanism of the
reaction.
The mathematical basis is very evident. A bimolecular re-
action is one in which the velocity is proportional to the concen-
trations of two variables. When one of the reacting substances
is sparingly soluble its concentration is limited by its solubility;
that is, the amount transposed is immediately replaced if an ex-
cess is always present, unless the velocity of solution be less than
that of transformation. Then the equation for a bimolecular
reaction becomes a = K(a — x) (b — x + x), in which @ and
b are the original concentrations, x is the quantity of each
transposed at the time ¢, and (b—x-+x) is a constant limited
by the solubility of the ester. That is, one variable may be
regarded as disappearing, and the equation becomes = K,
(a — x) in which K, = K times the molecular solubility of the
free ester. Kremann’s results would have shown this more
clearly if he had used an excess of the ester so that the concen-
tration would remain the same to the end of the reaction. If
this is done, the value for K, remains constant, as is shown in
the case of the methy] ester in the following experiment.
* Monatsh. f. Chem. (1905), 26, 315.
10 The Philippine Journal of Science 1918
TABLE I.—Saponification of methyl benzoate with NaOH 0.0920 Normal.
T=80°=+0.1° Corallin indicator.
paniten 2 iis 3 K= Sue
0 0;0920)5/ S22 ca8 2 e ohne
6 0.0610 0. 0685 4.369
12 0. 0400 0. 0693 4, 420
17 0.0280 | 0.0699 4, 458
23 0. 0180 0. 0709 4, 522
28 0. 0125 0.0711 4.535
83 0. 0085 0. 0720 4,592
38 0. 0058 0. 0725 4.624
43 0. 0042 0. 0718 4.579
50 0. 0027 0. 0705 4,497
63 0. 0015 0. 0654 4.172
18 0. 0005 0. 0668 4.261
Average com-
puted after dis-
carding the
first one and
last two values _| 0.0710 4.529
In order to compute K from K,, determinations of the solu
of methyl benzoate in water were made.
Freshly boiled, distilled water and pure methyl benzoate were
employed for the purpose. The water and an excess of the
ester were shaken violently, producing an emulsion, for three
hours at 30° in glass-stoppered bottles. Twenty-five cubic-
centimeter portions of the water were then saponified in the cold
with standard sodium hydroxide solution, and the excess titrated.
The following values were obtained.
N/10 NeOe ~ a5 i
. per 25 cc. olar solu-
Experiment No. saturated es- bility.
ter solution.
EST er I hc a OE al DONA th) Se an | 3. 88 0. 01552
Pe hse 1 Sry AYER OL A ee a As We Sate 3.96 0. 01584
WA Verag ele ane Fe Sa ads Ae gee eg 0. 01568
Any reaction between a difficultly soluble ester and a base
will be monomolecular so long as conditions are such that the
concentration of the ester is kept at the maximum allowed by
its solubility. It is, of course, apparent that the solubility of
the ester may be increased by the formation of alcohol in the
reaction mixture. However, the error from this source in dilute
solution is small.
vil, 4,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV ri
In order to test the correctness of the value for K as found in
Table I, the rate of saponification was determined in homo-
geneous aqueous solution by using a concentration not exceeding
the maximum solubility of the ester. The values for K in this
case were calculated according to the equation for a reaction of
the second order Ka x
: - The results are found in
t° a (a—x)
Table II.
TABLE II.—Saponification of methyl benzoate with NaOH.
NaOH = 0.0147. Ester =0.0147. T=380° +0.1°. Indicator corallin.
1 x
e % ai |e t a (a—x)
0 0 OSOUAT)} Goa eS
5 0. 0044 0. 0103 5. 184
10 0. 0066 0.008% 5.516
16 0. 0082 0. 0065 5. 345
26 0. 0098 0.0049 5. 232
36 0.0107 0. 0040 5.055
46 0. 0116 0.0031 5. 534
A VeETARE Ht o328 = 462. ES 5. 411
The values for K obtained by the two methods agree fairly
well in magnitude, considering that the small concentrations
used, when working in homogeneous solution, greatly magnified
the experimental error.
THE SAPONIFICATION OF THE METHYL ETHER OF METHYL SALICYLATE
The methyl ether of methyl salicylate was also investigated
in the same manner to test the validity of calculating the reaction
velocity constant in nonhomogeneous solution according to a
reaction of the first order. The solubility of the methyl ether
of methyl salicylate in water at 30° was first determined by the
same method as was used for methyl benzoate. The results are:
| Nil0 NaOH
d requir or 25 Molar
Experiment No. cc. saturated solubility.
solution of
ester.
12 The Philippine Journal of Science 1913
The data for the saponification of this ester with sodium
hydroxide in nonhomogeneous and homogeneous solutions are
found in Tables III and IV, respectively. Again the two
methods of obtaining the reaction velocity constant give fairly
satisfactory agreement.
TABLE III.—Saponification of methyl ether of methyl salicylate with NaOH
in nonhomogeneous solution. NaOH =0.1030. Ester (excess) =0.371
constant. T= 30° + 0.1. Indicator corallin.
| are |
——
tit x a—x t go RANE
| log 2 0. 0371
| | a—x
0} 0 | 0.1030 |----------------|----------------
4 | 0. 0270 | 0. 0760 0.07590 | 2. 046
9 | 0.0514 | 0. 0516 0. 07671 2.068 |
14 0. 0690 0. 0340 0. 07909 2.131
20 | 0. 0814 0. 0216 0. 07800 2.108
30 0.0921 0.0109 0.07479 2.016
40 0. 0960 0. 0070 0. 06716 1.810 |
Argenages 2 oir aw A Bee eas | 2.029
TABLE I1V.—Saponification of the methyl ether of methyl salicylate with
NaOH in homogeneous solution. NaOH =—0.0308. Ester =—0.0308.
T = 30° + 0.1. Indicator corallin.
1 x
t 2S ae ae +t ala—x)| -
Cel epee ee Be Mr yr ae ae
4.5 0.0078 0.0230 | 2.447
9.0 0.0132 | 0.0176 2.706
15.0| 0.0169 0.0139 2. 631
25.0 0. 0205 0. 0103 2.585
35.0 0.0228 0. 0080 2. 643
45.0 0.0240 0. 0068 2.547
| 55.0 0.0252 0.0056 2. 655
75.0| 0.0263 0. 0045 | 2.530 |
Averiges 2 == aaeeee 2.593 |
IV. THE EFFECT OF CONTACT ACTION
In order to determine the possible influence of contact action
on the saponification, the rate of change in the presence of large
excess of ester was compared with that in presence of small
excess, methyl salicylate being employed for this purpose.
The theoretically equivalent amount of ester was shaken for
about two hours with 25 cubic centimeters of N/10 sodium
hydroxide solution, the shaking apparatus revolving at about 20
vi, 4,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV | i>
revolutions per minute. The ester in this case did not emulsify,
but remained in one large globule, which at each revolution
rolled from one end of the tube to the other.
A second experiment using five times the theoretical equivalent
of ester was carried out simultaneously with hydroxide solution
of the same strength and at the same temperature, 30°. These
tubes were revolved at the rate of 120 revolutions per minute,
which was sufficiently vigorous to break up the ester into fine
globules which for the most part remained suspended in the
aqueous solution. ~The following results were obtained on
titration:
Experiment No. 2.
Five times the equiva-
lent amount of
ester; 120 revolutions
per minute.
Experiment No. 1.
Equivalent amount of
ester; 20 revolutions
per minute.
(a) 0.0278 0.0280
(b) 0.0280 0.0283
Average 0.0279 0.02815
While the amount transposed in experiment 1 was found to be
slightly less, the difference is not greater than experimental
error. Contact action is therefore excluded.
Vy. THE SAPONIFICATION OF METHYL SALICYLATE
When methy] salicylate is shaken with aqueous sodium hydrox-
ide, there exist in solution the following substances, the con-
centrations of which are represented by the symbols following
them: Free base (n), free ester (e), sodium methyl salicylate
(m), di-sodium salicylate (d), and mono-sodium salicylate (s).
If such a reaction mixture is titrated with a strong acid, using
Congo red as an indicator, all the sodium which exists in the
carboxyl group will be titrated as combined, while that existing
as free base or substituted in the phenol group will be titrated
as free. That is, if a represents the total sodium and « the
combined sodium,
x =s-+d (3)
a —x=m-+n+d. (4)
We have also established the relationships
=} 1 ae ts, 2
— = 1=0.001 (1)
= =r=0.03 (3)
e =0.005 (7)
* Poirrier blue is the only known indicator for the acidity of phenol.
Imbert et Astruc, Compt. rend. Acad. sci. (1900), 130, 35.
14 The Philippine Journal of Science 1913
By solving algebraically the simultaneous equations: (1), (2),
(3), (4), and (7), we may express n, the free base in our ex-
periment, in terms of « as follows:
V X2—ax-+0.018824— (x-+0. 0428)
n=—— 5 , (8)
in which a=0.0944. (Table II.)
Now, when methyl salicylate is saponified, the rate of the
reaction will be proportional to the product of the free base
and the free ester; that is,
it = K en, (9)
in which xz, is the amount of ester hydrolysed and K is the
reaction velocity constant.
However, upon consideration it will be apparent that this
reaction is accompanied by another saponification reaction which
results in the same products. For it is erroneous to suppose, as
ONa
/ COOCHs,
can exist in the presence of free NaOH without undergoing
saponification, according to the equations
CsHz:ONa:COOCH3-++Na0H —C,H,-ONa:;COONa+CH;0H
CsHs ONa:‘COONa+H:20 sC,H,-OH-COONa+Na0OH.
The rate at which this saponification takes place will in all
probability be different from that at which the free ester is
saponified. That this rate is appreciable cannot be doubted,
since it is impossible to assign to the sodium in the phenol
position per se the peculiar property of entirely protecting the
adjacent —COOCH, group from attack. If x, is taken to rep-
resent the concentration of the substance transposed by this
reaction, we can express the velocity of this saponification by
the equation
Goldschmidt does, that sodium methy] salicylate,
dx2__
C=
in which K, is the reaction velocity constant and m vn is the prod-
uct of the concentrations of the reacting substances. But from
(1) and (7),m=5n. Substituting this value in (10), we obtain
Kim n, (10)
-
dx, 2
ew Ki on (11).
Now, if x, represents the amount of free ester transformed,
and «, the amount of sodium methyl ester transformed, their
vin, 4,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 15
sum will represent the total result of*hydrolysis at any time ft.
This may be obtained experimentally by titration, and is the
quantity which we have represented by the symbol x. The fact
that x represents di-sodium salicylate as well as mono-sodium
salicylate is of no. moment in this connection since both are prod-
i c s . ks dx B00! dx2
ucts of saponification. Then, if x=x1+ x:, ah wee = are
Adding (9) and (11),
dx _ 2
qe en-++5 K; n (12).
Substituting in (12) the value 0.005 for e and the value of n
obtained in (8), we have
dx 0) OOskE
dt
+ BKip
§ | V2 —0.0944xf0. 018824 x0. 0428 |
= 0944x-+0.018824—x—0. 0428 |.” (13).
Ko [/x2—0.0944x-+0. 018824—x—0.0428] +
Ks [1/x2—0.0944x-+0, 018824—x—0, 0428], 16 (I).
The integral of this differential equation is a very complicated
expression containing the two constants in several different
forms, and it would be extremely difficult to determine them
from the integral expression after substitution of the experi-
mental values for ¢ and x in Table V. It is possible, however,
to get approximate values for K, and K, by the application of
Simpson’s rule to the differential equation. The degree of ap-
proximation can afterwards be tested, and the values of the
constants modified, if necessary.
In applying Simpson’s rule in this case, the method of pro-
cedure is as follows:
Putting the equation into the form of a definite integral
te Xz dx II).
i es -J,. Ke [2]-FKa [ZF es
we see that the time ¢ is the area under the curve plotted between
values of x as abscissas and the values of Pea ARSaVAG
as ordinates.
** In the following equations, the term inside the brackets will be expressed
by Z for the sake of brevity.
16 The Philippine Journal of Science 1913
Taking different intervals of time from the experimental data
in Table V, we can form as many independent equations as we
please. Six different intervals were taken; namely,
t—600—65=535 min., t—540—65=475 min., t—480—65=—415
min., t=600—185=—415 min., t=600—245=—335 min., and t=600
—305=295 min,
The differences between the corresponding values of x were
i
K, [Z1-+K, (ZI
computed. For example, the equation for t=535 min. is
divided into 10 equal parts and the values of
600
i ab 585 FL (0+ Yn) -+2(Vo+ Vet YoYo)
5)
+4(Y,+Y,+Y;+Y,+Y,) ]
1
che Syalues (Ob Lye, ay..y eve, .are K, (0.0613) + K, (0.00376)
1
K, (0.054) +K, (0.00292)
In summing up the values of y, the denominator was factored
in such a way as to make one factor the same as the numerator
and the other containing K, and K, to the first power. Of course,
factoring exactly is impossible, but the difference between the
numerator and the first factor of the denominator was very
small and canceling them with each other allowable.
To illustrate:
, ete.
0.00567 1 |
Vital? aie l= (0.0008067) +Ksz (0.00001398) 3 oe
0.00543 1
== [= (0.000877+-Ks ae
Solving for K, and K, between these equations
K:=0.00454, K:—0.0223.
Proceeding in this way with the other equations, a set of values
of K, and K, may be determined.
Since in the expression for y the effect of K, is very small
compared with that of K.,, K, being multiplied by the square of
the coefficient of K,, a small quantity in itself, we are justified
in assuming its value as correct and substituting it in the four
other equations to determine K,,.
vi, A,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 1
The four remaining equations are:
0.00598 1
ed eee | ae)
0.00845 1
Sl == eee
0.00252 1
3 “SEES (18)
0.00191 [ 1
3 SUSE
t=335=
t=295—
Peel PS
PEE ee
eG
ame fan fed se Pedant eats oad Pec ed
>So ee eee
Bee eae Te eS er re ea
BEE fond Ty ony Jay CO i”
Pemieeneeee erst penn Bua dseemse5eS550000581 (0
Fic. 2—A curve for the graphic Tuisaaination of t, to test 3 accuracy of the
values: K2=0.0053; K=6.86; K3=0.0223; K,=0.1605.
115512——2
18 The Philippine Journal of Science 1913
Substituting 0.0223 for K, in (16), (17), (18), and (19), we
obtain, for K,, 0.00498, 0.005176, 0.005589, and 0.005489, respec-
tively. The mean of the five values of K is 0.00516.
Now, putting t,—600, t,—305, x,=—0.0861, and x,—0.067 in
equation II and applying Simpson’s rule, we get t=311.47 min-
utes instead of 295 minutes, the observed value. Leaving K, as
it is and changing K, to 0.0053, we obtain for the same difference
between the values of xz, 303.6 minutes, an error of 2.5 per cent.
Plotting the values of x as abscissas and the values of
KCTS KE as ordinates, using K,—0.0223 and K,—0.0053,
we obtain a smooth curve, which shows that the values of K, and
K, are at least very good approximations (fig. 2). We can
now test the accuracy of the constants by computing the values
of ¢ from the area under this curve. For example, the area
under the curve from x—0.0516 to x—0.0861 gives 400.54 min-
utes instead of 415 minutes, an error of 3.5 per cent.
Similarly, values of ¢ computed from the curve between dif-
ferent values of x agree well with the observed values of t,
except for the first three values of x. The values of ¢ from
x=0.04 and x=0.069, for instance, show a discrepancy of 25 per
cent.
This greater discrepancy during the earlier part of the sapon-
ification is undoubtedly due to the excessive velocity of the
transformation as compared with the rate of solution.
TABLE V.—Saponification of methyl salicylate with NaOH 0.0944 Normal.
T=30° + 0.1. Congo red indicator.
t (inter-
al eer centr ssa 6 |
0} o 050944: || (0;00218) |25 =i eal eee
65| 0.0268! 0.0681] 0.00194/_________|_____________
12540804001) (1050544010007 86) | seeeeee | amen ama
E85} OF 0516) |) 100428) | (81000184 ean aeataeen | Mae enema
245 | 0.0609] 0.0385} 0.00176 |_--_______|_-__--_-______
305 | 0.0670 | 0.0274} 0.00176 295 0. 005489
365 | 0.0721] 0.0223 | 0.00176 335 0. 005589
415} 0.0769] 0.0175 | 0.00174 415 0.005176
480 | 0.0806] 0.0138 | 0.00168 415 0. 004540
540 | 0.0830] 0.0114/ 0.00176 535 0. 004980
GOOY'|' | NOLOBGI I” VOuOOgey ase tea cell] Jet Ln | ep
ie Mean 0. 005160
vill, A,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 19
If we take the values K,—0.0053 and K,=0.0223, K=6.36 and
K,=0.1605. This value of K agrees very well with the value
calculated by Goldschmidt. His whole calculations, however,
ignore the possibility of any saponification of sodium methyl
salicylate taking place. While such a supposition was not jus-
tified by any facts at his command, yet it proved to be nearly
true. That is, the reaction velocity constant of the saponifica-
tion of sodium methyl salicylate proves to be only about 0.1605
or about 1/40 of that of methyl salicylate. His error, therefore,
did not prove great enough to invalidate his mean numerical
value for Ky, although the constancy of his values left much
to be desired.
It is rather startling to find that sodium methyl salicylate is
saponified so extremely slowly as compared with the free ester.
In the following paper,” an investigation is described which
throws some light upon these facts.
VI. HYDROLYSIS OF METHYL SALICYLATE WITH SODIUM CARBONATE
Methyl salicylate was saponified with a pure, freshly prepared
solution of 0.3998 normal sodium carbonate. The temperature
ee | Bisel
femooe cect
| Zee ae ae eee
Ge Sa SS ee
_ a SS eee eee
ic
dee ae se Ee 200-0800
Fic. 3.—Saponification of methyl salicylate and benzoate with NaOH (above)
and Na2CQz3.
*“ Gibbs and Pratt, This Journal, Sec. A (1913), 8, 33.
20 The Philippine Journal of Science 1913
was kept at 25°. Saponification, with a large excess of the ester,
was carried on in small bottles filled to the neck with the
standard solution. A separate bottle was used for each titra-
tion, and all were kept tightly stoppered with glass stoppers
until titrated. By this means no carbon dioxide was allowed
to escape. Under these conditions it is theoretically possible to’
calculate the concentration of the free base and the velocity
constants, but the complexity of the mathematical treatment
necessary is such as to render it impractical. The experimental
data are given in Table VI for purposes of comparison with
Table VII, which contains the same data for methyl benzoate.
It will be seen that a similar relationship exists between the
rates of saponification of methyl benzoate and methyl salicylate,
whether sodium hydroxide or carbonate is used for saponifica-
tion (fig. 3). Saponification practically ceases when all the
carbonate has been converted into the bicarbonate.
TABLE VI.—T=25°+0.1. Methyl salicylate=eucess. Na:CO:=0.3998 N.
= x. anes 1000 Kmono.
1 0.0130 0. 3868 0. 240
3 0. 0250 0. 3748 0. 155
5 0. 0334 0, 3664 0. 126
8 0. 0467 0, 3531 0.112
12 0. 0572 0.3426 0. 093
20 0.0777 0.3221 0.079
30 0.0919 0.3079 0. 063
50 0. 1180 0. 2880 0. 047
100 0. 1539 0. 2459 0. 035
190 0.1797 0.2201 0. 023
TABLE VII.—WMethyl benzoate=eucess. NazCO;=0.3998 N. T=25°+0.1.
a x a—x. 1000 Kmono.
1 0. 0098 0.3900 0.180
3 0.0145 0. 3853 0. 090
5 0. 0215 0. 3783 0. 080
8 0. 0305 0. 3693 0. 072
12 0. 0335 0.3663 0. 053
20 0. 0394 0. 3604 0. 035
30 0. 0450 0. 3548 0.029
50 0. 0748 0.3250 0.027
100 0. 1267 0.2781 0. 027
190 0. 1982 0. 2016 0. 026
vu, 4,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 21
VII. THE HYDROLYSIS OF METHYL SALICYLATE IN WATER
MEASUREMENTS AT 30°
The methyl salicylate employed was especially purified by
shaking with sodium hydrogen carbonate solution, drying over
fused calcium chloride, and distilling at 6 millimeters’ pressure.
A few determinations carried on without precautions to insure
great accuracy showed that saturated solutions of salicylic acid
in water and in methyl salicylate contained at 30° about 0.32
gram per 100 cubic centimeters of the former solvent and 9.81
grams in the latter, a ratio of about 1 to 30 or 31. Saturated
aqueous solutions of salicylic acid shaken with methyl] salicylate
until equilibrium was reached have the following distribution
of salicylic acid.
One volume water and one-half volume methyl salicylate
gave 6 per cent of the salicylic acid in the water and 94 per
cent in the ester as the average of a number of determinations.
One volume of water and one volume of ester gave about 3
per cent in the water and 97 per cent in the ester, a ratio of
about 1 to 32.
Conductivity measurements. —Conductivity measurements
were made at 30° in small cells in one end of which the electrodes
were sealed (fig. 4). After the introduction of the solution,
the other end was sealed.
|] aa
Fic. 4.—Conductivity cell.
The cells were standardized at 30° by means of N/50 potas-
sium chloride solution, and the data given in Kohlrausch and
Holborn ** and the Kohlrausch methods and standards were
employed in the manipulation.
It is realized that measurements at 30° introduce some com-
plications, but at lower temperature a serious error was some-
times encountered, because of the construction of the cell which
permitted a short circuit at the point where the electrodes were
sealed into the glass due to the condensation of moisture from
the humid atmosphere of this locality.
The first conductivity measurements, recorded in Table VIII,
were made in a cell charged with 15 cubic centimeters of water
Das Leitvermégen der Elektrolyte. Leipzig (1898).
929 The Philippine Journal of Science 1913
and 0.5 cubic centimeter of methyl salicylate. While the con-
ductivity of the aqueous solution of methyl salicylate can be
estimated in this experiment, it is obviously impossible to follow
the hydrolysis with any degree of accuracy, for the reason
that a considerable proportion of salicylic acid is removed from
the aqueous solution by the methyl] salicylate.
The first measurement, to, was made after vigorously shaking
together the methyl salicylate and the water for one-half minute.
The tube was then placed on a revolving wheel and agitated
continuously between successive observations.
In the following table, ¢ is the time in minutes; R, the re-
sistance in ohms; ¢ the dilution, that is, the number of liters
containing a gram molecule; A, the molecular conductivity; a,
the degree of dissociation; and K ae the affinity constant of the
methyl ester of salicylic acid.
TABLE VIII.—Conductivity of methyl salicylate in aqueous solution.
Cell No. 1. Constant = 0.1549. Temperature = 30°.
a, | R=ohms. _ £108. A, a, Ky, |
0 17, 040 200 0.80 0.00212 | 2.2-10-11
116 16, 360 200 0.91 0.00247 | 2.9-10-11
198 18) 400{)05 oh | 6k Ian Se
235 12,200: |o.-2! 242]. ene ae
284 11900; [enc coca ceut ss. SE Se ee
331 Ut ie ere
649 8/100 fac aaceses to nas sie | a
At this time, the cell was placed on an open steam bath to
hasten the action, and at =1768 the resistence had dropped
to 355 ohms, a point approaching equilibrium.
The tube was opened, and the contents analyzed as follows:
Water solution, 15 cubic centimeters.
Substance.
Amount in
100 ce.
Methyl salicylate 0.0927
Salicylic acid (almost all present as salt) 0.0792
Methyl alcohol 0.0181
Methyl salicylate solution, 0.5 cubic centimeter in volume.
* 0.272
Salicylic acid
* This determination is perhaps not very accurate.
In order to avoid some of the difficulties experienced in the
first experiment, a second cell was constructed of glass which
viu, A,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 23
was more resistant to the solvent action of acids, and the
amount of methyl salicylate was so reduced that the quantity
of salicylic acid which it would remove from the water would
be negligible. The temperature was maintained at approx-
imately 30° throughout the experiment.
The cell was charged with 15 cubic centimeters of water and
2 drops of pure methyl salicylate and then carefully sealed.
A very small quantity of the ester remained undissolved.
The first reading, t, was made after shaking the cell vigor-
ously for one-half minute. In Table IX, the data given are:
Column 1. t=time in minutes.
2. The resistance of the cell in ohms.
3. The concentration of the ester taking the molar solubility as
0.005.
4. The molecular conductivity of the ester corrected for the con-
ductivity of the water.
5. The degree of dissociation of the ester, Aco = 386.
6. The affinity constant (K,) of the ester calculated from the
preceding data.
7. K, the specific conductivity, as calculated from the resistance
capacity of the cell and the data in column 2.
8. The concentration of the salicylic acid estimated, from K in
column 7, upon a curve plotted from values calculated from
the data in Kohlrausch and Holborn.
9. The molar concentration of the salicylic acid calculated from
data in column 8. This value is also X, the amount of
methyl salicylate hydrolyzed in time ¢.
10. The molecular conductivity of the salicylic acid solution cal-
culated from the data in columns 2 and 8 and the resistance
capacity of the cell and not corrected for the conductivity
of the water and the methyl salicylate in solution. These
values give some idea of the accuracy of the work.
; - : OH
Me KL is the velocity constant for the reaction CHK COOCH; +H:20
= CeHKC Coon + CH;0H caleulated from dx/dt=K_e in which
the constant e = 0.005, the solubility of methy] salicylate in water
te} x
at 30°. Therefore | oe aE
While the values for e are constant, limited by the solubility
of the methyl salicylate, it seems more accurate to regard e as
a variable which, as it diminishes, is regularly increased by
another variable so that at each interval of time it assumes
the same value.
94 The Philippine Journal of Science 1918
TABLE IX.—Conductivity data for methyl salicylate, the dissociation in
aqueous solution, and the rate of hydrolysis. Furst series.
Cell No. 2. Constant= 0.1670. Temperature 30°.
1 2 3 4 5 6 7 8 9 10 11 |
: 3
Th ay Is ae Afor| %for Ka anak ioral a ale Idee
60 ohms. | otey, |ester. | ester. | for ester. Pie Siar Sal H et
0 | 27900] 200 | 0:27 |\0. 00057 |/4. 7-10—ae |e | el eee
Si |Jeaano}|) e200) OV SE il O!OD14 (slo slo 1 [essen | ore | rte em Re
MAACO! AOE) | OWE WeeGoriam feet ees
Dy aeal| enn || ue aoe WGemoiy—n | - L [ise
Deer 00) |e ae | i aepmare Leet Ste O16) | Jee aL el Oe |
As || TeLCUT) set ene aie [Deusnatoeue 0.129 | 29,900 | 0.04834 |= (387) |____________
BES UlsG RTO | eceuored | Mewtwo st |s Neenah 0.274 | 14,500 | 0.04689 | 397.1 |6.3-10—7
07s BY SOSH | ences Mace nt en us hei 0.283 | 13,900 | 0.04720 | 393.8 |5.9-10—7
ABA lB gs) | aoe al seers a Ne yi tan Oe een 0.304 | 13,200 | 0.04758 | 401.1 |5.6-10—7
Bag) || (200 ee | [et Py 0.321 | 12,500 | 0.03800 | 401.6 | 4.9-10—7
BOT |r 980) |e | Mae egbScas Tee anh oe 0.835 | 11,900 | 0.04841 | 399.0 | 4.7-10—7
eo 1 Qui e eee Joti acl Slane Met 0.442 | 8,900 | 0.031124 | 393.2 | 4.4-10—7
APSO | GS B20) | eee eee ae ee Ak 0.475 | 8,100 | 0.031245 | 384.4 |3.9-10—7
ROG We Mis 180) [esis [che hal al ele ee ae 0.525 | 7,300 | 0.031370 | 382.5 | 3.6-10—7 |
Asverage . 2.2220) <5 22 ee so Se ee Be eae eee lee 4.9-10—7
a Value at infinite dilution = ACO.
The hydrolysis was continued for twenty-three days longer,
but the changes in the resistance of the solution were so un-
certain, undoubtedly due to the action upon the glass, that the
experiment was discontinued.
Analysis of the contents of tube.
Compound. Calculated to 100 ce.
Methyl salicylate 0.0739
Salicylic acid 0.0048
The percentage of methyl salicylate is slightly less than the
solubility, and the amount of salicylic acid formed from the
methyl salicylate at the end of twenty-three days is about two
and one-half times the quantity shown by the conductivity at
the expiration of twelve hundred sixty-nine hours.
The results of a duplicate experiment performed in a third
cell are recorded in Table X.
vil, A,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 25
TABLE X.—The hydrolysis of methyl salicylate in aqueous solution.
Second series.4
Cell No. 8. Constant=0.1761. Temperature 30°.
ei 2 7 8 9 11
xX
. €108 Li
t, R. | K=CR. “108 See eee
4 salicylic | salicylate. Bet
TD) TEED) COSTS ieee a ee ee ee
117 | 7,800 | 0.0302257 17, 000 (05 0s0b88 )|/ =a snbeees |
429 | 6,700} 0. 0302628 14, 700 0. 030680 | 5.3-10—7
669 | 6,100 | 0.0302887 13, 700 0.030730 | 3.6-10—7
934 | 4,300} 0.0304095 9, 600 0. 031042 | 3.7-10—7
1,346 | 2,900 | 0.0306072 6, 400 0.031563 | 3.9-10—7
1,896 | 1,970} 0.0308938 4,100 0. 032439 | 4.3-10—7
2,926 | 1,150} 0.0315310 2,200 0.034546 | 5.2-10—7
lea IAN CTH 6 SoS 2 Ss ee ee nee aen ese 4.3-10—7
* The column numbers correspond to those in Table IX.
Great accuracy cannot be claimed for Ky for the reasons that
the action of the solution upon the glass and the method
employed for estimating the concentrations in column 8 will
introduce unavoidable errors. The corrections for the conduc-
tivity of the water and that of the dissolved methyl salicylate are
slight and have less influence than the former causes for inac-
curacy. Slight changes in the temperature for such a long
period of time were unavoidable, and the high temperature
coefficient, which will be shown later to be one of the factors
of this reaction, introduces a considerable source of error. On
the whole, the approximation of Ky is very satisfactory under
the circumstances, and the decreasing values may be due to the
action upon the glass which is greatest at the beginning.
The value of K,, the affinity constant of the methyl ester of
salicylic acid, is problematical and is about the magnitude 10-":.
Calculated from the hydrolysis constant of the sodium salt, 0.001,
as previously determined, the value is
1-2=10-4
10-3
This value practically agrees with that obtained after shaking
the ester with water for three or four hours.
Goldschmidt and Scholz’s statements that the hydrolytic con-
stant of sodium methyl salicylate, 0.001, is considerably larger
than that of sodium phenylate, that the acid character of the
=K=1.2-10-,
26 The Philippine Journal of Science 1913
phenol is greatly weakened by the introduction of the COOCH,
group in the ortho position, and that the affinity constant of
the ester is probably one-tenth that of phenol are essentially
correct.
Naumann, Miiller, and Lantelme'® have determined by the
distillation method the percentage of hydrolysis of sodium
phenylate at 100°, and the hydrolysis constant calculated from
their values gives about the average 1.5.10°. It is possible
that at 30° the temperature coefficient will reduce this figure
to less than one-tenth of its value, in agreement with that given
by Walker ;'® namely, 0.85.10-* at 25°.
Since the solubility of this ester at 100° was required in the
study of the hydrolysis at this temperature, it was determined
as follows:
One liter of pure water was boiled for thirty minutes with an
excess of methyl salicylate. The ebullition was stopped and the
ester then almost entirely settled to the bottom, leaving a small
quantity floating. Small samples were syphoned into small
weighed flasks, neutralized, and then saponified for two and
one-half to three hours and titrated, employing phenolphthalein
as indicator. The results are tabulated as follows:
TABLE XI.—The solubility of methyl salicylate in water at 100°.
| Weight N/10 3 Molar
of NaOH Eater ey solubility=e.
sample. |required. ‘| Average.
Grams. Per cent.
61.19 7.06 | 0.1754
60. 94 6.48| 0.1615
53.20 7.45| 0.2128 | 0.0117
| 51.96 5. 60 0. 1638
MEASUREMENTS AT 100°
The hydrolysis was carried on in small flasks fitted with
return condensers. Small quantities of methyl salicylate were
from time to time added to the boiling solution, in order to
avoid the presence of great excesses of the ester which would
interfere with the accurate determination of the salicylic acid
in the aqueous solution. Small quantities of the water solution
were removed at intervals, and the salicylic acid determined
by the colorimetric method.
* Journ. f. prakt. Chem. (1907), n. s. 75, 68.
* Introduction to Physical Chemistry. London (1910), 36.
vi, 4,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV Ht |
The results are recorded in Table XII. ¢ is the time in min-
utes; x is the amount of methyl salicylate, expressed as molar
concentration, hydrolyzed in time t; Kj, is the reaction velocity
constant calculated from the formula Ky ==. The value for
e is taken as 0.0117.
TABLE XII.—The hydrolysis of methyl salicylate at 100°.
1 2 3 4
Salicylic
£. | acid in 100 x a
60 jcubic centi- K ~et
meters.
1 0. 00255 0. 000185 2.7- 10-4
2 0. 00637 0. 000462 3.3° 10-4
5 0. 02146 0.001555 4,4-10-4
t 0. 02416 0.001751 3.5 - 10-4
24 0. 11716 0. 008492 5.0 10-4
30 0. 12264 0. 008884 4.2-10-4
48 0. 19320 0.01400 4.2-10-4
72 0.21470 0. 01556 3.9-10-4
96 0. 25760 0. 01867 2.8- 10-4
120 0. 32200 0.023383 | . 2.8-10-4
168 0. 38640 0. 02800 2.7°10-4
Average____--_------- 3.6° 10-4
It is to be noted that about one thousand times the quantity
of methyl salicylate is hydrolyzed in a given time at 100° as
at 30°, an extremely high temperature coefficient.
The hydrolysis in N/10 solutions of sulphuric acid measured
in the same manner in one experiment showed that the rate
was considerably more rapid. Since the measurements have
not been repeated, we are not justified in making any further
statements.
Attempts were made to follow the rate of hydrolysis at 100°
in sealed tubes fitted with electrodes by means of conductivity
measurements, but the glass employed was so readily attacked
that the measurements were of no significance. While the
results are not satisfactory for the purposes in view, they may
be of some interest and are briefly described as follows:
Sealed tubes containing equal quantities of methyl salicylate
and conductivity water were agitated in a steam bath at 100°
from October 7, 1908, to December 2, 1908—a period of fifty-
six days—and the contents roughly estimated. Determinations
are calculated to 100 cubic centimeters of solution.
93 The Philippine Journal of Science 1918
Aqueous portion.
Methy! salicylate
portion.
Substances.
| Tube Tube Tube Tube
No. 1. No. 2. No. 1. No. 2.
Salicylic: acidteca rae ee 0. 497 0. 51 trace
Sodium(salicylates222 2-ee ss ee eee none none |222. 24
The following experiments were more carefully performed.
Tubes 1 and 2, of the shape shown in fig. 5, were constructed
with platinized platinum electrodes.
trace
Fic. 5.—Conductivity cell.
The cell constants at 30° were: No. 1, 0.1913; and No. 2,
0.2158 Kohlrausch units.
Equal quantities of water and methyl salicylate were sealed
in the tubes. The water employed had a specific conductivity
of 1.9 10°. The U-shape of the cell permitted pouring the
water from the elongated leg into the leg containing the elec-
trodes, where its conductivity could be measured.
The two cells were put into a steam bath, which remained
constant between 99° and 100°, and continuously rotated for
three hundred seventy-two hours for cell 1 and seven hundred
ninety hours for cell 2. At intervals, cell 1 was cooled to 30°
and the resistance measured. This cell broke after three hun-
dred eighty-four hours.
The resistances measured at intervals were as follows; tem-
perature during measurements, 30°.
TABLE XIII.—Resistance of cells during hydrolysis in water at 100°.
R.
Time. Cell No. 1, Cell No. 2,
5 ce. water | 10 cc. water
5 ce. ester. | 10 cc. ester.
136 ™
0 0 238007 |e eee
3 15 640 ees Soe eee
22 45 TRAM: Ae eee
46 45 120) Sa kee eee
93 45 TUT 2 eee: See
128 15 10))| 3-2 ee a See
205 15 B2ieaos Ree ee
272 15 AB Lill: ..2do 2 ees
372 15 AQ) |g 5 Serene ened
Loh Saale ee! tubejbroken|Sssssss= sae
790 (| ES aes aes 38
vil, 4,1 Gibbs, Williams, Galajikian: Methyl Salicylate IV 29
It is evident that equilibrium was practically established in
about four hundred hours.
Cell 2 was opened and analyzed after seven hundred ninety
hours at 100°. It showed no internal pressure. The analysis
is as follows:
Aqueous portion.
Substance. Gram per 100 ce.
Free acid, calculated as salicylic 0.0055
Total salicylic acid 0.96
Methyl alcohol (by calculation) 0.307
Methyl salicylate 0.074
Almost all of the salicylic acid in the aqueous portion was
present as alkali salts due to the action upon the glass.
Methyl salicylate portion.
Salicylic acid 0.425 gram per 100 cc.
The total amount of salicylic acid produced was 1.385 grams
per 100 cubic centimeters, which is equivalent to 1.526 grams
of methyl salicylate hydrolyzed.
Method of analysis.—The two layers, water and methy] sali-
cylate, were separated and filtered. The salicylic acid in the
ester portion was titrated with N/50 sodium hydrogen carbonate
solution, employing Congo red as an indicator. The acidity of
the aqueous layer was determined in the same manner. The
total salicylic acid in the aqueous portion was determined as .
follows: An aliquot part was made alkaline with sodium hydro-
gen carbonate and then shaken out repeatedly with chloroform
to remove dissolved ester. It was then acidified with sulphuric
acid, and the salicylic acid extracted with chloroform and de-
termined colorimetrically. The methyl salicylate in the aqueous
solution was determined colorimetrically by the method pre-
viously described.”°
Aliquot parts of the aqueous solution were gently ened, and
the alkali carbonates determined by titration.
SUMMARY
The results of the investigation of the saponification of some
difficultly soluble esters with sodium hydroxide, and with pure
water, in homogeneous and nonhomogeneous solutions and the
mathematical considerations involved are described.
1. Carbon dioxide is found in small amounts as the result of
the alkaline, but not of the acid hydrolysis of methyl salicylate
» Gibbs, This Journal, Sec. A (1908), 3, 357.
30 The Philippine Journal of Science 1913
at room temperatures. The amount is so small that it is neg-
ligible in the consideration of the rate of saponification.
2. The constant for the hydrolytic dissociation of sodium
methyl salicylate is about 0.001, which is the value given by
Goldschmidt.
3. The solubilities of methyl benzoate and the methyl ether
of methyl salicylate in water at 30° are 0.01568 and 0.0371, re-
spectively. The solubilities of methyl salicylate in water at 30°
and 100° are 0.005 and 0.0117, respectively.
4. The saponification constants for methyl benzoate and the
methyl ether of methyl salicylate in homogeneous solution cal-
culated according to the equation for reactions of the second
order are 5.411 and 2.593, respectively. In nonhomogeneous so-
lution, calculated according to the equation for reactions of the
first order, they are 4.529 and 2.029, respectively; therefore,
the saponification constants of difficulty soluble esters can be
approximated by the second method.
5. The rate of saponification of a difficultly soluble ester, when
the ester is present in excess of its solubility, is not affected by
contact action. 2
6. The saponification velocity constant of methyl salicylate
with sodium hydroxide in nonhomogeneous solution was de-
termined to be 6.36, and that of sodium methyl salicylate was
found to be 0.1605.
7. The saponification of methyl benzoate and methyl] salicylate
in sodium carbonate solution has been studied for purposes
of comparison with the above data. ;
8. The affinity constant of methyl salicylate calculated from
the conductivity measurements at 30° is of the magnitude 10.
This value agrees with that calculated from the hydrolysis con-
stant of the sodium salt.
9. The hydrolysis of methyl salicylate in pure water at 30°
and 100° has been investigated by measurements of the con-
ductivity of the solutions. At 30° the rate is 4.6°107:; and at
100°, 3.6:10%.
ILLUSTRATIONS
TEXT FIGURES
Fig. 1. Apparatus for detecting carbon dioxide formation.
2. A curve for the graphic determination of ¢, to test the accuracy of
the values: K.=0.0053; K=6.36; K:=0.0223; K.=0.1605.
3. Saponification of methyl salicylate and benzoate with NaOH (above)
and Na-;COs.
4. Conductivity cell.
5. Conductivity cell.
31
THE MUTUAL INFLUENCE OF HYDROXYL AND CARBOXYL AND
SOME RELATED GROUPS IN THE ORTHO POSITION
A STUDY OF THE ABSORPTION SPECTRA OF PHENOL, O-CRESOL, O-HYDROXY-
BENZYL ALCOHOL, SALICYLIC ACID AND ITS METHYL ESTER, METHYL
ETHER OF SALICYLIC ACID AND ITS METHYL ESTER, BENZYL
ALCOHOL, BENZYL ACETATE, BENZYL METHYL ETHER,
BENZYL CHLORIDE, AND METHYL BENZOATE
By H. D. Gipps* and D. S. PRATT
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
Five text figures
The following investigation was undertaken with the view of
throwing some light upon the behavior of the compounds which
exist in solution during the saponification of methyl salicylate
described in the previous paper.’
If it be true that the strengths of carboxylic acids are de-
_ termined by the reactivity of the carboxylic >C=O group, it
should be possible to compare spectroscopically certain analogous
acids which show ultra-violet absorption bands. Baly and
Schaefer * state:
There are thus two influences at work which determine the affinity of the
carbonyl group in carboxylic acids, namely, (1) the nature of the adjacent
carbon atom, and (2) the condition of the hydroxylic oxygen.
It is to be expected that these influences would change the
relative position and persistence of ultra-violet absorption bands,
and that a study of a series of closely related compounds in
which they are varied, both collectively and separately, would
result in a clearer understanding of the chemical and physical
behavior of the compounds in solution.
The astonishingly great difference between the saponification
rates of methyl salicylate and its sodium salt (6.63 and 0.161,
respectively) must be due to a decreased activity of the carbonyl
which in this case is attributed to a change in the equilibrium
of forces between this group and the hydroxyl group in the
ortho position.
* Associate professor of chemistry, University of the Philippines.
* Gibbs, Williams, and Galajikian, This Journal, Sec. A (1913), 8, 1.
* Journ. Chem. Soc. London (1908), 93, 1814.
115512 —3 33
84 The Philippine Journal of Science 1918
The analogies existing between methyl salicylate and aceto-
acetic ether are very striking. The chemical relationships have
been pointed out by Freer,‘ and determinations of the affinity
constants of the acids and the hydrolysis constants of their
sodium salts show the former to be of the magnitude 10-" and
the latter 0.001 in each case.
The expressions suggested by Hantzsch ° for the valence isom-
O O
CH:C/\ Me CH3C/:.Me
HCl) 20 Hc] |O
\4
C: OC:H; C- OCH;
erism in the aci-salt in explanation of the absorption band in
acetoacetic ether can be applied to methyl salicylate, the cor-
responding form showing the conjugated linking being:
O O
U\/~ Me 4N 1". Me
| | fo | | Jo
WNL NaN
S »
OCHs OCH;
There is no doubt that methyl salicylate in the presence of
alkali behaves very differently from the other phenolic com-
pounds discussed in this paper.
Phenol, o-cresol, salicylate acid, and o-hydroxybenzy] alcohol
in the presence of alkali show a reduction in the persistence of
the characteristic absorption band (discussed later), while aceto-
acetic ether shows no band in the absence of alkali, but develops
a characteristic band which increases in persistence with the in-
creasing concentration of alkali salt. Methyl salicylate shows
no appreciable change in the persistence of its band with alkali,
the effect of increasing concentration of the latter being to
shift the band toward the red. If the intramolecular vibration
producing this band is to be attributed to the conjugated linking
as above represented, it is clear that an excess of alkali has ©
*Am. Chem. Journ. (1892), 14, 407.
° Ber. d. deutschen chem. Ges. (1910), 43, 3058.
VII, A, 1 Gibbs and Pratt: Hydroxyl and Carboxyl 35
a beneficial rather than a prejudicial action. The effect of the
alkali is to reduce the phenolic condition, which we will show
can be practically eliminated.
This is actually the case in phenol, o-cresol, o-hydroxybenzyl
alcohol, and sodium salicylate. The primary effect of the alkali
upon salicylic acid is the formation of the sodium salt, and this
is manifested in the absorption spectrum by a shift of the band
toward the shorter wave length, a position nearer the character-
istic band of phenol.
It is evident that the carboxylic C=O group has not the effect
in the di-sodium salt of salicylic acid that it has in the sodium
salt of the ester.
The above representation for sodium methyl salicylate indi-
cates that the free affinities of this compound are so bound that
in effect its equilibrium more closely resembles that of an ether
than of an ester. By this assumption the greatly decreased rate
of saponification of sodium methyl salicylate is capable of ex-
planation. Salicylic acid, on the other hand, shows no similar be-
havior in the presence of alkalies, and presents no corresponding
analogies to acetoacetic ether, although the absorption spectra
of the free acid and ester are identical. When methyl is em-
ployed instead of sodium to replace the hydroxylic hydrogen of
methyl salicylate forming the methyl ether of methyl salicylate,
the equilibrium is disturbed in a different manner due to the
fixation of the labile hydrogen atom, and this is manifested by a
shift in the absorption band toward the shorter wave lengths
and a decrease in its persistence, indicating decreased activity.
This decreased activity cannot be attributed to the phenol portion
of the molecule, for the absorption spectrum of phenol is not
altered in this way by its change to anisole, but is due to the
reduction of the influence upon the >C=O group.
The strength of salicylic acid is diminished by the change of
the hydroxyl group to methoxyl. This is shown in the absorption
spectra of these compounds by a decided shift in the absorption
band of the former toward the shorter wave lengths. The ab-
sorption bands of neither of these compounds are altered by the
change of the carbonyl group to its methyl ester. It is evident
that the strength of the acid is affected by any neighboring
group which will influence the potential activity of the >C=O
group of the carboxyl. The absorption spectra of salicylic acid,
methyl ether of salicylic acid, and benzoic acid indicate the
strength of these acids to be in the order named, a fact which
is in accord with their affinity constants.
386 The Philippine Journal of Science 1913
The rates of saponification of the methyl esters of the above-
mentioned acids and the affinity constants of these acids are
tabulated as follows:
} Rate of saponi- Affinity
Aa feation ofthe constant
Salicylic acid 6.36 0.104
Methyl ether of salicylic acid >2.03—°2.60 0.0081
Benzoiec acid °4.58—°5.41 0.0067
"The affinity constants are taken from Derick, Journ. Am. Chem. Soc. (1912), 34, 76;
Lunden, ‘‘Affinitatsmessungen an schwachen Saduren und Basen,’’ Sammlung chem. u. chem-
tech. Vortrage (1909), 14, 1; and Ostwald, Zeitschr. f. physik. Chem. (1889), 3, 241.
> Calculated for reaction of the first order in nonhomogeneous solution.
© Calculated for reaction of the second order in homogenous solution.
These values show that the affinity constants are not in the
same order as the saponification constants. Similar irregular-
ities are shown in the values as given for propionic, butyric, ©
and isobutyric acids.
Rate of saponi-
: yi Affinit
ae “cinylester constants
Propionic 2.186 0.00145
Butyric 1.702 0.00175
Isobutyric 1.731 0.00159
Ape taken from Walker, Introduction to Physical Chemistry. London (1910), 163
an :
Since the affinity constants of benzoic acid and the methyl
ether of salicylic acid lie so close together, and we are at this
time most concerned with these two acids, we have redetermined
their constants and find that there is no question concerning their
relative values. The results are as follows:
The specific conductivity of the water was 1.19.10 at 25°.
TABLE I.—Benzoic acid. © co=3887.
/1000. A 100 oc K=100k
64 23. 48 6. 07 0. 0061
128 32. 93 8.51 0. 0062
256 45.89 11. 86 0. 0062
512 63. 09 16.31 0. 0062
1, 024 83. 80 21. 66 0. 0058
K=0. 0061
This value agrees with that found by Jones and others ® when
their figures are recalculated in terms of the Kohlrausch units.
* Pub. Carnegie Inst. Wash. (1912), 170, 116.
Vill, A, 1 Gibbs and Pratt: Hydroxyl and Carboxyl 37
TABLE I].—Methyl ether of salicylic acid. © co=387.
/1000. A. 100. | K=100k.
32 18.35 4.74 0. 0073
64 26. 30 6. 79 0. 0077
128 36. 81 9. 51 0.0078
256 50. 77 13.12 0.0077
512 69. 46 17.95 0. 0078
1, 024 95.00 24. 55 0.0078
K=0. 0077
This value agrees with that found by Ostwald? when his
figures are calculated with the Kohlrausch units. If the above
values are correctly given, it is evident that the affinity constants
of acids are not necessarily measures of the rates of saponifica-
tion of similar esters of the acids. At the present time suf-
ficient data are not available to explain these anomalies.
Our method of approaching this problem has included a study
of the hydroxyl group of phenol and its conversion in part and
almost wholly into its sodium salt, a study of benzoic acid and
of benzyl derivatives in which the >C=O has been replaced by
>CH,, and finally of various ortho combinations of these groups,
as found in o-cresol, o-hydroxybenzyl alcohol, o-hydroxybenzoic
acid, its sodium salts, methyl ether, and the methyl ester of this
ether.
PHENOL. FIG. 1
The absorption spectrum of phenol has been investigated
by Hartley and Huntington ;* Hartley, Dobie and Lauder;° and
_by Baly and Ewbank.*® The last authors observed a shift in the
absorption band in the presence of 4 equivalents of alkali, a
condition which Baly and Desh*! found in other compounds to
be indicative of enol-keto tautomérism.
We have photographed this compound in neutral and acid al-
cohol solution and in the presence of 0.1, 1, 5, and 500 equivalents
of sodium ethoxide, and have found that with the increase in
the concentration of the sodium salt of phenol and corresponding
decrease of free phenol, the absorption band becomes more
*Zeitschr. f. physik. Chem. (1889), 3, 266.
* Phil. Trans. Roy. Soc. London (1879), 170, 270.
* Journ. Chem. Soc. London (1902), 81, 929.
* Toid. (1905), 87, 1847.
“ Tbid. (1904), 85, 1029; (1905), 87, 766.
88 The Philippine Journal of Science 1913
Oscillation frequency (2):
3000 32 34 36 38 #4000 42 44 46
Relative thickness of layer in millimeters of 1/10,000 molar solution.
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 1.—Dash curve=phenol.
Dot curve=phenol with 1/10 equivalent of sodium
ethoxide.
Full ecurve=phenol with 5 equivalents of sodium
ethoxide.
shallow, is shifted slightly toward the red, and gives every in-
dication of disappearing entirely were all of the phenol in the
form of the sodium salt.
The relative proportion of the phenol and sodium phenolate in
water solution is obtained from the equation” = —0.85 x 10-4
in which n, e, and d are the concentration of the free base,
phenol, and sodium salt, respectively. With 5 equivalents of
alkali, approximately 98 per cent of the phenol is in the form
of the sodium salt. We have not determined this hydrolysis
constant in alcohol, but do not believe it to be very different.
Under these conditions, the band characteristic of enol-keto
tautomerism has diminished to a fraction of its original per-
sistence, and a shallow band in the benzene region of the spec-
trum has made its appearance. The latter band also makes its
* Walker, Introduction to Physical Chemistry. London (1910), 336.
VIII, A, 1 Gibbs and Pratt: Hydroxyl and Carboxyl 89
appearance in the presence of 1 equivalent of alkali. It is evident
that the intramolecular vibrations of sodium phenolate more
nearly approach those of the benzene ring. In fig. 1 the curve
with 0.1 equivalent of alkali is plotted from dilution log. 3.5 to
log. 2.3 which is the range obtained with 0.01 molar concentra-
tion. It is obvious that a dilution of this solution will change
the value of d, so that this curve could not be farther continued
with accuracy by this method.
The curve obtained with 1 equivalent of alkali is not plotted
in fig. 1 since it falls between the curves of 0.1 and 5 equivalents.
Similarly, that with 500 equivalents is omitted since it lies near
that with 5 equivalents, but shows a further decrease in per-
sistence of the band. The curve obtained in alcohol saturated
with hydrogen chloride follows the curve of neutral phenol,
except that the persistence of the transmission band at 1/A—4180
is reduced from log. 3.34 to log. 2.82. It is thus seen that acids
and alkalies have a somewhat similar effect in reducing the per-
sistence of the absorption band of phenol, which is to be inter-
preted as producing a more stable molecule.
To test the validity of this assumption, we have exposed to
the sunlight tubes of phenol and phenol dissolved in a large excess
of a concentrated solution of sodium hydroxide, and find that the
former colors in a few hours while the latter fails to show any
coloration after weeks of exposure. Sodium phenolate in solu-
tion is colored rapidly, but, in the presence of an enormous excess
of alkali, the hydrolysis and also the ionization are at a minimum,
and we probably have the stable form C,H.ONa. If it be granted
that the oxidation of phenol is capable of explanation by reason
of the transformation
HO-C,H,:Hs0:C,H,:H,
the two hydrogen atoms being oxidized with the formation of
quinone, then it is readily seen that sodium phenolate will resist
this transformation since the sodium atom has greater affinity
for the oxygen than for the carbon.
O-CRESOL. FIG. 2
The absorption spectrum of o-cresol has been investigated by
Hartley * and by Baly and Ewbank. The latter authors ob-
served the shift in the absorption band toward the red, which
takes place in the presence of alkalies.
*% Journ. Chem. Soc. London (1888), 53, 641.
40 The Philippine Journal of Science 1913
Oscillation frequency Se
3000 32 34 36 38 4000 42 44 46
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Relative thickness of layer in millimeters of 1/10,000 molar solution.
Fic. 2.—Full curve=o-cresol in alcohol.
Dot curve=o-cresol with 1 equivalent of sodium ethoxide.
Dash curve=o-cresol with 5 equivalents of sodium ethoxide.
Dash and dot curve=o-cresol in aqueous solution with 5
equivalents of sodium hydroxide.
The curves for o-cresol in alcohol and in the presence of alkali
as shown by Hantzsch * cannot be correctly attributed to this
compound. It is probable that acetoacetic ether was photo-
graphed instead of o-cresol, since the curves correspond with
his data for the former compound. We have photographed
o-cresol in alcohol solution and in the presence of 1 and 5
equivalents of sodium ethoxide, and in water solution in the
presence of 5 equivalents of alkali. It is to be noted that an
absorption band in the benzene region makes its appearance in
the presence of alkali, a fact not noted by previous investigators.
This band corresponds to that observed with phenol in the
presence of alkalies, but appears at slightly greater concentra-
tions.
* Ber. d. deutschen chem. Ges. (1910), 43, 3071.
Vil, A, 1 Gibbs and Pratt: Hydroxyl and Carboxyl 41
The persistence of the band heading at 1/A=3480 is much
greater in alkaline aqueous solutions than in the corresponding
alcohol solutions, a condition which points to the conclusion that
the hydrolysis of the sodium salt is greater in aqueous than in
alcoholic solutions.
O-HYDROXYBENZYL ALCOHOL. FIG. 3
This compound was photographed in neutral alcohol solution
and also in the presence of 5 equivalents of alkali. See dot and
dash curve and dot curve, fig. 3. The conditions existing in
phenol and o-cresol are also found in this compound. The portion
of the curve for 5 equivalents of alkali lying below log. 1.7 was
obtained by photographing a 1/1000 molar solution. Since this
concentration was obtained by diluting a 1/100 molar solution,
Oscillation frequency (3).
~ 3000 32 34 36 38 4000 42 44 46
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Relative thickness of layer in millimeters of 1/10,000 molar solution.
Fic. 3.—Dot and dash curve=o-hydroxybenxyl alcohol.
Dot curve=o-hydroxybenxyl alcohol with 5
equivalents of sodium ethoxide.
Full curve=methyl ether of salicylic acid and
methyl ether of methyl salicylate.
Dash curve=methyl ether of salicylic acid
with 5 equivalents of sodium methoxide.
4? The Philippine Journal of Science 1913
it is clear that the degree of hydrolysis must be different. The
two portions of the curve do not quite join, but the variation is
so slight that it is not shown in the chart.
METHYL ETHER OF SALICYLIC ACID, AND THE METHYL ETHER OF
METHYL SALICYLATE. FIG. 3
The methyl ether of salicylic acid may be obtained easily and
with a good yield by the following method. One hundred grams
of salicylic acid and 70 grams of sodium hydroxide are dissolved
in 300 cubic centimeters of water. This concentration of alkali
converts about 97 per cent of the acid into the di-sodium salt.
One hundred grams of methyl sulphate are added in small por-
tions with constant shaking, keeping the temperature below 40°.
When the methyl sulphate has disappeared, the solution is
strongly acidified with hydrochloric acid and extracted with
ether. The ether layer is separated, washed with water, and the
ether removed by evaporation. The residue is heated for one
hour on the water bath with an excess of lime water and filtered.
The insoluble residue of calcium salicylate is repeatedly extracted
with boiling water, and the combined filtrates acidified with
hydrochloric acid. The methyl ether of salicylic acid is deposited
upon cooling in large monoclinic plates. It should be recrystal-
lized from water until ferric chloride shows no trace of salicylic
acid. Its methyl ester is easily obtained with methyl alcohol
and hydrogen chloride, and boils at 245-246°. This boiling point
agrees with that found by Schreiner * and not with the lower
value given by Folsing.1° The ester-ether was saponified, and
the resulting acid identified as the methyl ether of salicylic acid.
The absorption spectra of these two compounds in neutral alcohol
solutions are identical. We have photographed them in the
presence of 1 and 5 equivalents of sodium ethoxide. Under
these conditions the absorption band heading 1/\=3440 in the
methyl ether of salicylic acid is shifted toward the shorter wave
lengths to 1/A=3640, both concentrations of alkali giving prac-
tically identical results. The persistence of this band is, at the
same time, reduced, and the incipient band in the benzene region
of the spectrum is lost. It is to be noted that, while alkali causes
a shift toward the red in the compounds previously discussed,
the shift in this instance is in the opposite direction. The former
shift is characteristic of enol-keto tautomerism, and is not shown
when the labile hydrogen atom is replaced by an alkyl group,
* Ann. Chem. Pharm. (1879), 197, 1.
° Ber. d. deutschen chem. Ges. (1884), 17, 486.
VII, A, 1 Gibbs and Pratt: Hydroxyl and Carboxyl 43
while the latter may be an ionization phenomenon. Baly and
Schaefer 7 have pointed out from a study of cinnamylideneacetic,
cinnamylidenemalonic, and other acids that the addition of alkali
decreases, while the addition of acids increases, the free affinity
of the carbonyl group, and state that the natural deduction
from this is that the more the substance is ionized the less the
free affinity possessed by the carbonyl group.
The amount of free affinity of the carbonyl group is greatest when the
acid is not ionized and least in the easily ionized sodium salt.
The absorption curve of the methyl ether of methyl salicylate
is neither shifted nor altered in any way in the presence of alkali.
This behavior is to be expected from a nonionizable compound
of this type.
It is interesting to note that the absorption bands heading at
1/A=3440 of phenol, o-cresol, and of o-hydroxybenzy! alcohol,
all in presence of 5 equivalents of alkali, almost coincide with
that of the methyl ether of salicylic acid in neutral solution and
of the methyl ether of methyl salicylate, and further that these
5 curves all show an incipient band in the benzene region. It
is evident that under these conditions the internal molecular
vibrations of these compounds are remarkably similar. In
phenol, o-cresol, and o-hydroxybenzyl alcohol, the enol-keto
tautomerism exists without the modifying influence of the car-
bonyl group, and the absorption curves of these three compounds
and of their methyl ethers are almost identical. The replacement
of the hydroxylic hydrogen atom of these compounds by sodium
is thus seen to produce much the same effect as the adjacent
carbonyl group produces in their ethers.
SALICYLIC ACID AND METHYL SALICYLATE. FIG. 4
The absorption spectra of these compounds have been de-
scribed by Hartley and Huntington '® and Hartley,’® but, for
purposes of comparison with the other compounds described in
this paper, we have photographed salicylic acid in alcohol, and
its methyl ester 2° in neutral water and in alcohol solutions,
" Journ. Chem. Soc. London (1908), 93, 1808.
= Loc. cit.
* Journ. Chem. Soc. London (1888), 53, 641.
*° Methyl salicylate was photographed in absolute alcohol solutions, and
in aqueous solutions which contained sufficient alcohol to complete the
solution. One-tenth molar solutions were made in 50 per cent alcohol,
one-hundredth in 35 per cent alcohol, and one-thousand in 3.5 per cent
alcohol.
AA The Philippine Journal of Science 1913
Oscillation frequency &.
28 3000 32 34 3 8638 4000 42 44 46
10,000
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Relative thickness of layer in millimeters of 1/10,000 molar solution.
Fic. 4.—Full curve=salicylie acid and methyl sali-
eylate.
Dash curve=methyl salicylate with 1 equiv-
alent of sodium ethoxide.
Dot curve=salicylie acid with 5 equivalents
of sodium ethoxide.
Dot and dash curve=salicylic acid with 300
equivalents of sodium ethoxide.
Dash and cross curve=methy] salicylate with
500 equivalents of sodium ethoxide.
salicylic acid in alcohol in the presence of 5 and 300 equivalents
of sodium ethoxide, and methyl salicylate in alcohol in the
presence of 1/10, 1, 3, and 500 equivalents of sodium ethoxide
and in the presence of hydrogen chloride. We have observed
that the curves obtained with water and with alcohol as the
solvent are practically identical and in accord with data given
by Hartley.
The activity of the carbonyl group of salicylic acid is reduced
in the easily ionized sodium salt and also by the fixation of the
labile hydrogen atom by methyl. This is shown in the charts
of the absorption spectra both by a reduction in the persistence
VIII, A, 1 Gibbs and Pratt: Hydroxyl and Carboxyl 45
of the absorption band of salicylic acid at 1/A=3300 and by a
- shift of this band to 1/A=3400, a position which corresponds to
the same band shown by salicylic acid in the presence of 5 equiv-
alents of sodium ethoxide. In the latter case the salicylic acid
is almost entirely in the form of the mono-sodium salt (the
actual amount of the salicylic acid in the form of the di-sodium
salt is about 11 per cent of the whole), and the shift to the
shorter wave lengths may be due to the ionization phenomenon
previously mentioned. With 300 equivalents of alkali, the sali-
cylic acid in one-thousandth molar solution is approximately 9.2
per cent in the form of the mono-sodium salt and 90.8 per cent in
the form of the di-sodium salt for n x s/0.03=d where
n=concentration of the free base,
s=concentration of the mono-sodium salt,
d=concentration of the di-sodium salt.
These values are computed for aqueous solutions since the
hydrolysis constant in alcohol is not available. We believe the
error thus introduced has no bearing on the general consider-
ations.”+
The absorption curve under these conditions is, therefore,
that of di-sodium salicylate. The absorption band is much
broadened; and the shift toward the shorter wave lengths, found
in the presence of 5 equivalents of alkali, is more than counter-
balanced by the shift toward the red which is characteristic of
the enol-keto tautomerism. Since this absorption band has
almost entirely disappeared, it is evident that the free affinity
of the carbonyl group is approaching a minimum.
The curve for methyl salicylate in the presence of a small
quantity of alkali, 1 equivalent, shows a shift toward the red
and a decrease in the persistence of the large absorption band.
In the presence of greater excess of alkali, the shift toward the
red is increased, while no further reduction in the persistence
is to be noted. The presence of acid causes no appreciable change
in the absorption spectrum of methyl salicylate. Since the
ionization constant of this compound 2 is very small; namely,
1.210", it appears probable that no measurable effect is to
be expected. All of the curves which have any significance are
plotted in fig. 4. :
“In one-thousandth molar alcohol solutions the addition of 10 per cent
of water was necessary to keep the salts in solution.
* This Journal, Sec. A (1913), 8, 1.
46
The Philippine Journal of Science
Oscillation frequency ay
3000 32 w% 36 38 4000 42 44 46
w
OX)
tw Ls)
oS for)
wy
DN)
100
>
Sc
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
w
o
Fic. 5.—Curve I=methyl benzoate.
Curve II and dot curve=benzyl] alcohol.
Curve II and dash-two-dot curve=benzyl acetate.
Curve II and dash curve=benzyl methyl ether.
Dash-dot ecurve=benzyl chloride.
Relative thickness of layer in millimeters of 1/10,000 molar solution.
1913
VIII, A, 1 Gibbs and Pratt: Hydroxyl and Carboxyl AT
BENZYL ALCOHOL, BENZYL ACETATE, BENZYL METHYL ETHER,
BENZYL CHLORIDE, AND METHYL BENZOATE. FIG. 5
The absorption spectra of benzyl alcohol and benzyl ethyl ether
have been studied by Baly and Collie, and since it did not seem
probable that the absorption band at 1/A=3600 was correctly
ascribed to this type of compounds by these authors and also
for the reasons given above, we have included a study of benzyl
alcohol and 4 closely related compounds in this investigation.
Benzyl alcohol, acetate, methyl ether, and chloride were dissolved
in pure ethyl ether and shaken repeatedly with dilute aqueous
alkali, and then with water until neutral. The ether layer was
dried with anhydrous copper sulphate, the ether evaporated, and
the residue fractioned several times under reduced pressure.
This procedure was found necessary to obtain pure compounds.
The substances thus prepared show only one absorption band
which lies in the benzene region of the spectrum and heads at
1/A=3850 in each case. The persistence of this band decreases
in these compounds in the order in which they are mentioned
from the maximum shown by benzyl alcohol. From log. 3.0 to
4.8, and 1/A=3600 to 3850, the curves of the first three com-
pounds are identical while that of benzyl chloride apparently
shows slightly greater general absorption. The divergence in
the curve of the latter may be due to traces of impurities. No
indication of an absorption band in this region of the spectrum
is shown by any of these compounds. There is no doubt that
their true absorption spectra bear little resemblance to the
descriptions of Baly and Collie. Absorption bands outside of
the benzene region of the spectrum are not to be expected in
compounds of this type.
The absorption curve of methyl benzoate is very similar to
those of the benzyl derivatives, but appears at greater dilution,
and the absorption band heads nearer the visible region of the
spectrum; namely at 1/A=3700. The absorption spectrum of
the free acid has been described by Hartley and Huntington,”+
and it shows no noteworthy differences from that of methyl
benzoate.”*
* Journ. Chem. Soc. London (1905), 87, 13438.
* Loc. cit.
* Baly and Collie (loc. cit.) state: “The spectrum of benzoic acid has
been observed by Hartley and Huntington, and only shows general ab-
sorption rather strongly. This is only to be expected from the presence
of the ketonic oxygen in the £-position,” a statement which does not
seem to be strictly in accord with the facts.
a 1 ow » Vs
oe) 1
ie i
‘
1
.
‘aa
vid!
-
cr i +
“ !
vi t
t ‘
‘ .
: j *
e,
‘
Wht re
ee
; in
A ¥
Fig. 1.
ILLUSTRATIONS
TEXT FIGURES
Dash curve = phenol.
Dot curve = phenol with 1/10 equivalent of sodium ethoxide.
Full curve = phenol with 5 equivalents of sodium ethoxide.
. Full curve = o-cresol in alcohol.
Dot curve=o-cresol with 1 equivalent of sodium ethoxide.
Dash curve = o-cresol with 5 equivalents of sodium ethoxide.
Dash and dot curve = o-cresol in aqueous solution with 5 equivalents
of sodium hydroxide.
. Dot and dash curve = o-hydroxybenzyl alcohol.
Dot curve = o-hydroxybenzyl alcohol with 5 equivalents of sodium
ethoxide.
Full curve = methyl ether of salicylic acid and methyl ether of
methyl salicylate.
Dash curve = methyl ether of salicylic acid with 5 equivalents of
sodium ethoxide. ,
. Full curve = salicylic acid and methyl salicylate.
Dash curve=methyl salicylate with 1 equivalent of sodium
ethoxide.
Dot curve = salicylic acid with 5 equivalents of sodium ethoxide.
Dot and dash curve = salicylic acid with 300 equivalents of sodium
ethoxide.
Dash and cross curve = methyl salicylate with 500 equivalents of
sodium ethoxide.
. Curve I = methyl benzoate.
Curve II and dot curve = benzyl alcohol.
Curve II and dash-two-dot curve=benzyl acetate.
Curve II and dash curve = benzyl methyl ether.
Dash-dot curve = benzyl chloride.
1155124 49
THE ABSORPTION SPECTRA OF PHENOQUINONE, 2,5-DIANI-
LINOQUINONE, 2,5-DIANILINOQUINONEANIL, AND
2,5-DIANILINOQUINONEDIANIL
(AZOPHENINE)
By D. S. Pratt and H. D. Grpss’
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
Two text figures
In the study of the compounds which cause the red color of
phenol? it was pointed out that the coloration is due to the
oxidation of phenol to quinone with the subsequent condensation
to phenoquinone, although physico-chemical methods would be
necessary to prove the presence of the latter compound. The
most satisfactory method appeared to be based upon the absorp-
tion spectra of the compounds in question.
Phenoquinone, crystallized from ligroine, was dissolved in ab-
solute alcohol, and the absorption spectrum photographed in the
manner described in our previous work. The absorption curves,
plotted with logarithms of the dilutions and oscillation frequen-
cies, are shown in fig. 1, and the curves of quinone and ‘phenol
in alcohol are included for purposes of comparison.
In alcohol, the color band shows in one-tenth molar solution
and closely resembles that of quinone. Dilutions of this solu-
tion to hundredth and thousandth molar concentrations give
curves that are not continuations of the tenth molar and of each
other. This discontinuity upon dilution is not shown by quinone
and phenol, and since these compounds follow Beer’s law it is
evident that dilutions of phenoquinone solutions do not give the
expected concentrations of phenoquinone. This is due to disso-
ciation which may be expressed by the equilibrium equation:
C,H,0,+2C,H,0H = C,H,0O,-2C,H,OH.
In order to test the validity of this assumption, we have dis-
solved in alcohol quantities of quinone and phenol calculated for
tenth molar solution of phenoquinone and find that the absorp-
tion curve of this solution coincides with that obtained by dis-
* Associate professor of chemistry, University of the Philippines.
* Gibbs, This Journal, Sec. A (1908), 3, 364.
*This Journal, Sec. A (1912), 7, 871; (1918), 8, 338.
51
52 The Philippine Journal of Science 1913
solving phenoquinone crystals in alcohol. These two solutions
are in fact identical. Since the curve obtained with tenth molar
solutions so closely resembles the quinone curve, and for other
reasons, it is evident that the actual amount of phenoquinone in
solution at this concentration is very small.
If the above equilibrium reaction is correctly represented, an
increase in the concentration of phenol should result in a greater
concentration of phenoquinone, and in phenol as a solvent the
dissociation of phenoquinone should be at a minimum. The
curves obtained with an excess of 8 equivalents of phenol and
in pure phenol show this assumption to be justified. The most
striking characteristic of these curves is the change from a
definite absorption band shown in quinone to a mere step off
in phenoquinone in phenol and also the greatly reduced concen-
tration at which the incipient band appears. From this it is
evident that the red color of phenoquinone is largely due to
general absorption, and it is probable that the isorropesis present
in phenoquinone is quite different from that in quinone. This
difference, it seems to us, is due to a loss of the free affinities of
the two carbonyl groups, and may be best expressed by the
oxonium structure
H OGHs
Nae
GeH50 7) oH
This representation accounts for the instability of the com-
pound, the dissociation in solution, and the formation of its very
unstable salts better than the formulas of Jackson and Oenslager *
and of Willstatter and Piccard.®
The conditions existing in dianilinoquinone, dianilinoquinone-
anil, and azophenine are quite different. In all of these com-
pounds the quinone absorption band is well marked, and in
“Ber. d. deutschen chem. Ges. (1895), 28, 1614; and Am. Chem. Journ.
(1896), 18, 1.
5 Ber. d. deutschen chem. Ges. (1908), 41, 1458.
VIII, A, 1 Pratt and Gibbs: Absorption Spectra 53
azophenine the isorropesis occurring between the two unsatu-
rated nitrogen atoms in the para position produces the same
effect as the carbonyl groups. Since the absorption bands are
well developed and in much the same positions when phenol is
employed as the solvent, it is evident that the absence of a well-
marked phenoquinone band in this portion of the spectrum is
not to be attributed to this solvent.
The dilution at which the band characteristic of the quinoid
structure makes its appearance is dependent upon the nature of
the adjacent groups, since this band is shown in tenth molar
solutions of quinone and in thousandth or ten-thousandth molar
solutions of the other compounds mentioned. The argument
employed by Baly, Tuck, and Marsden ® that the bands of the
Oscillation frequency (4 Ne
2000 22 24 26 28 3000 32 34 36 38 4000 42 44 46
Relative thickness of layer in millimeters of 1/10,000 molar solution.
Fic. 1.—Full curves=phenoquinone.
The upper in alcohol, the middle in alcohol with 8 equiv-
alents of phenol, and the lower in pure phenol.
Dot curve=quinone in alcohol.
Dash curve=phenol in alcohol.
* Journ. Chem. Soc. London (1910), 97, 588.
54 The Philippine Journal of Science 1913
nitrophenols in presence of alkali are not quinone bands for the
reason that they appear at greater dilutions than in quinone
itself is thus seen to be without weight.
In order to prove that phenoquinone is produced in phenol
by oxidation, we have exposed colorless phenol in open vessels
to the action of sunlight until it developed a decided red color,
after three or four days, and then photographed its absorption
spectrum. The curve was found to coincide with that of pheno-
quinone dissolved in phenol. The proportion of phenoquinone
formed by the action of sunlight and oxygen in a given time can
be estimated by comparison with the curves shown in fig. 1.
Fig. 1. The curves of quinone, phenol, phenoquinone in alco-
hol, phenoquinone plus 8 equivalents of phenol in alcohol, and
phenoquinone in pure phenol are shown. Our curve of quinone
practically agrees with that given by Baly and Stewart,’ except
that the small band in the benzene region heading at 1/A=4100
is not shown in their charts. Hartley, Dobbie, and Lauder ®
show this band highly developed, but it is probable that the pure
compound will show no band in this region of the spectrum.
Since quinone is so readily reduced by alcohol in ultra-violet
light, it is reasonable to attribute this incipient band to the
presence of small quantities of quinol.
The curves of phenoquinone in alcohol in tenth, hundredth,
and thousandth molar concentrations have been previously de-
scribed. The absorption band at 1/A=3700 is due to phenol
and that at 1/A=4100 to quinone. The curve of phenoquinone
with 8 equivalents of phenol obtained with hundredth molar
solution is not shown on the chart, since it is almost a straight
line and lies very close to that of hundredth molar phenoquinone,
The phenol band at. 1/A=3700 shows in this solution at log. 1.1,
since the phenol is present at one-thousandth molar concentra-
tion.
Fig. 2. Since dianilinoquinone is insoluble in alcohol and in
the usual diactinic solvents, it is necessary to employ glacial
acetic acid to cover approximately the full range of the absorp-
tion spectrum. In order to obtain comparisons of the color
band of this compound with those of dianilinoquinoneanil and
azophenine, we have also used solutions in aniline and in phenol.
The curves are shown in fig. 2.
*Tbid. (1906), 89, 507.
* Rep. Brit. Assoc. (1902), 99.
VIII, A, 1 Pratt and Gibbs: Absorption Spectra
Oscillation frequency (5).
2000 22, 24 26 28 3000 32 34 38 $000
fv
i)
~~
®
S
uw 8
s he
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
5
Fic. 2.—Full curve=2,5-dianilinoquinone.
Dot curve=2,5-dianilinoquinoneanil.
Dash curve=azophenine.
55
Relative thickness of layer in millimeters of 1/10,000 molar solution.
56 The Philippine Journal of Science 1913
It is to be noted that the curves for dianilinoquinone are
similar within the limits of the solvent in each case. The great-
est variation due to the solvent is found in azophenine. The
color band in phenol and in glacial acetic acid is much extended
toward the red, and the general absorption is greatly increased
over the curve shown in aniline. This condition is probably
due to the acid nature of the solvents, phenol and acetic acid.
The color bands of these three compounds are well defined in
each solvent, and clearly indicate quinoid structure, which
accords with the formulas assigned to them.
ILLUSTRATIONS
TEXT FIGURES
Fic. 1. Full curves=phenoquinone. The upper in alcohol, the middle in
alcohol with 8 equivalents of phenol, and the lower in pure
phenol.
Dot curve=quinone in alcohol.
Dash curve=phenol in alcohol.
2. Full curve=2,5-dianilinoquinone.
Dot curve=2,5-dianilinoquinoneanil.
Dash curve=azophenine.
57
PHILIPPINE FRUITS: THEIR COMPOSITION AND
CHARACTERISTICS
By D. S. Pratt and J. I. DEL RosARIo
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
Sixteen plates
INTRODUCTION
From the days of the earliest explorer, tropical fruits have been
held in high esteem. The reports of those who had eaten these
food products were often grossly exaggerated, but they served
to stimulate the spread and cultivation of many important varie-
ties. Improvements in transportation and a growing demand
have resulted in placing many tropical and semitropical fruits
in northern markets. Other varieties are equally valuable, and
doubtless in time will form the basis of an extensive export
trade when methods of preserving and canning are more per-
fectly understood.
Practically no systematic work has been carried out in study-
ing the chemical composition of tropical fruits, and few data
are available concerning any except the citrus fruits, the banana,
and the pineapple. It is hoped that complete analyses with
descriptive notes and illustrations of our principal fruits may
serve a useful purpose in calling attention to the economic
possibilities involved, and aid future work in this important
commercial field.
The term ‘fruit’ as popularly understood includes the edible
portion of many shrubs and trees both wild and cultivated. In
a narrower sense the berries and vegetables are excluded, al-
though the line of demarcation is not sharp and is often depend-
ent upon the condition of the food product in question. Thus
many fruits in a partially matured state are cooked and served
as vegetables.
The chief characteristics of fruits are their color, texture,
odor, flavor, and nutritive properties. All varieties contain a
high percentage of water, holding in solution sugars and acids,
together with small amounts of mineral matter. The individual
odor and taste are dependent upon traces of compound ethers
and esters present in amounts that preclude identification in
most cases, but which are very important in making the fruit
59
60 The Philippine Journal of Science 1918
palatable. The solid portion comprises the usual cellulose plant
structure. Fruits also contain a group of substances called pectin
and pectose, the exact nature of which has not been definitely
determined. The latter gives to unripe fruits their character-
istic hardness and indigestibility. During the course of ripen-
ing, insoluble pectose is gradually transformed into soluble pectin,
a carbohydrate related to starch and sugar. Pectin gelatinizes
upon boiling, and fruit rich in this peculiar class of compounds
may be utilized in making jelly, as it is upon them that the
setting power of the juice depends.
The nutritive value of fruits lies chiefly in the sugars present,
although the acids and salts exercise an important function in
the digestive processes. The high water content, with corre-
spondingly low percentages of proteins, carbohydrates, and fats,
indicates a much less important place for fruits in a dietary
than they actually deserve. A relatively high amount of iron is
present in almost all varieties and may thus be added to the
diet without replacing staple articles of food. It must also be
remembered that fruits supply bulk and exert a beneficial laxa-
tive tendency. These properties are all of value in opposing the
conditions favorable to excessive intestinal putrefaction. In
warm climates especially, sound ripe fruit should form a part of
the daily food of the people.
METHODS OF ANALYSIS
The methods of analysis are of great importance in dealing
with complex material such as fruits, and without information
on the procedure followed the data obtained are often of little
value. For the purposes of this investigation, in every case not
specified, ripe fruits in sound condition were studied.
The edible and waste portions were carefully separated, and
the former passed through a meat grinder until uniform repre-
sentative samples could be obtained. The determination of total
solids was carried out by drying, first on a steam bath, then
to constant weight at 80°C.
Insoluble solids were determined by repeated extraction with
warm water of 20-gram samples on a folded filter and drying
the resulting solid at 80°C. The combined filtrates were titrated
with tenth normal alkali using phenolphthalein as indicator,
since this gives the most accurate total acidity. This value is
expressed in terms of the acid actually present, and also as sul-
phuric acid for purposes of comparison. The fruit acids were
VIL, A, 1 Pratt and del Rosario: Philippine Fruits 61
identified ' in every case, although traces of other acids, present
chiefly as salts, are probably also factors in the composition.
Sugars were determined both by copper reduction and by
polariscopic readings before and after inversion. Sucrose was
calculated by Clerget’s formula. The percentage of total invert
sugar after inversion divided by the percentage of acidity ex-
pressed in terms of sulphuric acid gives what may be called the
sugar ratio. This is a measure of the apparent degree of sweet-
ness, and is useful in comparing different fruits. Ten-gram
samples were used in the Gunning method for nitrogen. The
results are expressed as protein (nitrogen < 6.25). Starch was
determined by acid inversion when present in appreciable
amounts.
It is a common practice throughout the Islands for the native
fruit growers to send their products to market in an immature
condition. This is apparently done to avoid theft, and has re-
sulted in creating a demand for green fruits that are far inferior
in size and flavor to what could be expected under normal
conditions.
The many types of citrus fruits and bananas have been re-
served for a future publication, as the collection at present being
made by the Bureau of Agriculture is incomplete and specimens
are not available.
The botanical descriptions were made by Mr. E. D. Merrill of
the Bureau of Science.
The following abbreviations for the various native languages
are used throughout the paper:
Sp. Fil. Spanish Filipino.
ibe ae aOes
V. =— Visayan.
Il. — Tlocano.
Pamp. = Pampangan.
THE MANGO
MANGIFERA INDICA L. Plate I; Plate II, fig. 1. MANco; MAnca T.,
V., Il.; PAHO, V.
A large tree with glabrous, oblong or lanceolate leaves and
terminal panicles of small yellow flowers. Fruit large, yellow,
fleshy, ellipsoid to oblong-ovoid, equally rounded or narrowed
and somewhat pointed at one end, up to 18 centimeters long, the
*Cir. U. S. Dept. Agr., Bur. Chem. (1911), 76; (1911), 87; (1911), 88.
62 The Philippine Journal of Science 1913
pulp abundant, closely surrounding the large compressed seed
which is fibrous, especially along the edges. Tropical Asia.
The mango is one of the most important and delicious fruits
of the world, and takes the place in tropical countries of the
peach. It is consumed in immense quantities, and forms a
staple article of diet during its rather long season. The tree
is held sacred in India, and references to it are woven through
the native folklore and poems. In the Indian story of Strya
Bai? the daughter of the sun is represented as persecuted by a
sorceress, to escape from whom she became a golden lotus. The
king fell in love with the flower, which was then burnt by the
sorceress. From its ashes grew a mango tree, and the king fell
in love first with its flower, and then with its fruit. When ripe
the fruit fell to the ground, and from it emerged the daughter
of the sun who was recognized by the prince as his lost wife.
The seeds contain about 10 per cent tannin, and are used with
beneficial effect in certain cases of dysentery. The bark and
leaves contain a yellow dye of slight importance.
Mangos are prepared for consumption in a variety of different
forms. The green, strongly acid fruit is boiled with sugar or
pickled, is used in curries, and to flavor many fish products. The
largest demand is for the ripe fruit, and good specimens often
sell for 2 pesos? a dozen in the Manila market when bought in
small quantities. They are eaten by everyone, and are the best
fruit produced in the Islands. The pulp of a fully ripened
mango is rich golden orange, very juicy, and recalls slightly the
taste of a peach. It is excellent in salad or ice cream, and should
find an unlimited market if properly canned. Three types enter
the markets, differing slightly in size, shape, and flavor. The
most important and finest is the carabao (Plate I, fig. 1). The
pico (Plate I, fig. 2) is slightly smaller and lacks some of the
spicy flavor found in the carabao. The pahutan (Plate II, fig.
1) is decidedly smaller and slightly sweeter, but its low propor-
tion of edible pulp makes it less valuable for commercial purposes.
Other varieties are found in the different islands, but many have
a disagreeable taste resembling turpentine and are unimportant.
Among these may be mentioned the large mango known as
“juani”’ of Jolo and Mindanao.
The mango season begins about the first of April, and extends
through July, although the Filipinos often force the fruit by
building fires under the trees or chopping the bark. A few
? Cox, Mythology of the Arian Nations.
* One peso Philippine currency equals 50 cents United States currency.
VII, A, 1 Pratt and del Rosario: Philippine Fruits 63
inferior mangos are found in the markets of some localities
during the entire year.
CHICO
ACHRAS SAPOTA L. Plate II, fig. 2. CH1co; SAPODILLA PLUM; ZAPOTE,
BULLY-TREE; NASEBERRY.
A small tree with milky sap, the leaves thick, shining, entire.
Flowers small, fascicled, axillary. Fruit globose to ovoid, brown,
usually 4 to 5 centimeters in diameter, the pulp brownish,
granular, containing from 1 to 5 large, hard, shining black seeds.
Native of tropical America.
The chico is one of the best fruits grown in the Islands. Firm-
inger states that
A more luscious, cool and agreeable fruit is not to be met with perhaps
in any country in the world.
It is common in many parts of the Tropics, especially the West
Indies, Central America, Mexico, and India, and is highly
esteemed wherever known. The pulp is firm, abundant, and has
a sweet taste not unlike the flavor of maple. The unripe fruit
is high in tannin and gum, but these disappear during ripening,
and leave a juicy pulp that is excellent.
The gum is distributed throughout the tree, and is a valuable
commercial product. It is collected in many parts of Mexico and
Central America under the name “gum-chicle,” but especially in
Yucatan where an extensive trade has been built up. The milky
juice is gathered from incisions made in the bark, considerable
skill being necessary to avoid harming the tree. Tapping should
occur only once in three years. The juice is boiled to proper con-
sistence, and molded in bricks for export. Overheating causes
the gum to turn reddish, and reduces its selling value. The
first quality chicle is firm, almost white, aromatic, and nearly
tasteless. It is the basis of chewing gum and has a ready market.
There seems to be no reason why it could not be collected here,
and with cultivation form a considerable source of profit, al-
though at present the trees are too scattered to compete with
Yucatan. Good quality chicle sells for 35 to 45 cents a pound
in the New York market.
JAK
ARTOCARPUS INTEGRIFOLIA L. f. Plate III, fig. 1. Jak; LANCA,
NAncA, NANGcA, T.; ANANGCA, II.
A small or medium-sized spreading tree with abundant milky
juice. Leaves elliptic, obtuse, entire. Fruits solitary, very
large, up to 50 centimeters long, borne on the trunk and larger
64 The Philippine Journal of Science 1913
branches, oblong, compound, green, muricate, containing many
rather large seeds, each surrounded by the edible pulp. Tropical
Asia.
The name “jak” was given by the early Portuguese from the
Malay tsjka. It is the largest of Philippine fruits, and attains
a remarkable size. Specimens have been reported from Ceylon
and India that weighed over 50 kilograms, although the usual
size found in the markets is nearer 20. The fruit, or more
properly infructescence, is of irregular shape, with the green sur-
face broken up into roughly hexagonal knobs. The outer skin
exudes a sticky, milky juice when cut that contains a small
amount of caoutchouc. The interior of the fruit is yellow to
cream color, and is divided into segments each containing a seed.
The pulp has a strong odor said to be due to ethyl butyrate, and
a rather sickening sweet taste that seldom finds favor with
Europeans. The fruit is popular with the Filipinos, and is eaten
both cooked and as gathered. It is roasted or baked, and also
preserved with sugar as a sweetmeat.
Throughout the western coast of India and in lower Burma,
jak is the chief fruit during the hot weather. When the syn-
carps mature, the fleshy arils are readily separated. They may
be eaten at once, fermented to give an alcoholic beverage, or
dried in the sun. This produces chips that are easily preserved
until needed, and may then be boiled with salt to furnish a
satisfactory food.
The seeds contain a large amount of starch, and are eaten
after roasting, when they resemble Italian chestnuts. Flour
may be made from the mature seeds, a single fruit of average
size giving about 1 kilogram of chips and half as much flour.
The entire tree, but especially the wood, contains a yellow dye
of slight importance in India and Burma.
BREADFRUIT
ARTOCARPUS COMMUNIS Forst. (A. rima Blanco.) BREADFRUIT; RIMA,
Rimo, T.; PAKAK, II.
A medium-sized tree with large, pinnately incised leaves.
Fruits globose, green, muricate, compound, 10 to 12 centimeters
in diameter, seedless, the pulp rather stringy, soft. Polynesia.
The ripe pistillate inflorescence forms one of the chief native
foods in the South Sea Islands where it reaches a perfection
and excellence never attained in the Philippines. The structure
of the fruit resembles the jak, and the edible flakes are similarly
VIII, A, 1 Pratt and del Rosario: Philippine Fruits 65
used. It is of some importance in Ceylon and Burma where
it is cultivated. Firminger records that the sliced and roasted
breadfruit is “hardly distinguishable from an excellent butter
pudding.”
ARTOCARPUS COMMUNIS Forst. (A. camansi Blanco.) Plate III, fig. 2.
Very similar to the preceding variety, differing chiefly in
the fruits bearing numerous rather large seeds. Polynesia.
Unimportant.
CASOY
ANACARDIUM OCCIDENTALE L. Plate IV, fig. 1. CASHEW, Casu; Ca-
sty; Casdy, T.; Botidéco, Il.
A small tree with simple leaves and terminal panicles of
small flowers. Fruits consisting of two parts, the much en-
larged, soft, yellowish, obovoid edible pedicel which is usually
about 5 centimeters long, bearing at its apex the kidney-shaped
seeds containing a caustic juice, edible only after being cooked.
Tropical America.
The unripe fruit is very astringent, but when mature it be-
comes juicy and sweet, with the property of quenching thirst
that adds to its value. The outer skin is slightly irritant when
applied to the skin, and has a smooth oily surface. The pulp
is fermented in Brazil and made into an alcoholic beverage that
is said to resemble Madeira and have beneficial properties in
stimulating the liver. A similar intoxicating drink called “kaju”
is consumed by the natives in eastern tropical Africa, and the
juice is a source of very weak alcohol in Bombay.
The seed is enclosed in a grayish brown cellular shell that
contains an essential oil possessing a blistering action due to
the presence of cardol and anacardic acid. This oil has a slight
value as a preventive against white ants in wood, books, etc.,
and is used in the Andamans to color and preserve fish nets.
The kernel is edible after roasting, and so prepared is one of
the best nuts available. Cashew nuts are an article of commerce,
and are in demand for confectionery and flavoring purposes.
A fixed oil may be expressed from the nut that is very nutri-
tious and the equal of almond oil in every respect. The casoy
beans sell for 5 centavos a hundred in the provinces, and trees
bear after four years. The nuts are used at present to a very
slight extent, although there are possibilities of profit from this
source.
115512—_5
66 The Philippine Journal of Science 1918
TABLE I.—Analysis of casoy nuts.
Average weight of nut kernel, 2 grams.
Per cent.
Oil 57.38
Protein 18.00
Starch 5.28
Fiber 0.91
Ash 2.42
Moisture 16.01
Constants of casoy oil.
Refractive index 1.4664 at 29°.5.
Saponification number 190.0
Specific gravity 0.9114 at 28°.8.
Iodine number (Hanus) 36.66
The oil is of a light yellow color, possesses a bland taste, and
may be used for the same purposes as the best grade of olive
oil. <A yield of about 40 per cent may be obtained by pressing.
ANONA
ANONA MURICATA L. Plate IV, fig. 2. GUABANO; SOURSOP; GOYABANO,
GUANABANO, Sp. Fil.; GUAYABANO, II:
A small tree about 5 meters high, with oblong-ovate leaves 8-18
centimeters long. Fruit aggregate, fleshy, irregular, oblong-
ovate to conical, greenish, covered with soft scattered spines,
the flesh white, rather fibrous, subacid. Native of tropical
America.
The ripe fruit possesses antiscorbutic properties, and a pleas-
ant acid taste, although the pulp is rather stringy with black
seeds scattered throughout. The juice bears a slight resem-
blance to pineapple in taste, and may be used as a refreshing
beverage.
A fermented drink of agreeable taste not unlike cider is made
from the juice of this and the other species of anona in the West
Indies, where the fruits are plentiful. The fruit is one that
possesses possibilities of value if preserved or canned, as it is
excellent in salads and desserts and is available in sufficient
quantity.
ANONA SQUAMOSA L. Plate V, fig. 1. CUSTARD APPLE; SWEET SOP;
SUGAR APPLE; ATES, Sp. Fil.; Aris, II.
A small tree with simple, oblong-ovate leaves 6 to 12 centi-
meters long, pale beneath. Flowers 1 to 3, opposite the leaves,
2.5 to 3 centimeters long. Fruit soft, fleshy, glaucous, aggregate,
irregularly heart-shaped, 7.5 to 10 centimeters long, tubercu-
late, the flesh sweet. Seeds numerous, dark brown. Native of
tropical America. The ripe fruit easily separates into segments
WIE, A, 2 Pratt and del Rosario: Philippine Fruits 67
that contain a white, creamy pulp of sweet taste. The ates is of
considerable importance, and is the most widely grown anona in
the Philippines. The preceding species is of slightly more com-
mercial importance, as the proportion of edible pulp is greater
and better suited for canning or preserving.
ANONA RETICULATA L. BULLOCK’S HEART; ANONAS, Sp. Fil.
A small tree with lanceolate, acuminate leaves 12 to 30 centi-
meters long, the flowers 1.5 to 3 centimeters long, leaf-opposed.
Fruit 7.5 to 15 centimeters long, aggregate, fleshy, heartshaped;
the surface nearly smooth, greenish yellow, more or less reticu-
late; the flesh soft, yellowish-white, sweet. Native of tropical
America.
This species is of only slight importance in the Islands, and
seldom reaches the market, although in Jamaica and the other
West Indian Islands the closely allied Anona cherimolia is held
in high esteem. There is no reason why anonas should not be
grown more abundantly here, since the flavor is good and the
fruit valuable.
CAMIAS
AVERRHOA BILIMBI L. Plate V, fig. 2. CAMIAS, CALAMIAS, T.; Pras, II.
A small tree with pinnate, pubescent leaves, the leaflets up to
17 pairs, oblong, acuminate. Flowers purplish, small, racemose,
the racemes short, fascicled on the trunk and larger branches.
Fruit green, cylindric, 5 to 7 centimeters long, round or nearly
so in cross section, very acid. Tropical America.
The small cucumber-like fruit is well known throughout the
Philippines, and is eaten green, pickled, especially with fish, and
preserved. The strong acidity is due to oxalic acid, making
the juice of use in removing ink stains or iron rust, and in
polishing brass ware. This and the closely related bilimbi are
the only fruits of importance containing oxalic acid, emphasizing
their position in the oxalis family. The confusion in calling A.
bilimbi the camias, and A. carambola the bilimbi is to be noted.
BILIMBI
AVERRHOA CARAMBOLA L. Plate VI, fig. 1. Bitimpi, BILIMBiN, Ba-
LIMBING, T.; GARANGAN, V.; DALIGAN, II.
A small tree with pinnate glabrous leaves; the leaflets ovate,
about 5 pairs; the small purplish flowers axillary. Fruit green,
acid, oblong-ovoid, 5 to 7 centimeters long, longitudinally 5-lobed,
star-shaped in cross section. Tropical America.
68 The Philippine Journal of Science 1918
The general characteristics of this fruit are much like the
preceding, and its uses are the same. The sour juice is useful
as an antiscorbutic and as a cooling drink to allay fevers. Both
form excellent preserves, with a pleasant refreshing taste.
PINEAPPLE
ANANAS SATIVA Lindl. PrNa.
An erect perennial plant, the long spiny leaves forming a
rosette, the fruit solitary, peduncled, erect, borne in the center
of the rosette, fleshy, ovoid to cylindric, up to 40 centimeters
long, more or less scaly, crowned by a tuft of leaves. Tropical
America.
The fruit is so well known in every country that little need
be said regarding it. The dietetic value is high, not only due
to the available food material, but also to the presence of bro-
melin, a proteolytic enzyme closely related to trypsin. This fer-
ment converts albuminous matter into peptones and proteoses,
acting in acid, alkaline, or neutral media. The Philippine pine-
apples are of good size and flavor, although not equal to those
from Hawaii. The industry of growing and canning pineapple
is beginning to develop, and has great commercial possibilities.
The fiber is used extensively in weaving the well-known pina
cloth.
LIMONCITO
TRIPHASIA TRIFOLIATA DC.
A small spiny shrub with trifoliolate leaves and white flowers.
Fruit globose, aromatic, red or purplish, about 1.5 centimeters
in diameter, containing few seeds. Tropical Asia.
The limoncito was largely employed at one time for preserves,
but its use has gradually declined as other and more suitable
products became better known. It is eaten in India, and is very
commonly used as an ingredient of Chinese preserved fruits.
POMELO
CITRUS DECUMANA Murr. Plate VI, fig. 2. PomeLo, SHADDOCK, FORBID-
DEN FRUIT; SUHA, LUCBAN, T.; SvuA, II.
A medium-sized, usually spiny tree, the leaves simple, the
petiole foliaceous, often nearly as broad as the leaves. Flowers
white, fragrant. Fruit large, globose, green or yellowish, 10
to 15 centimeters in diameter, the pericarp very thick, the pulp
yellowish to pink, acid, usually containing numerous seeds in
each segment. Tropical Asia.
Vill, A, 1 Pratt and del Rosario: Philippine Fruits 69
A common product resembling grapefruit, but less succulent.
The segments are generally separated or shredded for salads,
and the fruit is preserved in sugar for jams, etc.
PAPAYA
CARICA PAPAYA L. Plate VII, fig. 1.
Erect, normally unbranched plants, 10 meters high or less,
the trunk soft, marked with large scars, the large palmately
lobed leaves crowded at the apex of the stem. Male flowers
slender, in pendulous inflorescences. Female flowers much
larger, axillary, or on separate trees. Fruit melon-like, globose
to oblong, green or yellow, smooth, up to 40 centimeters in length,
the pulp soft, yellow, the seeds very numerous, small, borne in
3 rows along the hollow interior. Tropical America.
The green fruit is used for pickling or as a vegetable, and,
when ripe, as a melon or in salads, desserts, ete.
The milky juice, especially of the green fruit, contains a
valuable enzyme first separated by Peckholt. It may be pre-
pared for use by drying the crude juice in flat trays exposed to
the heat of the sun, or a more active product made by precipi-
tating with alcohol and drying over calcium chloride. The dry
residue is marketed under the name papoid, and the more
active alcoholic precipitate as caricin, papain, or papayotin.
The proteolytic action is similar to that of pepsin, but is greatest
in alkaline solution, and is therefore valuable in stimulating
intestinal digestion.
The leaves and green fruit have long been employed to render
meat more tender. The method followed is to allow the sliced
fruit to remain on the meat some hours before cooking. The
leaves impart a characteristic flavor, probably due to the pres-
ence of the alkaloid carpaine.
The papaya varies in shape from ihe round female fruit to
the long cylindrical hermaphrodite, both of which are practi-
cally the same chemically. The male plant occasionally produces
bisexual flowers, and small globose fruits that are much inferior
in taste.
MELON
CUCUMIS MELO L. Plate VII, fig. 2; Plate VIII, fig. 1. MELON, Sp. Fil.;
ATIMON, CATIMON, V.
An annual, herbaceous, tendril-bearing vine, with small yel-
low flowers and subglobose to ellipsoid fruit 10 to 20 centi-
meters long, smooth or somewhat rough externally, uniform in
color or slightly mottled. Tropical Asia.
70 The Philippine Journal of Science 1913
Two types of melon are found in the market, the smooth
mottled one known as “melon” and the rough yellow surfaced
“mel6n-espanol”’. The latter has a much better flavor, but is less
used because of its higher cost. Neither form is equal to the
melon of temperate climates.
WATERMELON
CITRULLUS VULGARIS Schrad. Plate VIII, fig. 2.
The watermelon is too well known to require description or
comment. The Philippine product is small and of slightly in-
ferior flavor, depending upon the season.
MABOLO
DIOSPYROS DISCOLOR Willd. Plate IX, fig. 1. Masoto, AMAGA, T. V.;
TALANG, T. Pamp.
A medium-sized tree with oblong coriaceous leaves, which are
green above, paler and pubescent beneath. Flowers small, axil-
lary. Fruit subglobose, up to 10 centimeters in diameter, red
to yellow or brown externally, and velvety, the pulp rather firm
with a strong odor. Seeds large, usually 5 or more in the center
of each fruit... Indigenous.
The fruit has a peculiar fragrance resembling a perfume and
mealy pulp not unlike some varieties of apple. The taste is
sweet and appreciated by those who do not object to the odor.
Of slight importance as a food.
DUHAT
EUGENIA JAMBOLANA Lam. Plate IX, fig. 2. LumBoy, Sp.; DUHAT,
TPeVeneamp:
A medium-sized tree with elliptic, coriaceous, smooth leaves
and small flowers in short panicles. Fruit ellipsoid or oblong,
2 to 2.5 centimeters long, the pulp dark purple surrounding a
single oblong seed. Tropical Asia.
The duhat is eaten in large quantities by the Filipinos, espe-
cially by the children with whom it is very popular. A tincture
made from the seed is employed to some extent as a cure for
diabetes mellitus, but no important constituent that would justify
its use has been isolated. The juice is a promising material from
which to make wine, as the color and flavor are satisfactory and
the fruit available in sufficient abundance. The fruit may be
made into jelly equal in color and flavor to that of the guava.
TAMARIND
TAMARINDUS INDICA L. Plate XVI, fig. 2. TAMARINDO, Sp. Fil.; SAM-
PALOC, T. Pamp.; SALAMAGUI, I].; SAMBAG, V.
A large tree with pinnate leaves, numerous small leaflets,
and rather small yellowish flowers. Fruit a fleshy, cylindric,
VII, A, 1 Pratt and del Rosario: Philippine Fruits 71
olivaceous or brownish, indehiscent pod usually about 10 centi-
meters long and 2.5 centimeters in diameter, the few seeds
imbedded in the firm pulp. Tropical Africa.
Tamarind is an important food product in many tropical
countries, and is used in a great variety of ways. The young
pods are cooked with fish and rice. The brown paste surround-
ing the seeds in the mature bean is removed from the pods and
sold in balls weighing about 100 grams. These are used in
similar preparations, and to form a refreshing laxative drink
popularly supposed to benefit the liver, stomach, and blood. The
pulp is also largely used to adulterate guava jelley, as it is
much cheaper and supplies the requisite acidity. The substitu-
tion may easily be detected by the presence of tartaric acid in
the product as this is absent in true guava jelly. The composi-
tion of the ripe tamarind pulp is very interesting, since it con-
tains more acid and more sugar than any other natural food
product. The large amount of acid so masks the 40 per cent
of sugar present that. the taste is decidedly sour. Large quan-
tities of tamarind pulp are available in the northern provinces
that might profitably be converted into an alcoholic beverage, and
the seeds used as a source of oil. Tamarind oil was submitted
to the Agriculture Horticultural Society of India in 1856, and a
favorable report made at that time. The oil resembles linseed,
but has greater siccative properties, and is suitable for varnish
or paint. The seeds are also edible after soaking in water and
boiling to remove the outer covering, when the resulting flour
may be made into cakes and bread. The roasted seeds are supe-
rior to peanuts in flavor, and a valuable food. Indian tamarind
pulp is preserved by heating in sugar sirup until saturated, and
packing in earthenware pots glazed on the outside only. The
jars are then filled with more sirup, and stored until the fruit
becomes mellow, when it is shipped to the British market.
Similar methods are employed in Jamaica. The fruit is official
in modern pharmacopeeia as a laxative and refrigerant.
MACOPA
EUGENIA JAVANICA Lam. Plate X, fig. 1. Macopa, Macupa, T. V. II.
A medium-sized tree with oblong-ovate, glossy leaves; open
panicles of few, rather large, pink or white flowers; and
turbinate, pink, fleshy fruits about 4 centimeters in diameter.
Malaya.
The macopa is one of the most attractive appearing fruits
found in the market, but the pulp is tasteless and fluffy. Slight
importance.
792 The Philippine Journal of Science 1914
MANGOSTEEN
GARCINIA MANGOSTANA L. Plate X, fig. 2. MANGOSTAN; MANGGIS,
Jolo.
A medium-sized tree with oblong, coriaceous leaves and axil-
lary flowers. Fruits globose, 5 to 6 centimeters in diameter;
the persistent calyx refiexed; the pericarp rather brittle, purple;
the pulp free, white or translucent, in about-5 nearly free seg-
ments usually only one of which contains a seed. Malaya.
The mangosteen thrives only in the southern islands, and the
fruit reaches the Manila market in small quantities. It is
famed as one of the most delicious fruits grown in the Tropics,
perhaps in the world. The very juicy white pulp has a flavor
partaking of strawberry or grape, and is the only edible part.
It is easily removed from the thick purple rind, and resembles
in shape a small tangerine orange. Unfortunately, it cannot
be transported even with modern cold storage or when coated
with wax, as the white pulp rapidly melts and turns brown.
The seeds contain about 3 per cent of a valuable oil known as
“cocum” or “kokam butter,” which is used extensively in India.
The thick purple rind contains tannin, resin, and mangostin, the
last a yellow crystalline compound with medicinal properties.
The dried rind or entire fruit is included in the pharmacopeia
of India, and is much used as an astringent.
IBA
CICCA DISTICHA L. Plate XI, fig. 1. IBA, T; OTAHEITE or STAR GOOSE-
BERRY.
A small tree, the pinnately arranged leaves borne at the ends
of the branches, the flowers very small, racemose, the racemes
fascicled along the branches below the leaves. Fruits globose,
pale green, about 1.5 centimeters in diameter, the pulp firm, acid,
surrounding the hard stone. Tropical Asia.
The small fruits of the iba are very juicy, and, are eaten raw,
pickled, or cooked with sugar. When properly preserved, they
resemble the gooseberry. Of slight importance.
GUAVA
PSIDIUM GUAJAVA L. Plate XI; fig. 2. GuayABo, Sp.; BAYABAS, II. T.
A shrub or small tree with ovate leaves and axillary, pedicelled,
medium-sized white flowers. Fruit ovoid or globose to pyri-
form, smooth, green to pale yellow, 3 to 5 centimeters in diameter ;
the pulp pink or yellowish, containing numerous, small hard
seeds. Tropical America.
VII, A, 1 Pratt and del Rosario: Philippine Fruits 73
The guava is used largely in the form of jelly, the excellence
of which is too well known to require comment. The unripe
fruit and bark, especially of the root, are astringent and of some
slight importance medicinally.
SANTOL
SANDORICUM KOETJAPE (Burm.) Merr. (S. indicum Cav.) Plate
XII, fig. 1. SANTOL, T. V. II.
A medium-sized tree with trifoliolate leaves, the leaflets rather
large, paniculate; pale yellow flowers; and globose yellowish fruit
about 5 centimeters in diameter, the pericarp thick; the few
large seeds surrounded by a translucent, soft, white, fibrous
pulp. Malaya.
The santol is well known in all parts of the Islands, and
eaten to a large extent. The pericarp is peeled and eaten raw,
or cooked with sugar and candied to make “santol-paste.”” The
pulp is strongly acid and difficult to remove from the large seeds.
CHICO MAMEY
LUCUMA MAMMOSA Gaertn. Plate XII, fig. 2. CHico MaMiy, MAmiy,
T.
A medium-sized tree with milky juice, lanceolate leaves, and
axillary flowers. Fruit ellipsoid, brown, 15 to 20 centimeters
long, containing a single very large seed. Tropical America.
The chico-maméy is uncommon in the Philippines, growing
only in isolated localities, and rarely reaching the market. The
pulp is soft, has a sweet taste resembling a pear, and it suitable
for marmalade, ete. It is justly celebrated in the West Indies,
and should be cultivated here.
DATILES
MUNTINGIA CALABURA L. DATILES, RATILES, CEREZAS, MANZANITAS.
A small tree with ovate, somewhat viscid leaves, the flowers
axillary, solitary, white, long-pedicelled. Fruit globose, red, 1
to 1.5 centimeters in diameter, very sweet, the soft pulp con-
taining innumerable minute seeds. Tropical America.
The datiles grows abundantly, and is eaten largely by children.
It is of minor importance.
LANZONE
LANSIUM DOMESTICUM Jack. Plate XIV, fig. 1. LANns6ne, T. IL;
Bopgoa, V.
A small tree with pinnate leaves, the flowers small, borne in
short racemes on the trunk and larger branches. Fruits ellip-
74 The Philippine Journal of Science 1913
soid, about 3 centimeters long; the pericarp thin, pale-yellowish,
tough, with some milky juice; the pulp white or translucent,
watery; in 5 nearly free segments, only one of which usually
contains a seed. Malaya.
The lanzone is an excellent fruit growing in grape-like clus-
ters. The outer skin is rich in tannin and very bitter, but the
creamy white pulp is sweet and slightly aromatic. The edible
part resembles a small orange in shape and appearance, and is
eaten by both Europeans and Filipinos.
DURIAN
DURIO ZIBETHINUS L. Plate XIII, figs. 1 and 2. DURIAN, CIVET, CAT
FRUIT; DULIAN (Moro).
A tall tree with elliptic-oblong leaves, which are minutely
scaly beneath; rather large, fascicled flowers borne on the trunk
and branches; and large, ovoid fruits 20 to 30 centimeters long;
the pericarp woody, covered with strong, sharp, pyramidal
spines, splitting into 5 valves; the large seeds surrounded by
the cream colored, soft, rank-scented pulp. Malay Archipelago.
The durian is abundant in parts of Mindanao and the islands
of the Sulu Archipelago. During the season from May to Sep-
tember it is very plentiful in Jolo and Tawi-Tawi, selling at
prices ranging from 10 to 40 centavos per fruit.
It is spoken of with contempt by most Europeans, and extolled
as the “Emperor of Fruits’? by Wallace, who considered that
“eating durians is a sensation worth a voyage to the East.” The
creamy pulp is highly prized by the Malays and other Orientals.
The odor is difficult to describe, but may be said to resemble
decayed onions. The fruit is very nutritious, and is undoubtedly
a valuable food among people who have overcome their objection
to the fetid odor. The high percentage of a carbohydrate re-
sembling erythro-dextrine adds to the food value. This is present
in small granules that give a clear red with iodine.
CATMON
DILLENIA PHILIPPINENSIS Rolfe. Plate XIV, fig. 2. CaTm6n, T. V.
A medium-sized tree with elliptic, prominently nerved leaves;
very large white flowers, and globose, acid, green fruit. Fruits
about 5 centimeters in diameter, closely covered by the imbricate,
thickened, fleshy sepals, the pulp arranged in a close spiral.
Indigenous.
Catmon is plentiful in many parts of the Philippines, but
seldom reaches the Manila market. The heavy green sepals are
discarded, showing a light green pulp surmounted with pink
VIII, A, 1 Pratt and del Rosario: Philippine Fruits 75
filaments. The fruit is rather acid, and may be cooked with
sugar as a vegetable resembling apple sauce. The tannin con-
tent, especially of the unripe fruit, is rather high. Other uses
similar to tamarind pulp.
CONDOL
BENINCASA HISPIDA Cogn. Plate XV, fig. 1. Copén, T. V.; TANcUY,
ie
An annual, herbaceous, tendril-bearing vine with coarse large
leaves and large, yellow, solitary flowers. Fruit a pepo, ellipsoid,
glaucous, about 30 centimeters long; the pericarp firm; the seeds
borne in the center, numerous. Tropical Asia.
Condol is cooked in thick sirup and allowed to dry, giving a
popular sweetmeat. The fruit is never eaten raw, as the white
fluffy pulp has little taste and is unattractive.
CIRIHUELAS
SPONDIAS PURPUREA L. Plate XV, fig. 2. CIRULLAS, SIRIHUELAS, T.;
SPANISH PRUNE, HOG PLUM.
A gnarled deciduous tree, the leaves pinnate, the flowers very
small, purplish, appearing before the leaves. Fruit subellip-
soid, smooth, about 3 centimeters long, purplish, the pulp scant,
yellowish, surrounding the single large stone-like seeds. Trop-
ical America.
The skin is thick, and the scant pulp possesses a peculiar
sweetish taste. The fruit is sold in considerable amount during
the season, and is eaten largely by children. Unimportant.
BIGNAY
ANTIDESMA BUNIUS Spreng. Plate XVI, fig. 1.
A dicecious tree, 4 to 10 meters high, quite glabrous. Leaves
simple, glossy, 8 to 20 centimeters long, the spikes of small
flowers terminal or axillary, simple, slender, 5 to 15 centimeters
long. Flowers greenish, numerous. Fruit, when fresh, globose
or ovoid, red, acid, edible, about 8 millimeters long; when dry,
compressed and wrinkled, borne in rather dense cylindric spikes.
The fruit is plentiful in all parts, and is eaten with fish for
its agreeable acid flavor.
1918
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ILLUSTRATIONS
(Photographs by Martin)
PLATE I
Fic. 1. Carabao mango (Mangifera indica L.).
2. Pico mango (Mangifera indica L.).
PLATE II
Fic. 1. Pahutan mango (Mangifera indica L.).
2. Chico (Achras sapota L.)
PLATE III
Fig. 1. Jak fruit (Artocarpus integrifolia L. f.).
2. Breadfruit (Artocarpus communis Forst.; A. camansi Blanco).
' PLaTE IV
Fig. 1. Casoy (Anacardium occidentale L.).
2. Guayabano (Anona muricata L.>.
PLATE V
Fig. 1. Ates (Anona squamosa L.).
2. Camias (Averrhoa bilimbi L.).
PLATE VI
Fic. 1. Bilimbi (Averrhoa carambola L.).
2. Pomelo (Citrus decumana Murr.).
PLATE VII
Fic. 1. Papaya (Carica papaya. L.).
2. Melon (Cucumis melo L.).
PLATE VIII
Fic. 1. Melon espanol (Cucumis melo L.).
2. Watermelon (Citrullus vulgaris Schrad.).
PLATE IX
Fie. 1. Mabolo (Diospyros discolor Willd.).
2. Duhat (Eugenia jambolana Lam.).
PLATE X
Fig. 1. Macopa (Hugenia javanica Lam.).
2. Mangosteen (Garcinia mangostana L.)
PLATE XI
Fig. 1. Iba (Cicca disticha L.).
2. Guava (Psidium guajava L.).
79
80
FIG.
Fic.
Fig.
FIG.
Fic.
The Philippine Journal of Science
PLATE XII
. Santol [Sandoricum koetjape (Burm.) Merr.].
. Chico mamey (Lucuma mammosa Gaertn.).
PLATE XIII
. Durian (Durio zibethinus L.).
. Same as above.
PLATE XIV
. Lanzone (Lansiwm domesticum Jack).
. Catmon (Dillenia philippinensis Rolfe).
PLATE XV
. Condol (Benincasa hispida Cogn.).
. Cirihuelas (Spondias purpurea L.).
PLATE XVI
. Bignay (Antidesma bunius Spreng.)-
. Tamarind (Tamarindus indica L.).
&
1913
.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. ] [Puiu. Journ. Scr., Vou. VIII, A, No. 1.
Fig. 1. Carabao mango (Mangifera indica L.).
[ aan hoes ees re |
Beciog fees
5) (inl.
Fig. 2. Pico mango (Mangifera indica L.).
PLATE I.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | (Puiu. Journ. Scr., Vou. VIII, A, No. 1.
peer a
Ss (eMpale
Fig. 1. Pahutan mango (Mangifera indica L.).
5 Gil:
Fig. 2. Chico (Achras sapota L.).
PLATE Il.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | (Puiu. Journ. Sctr., Vou. VIII, A, No. 1.
Fig. 1. Jak fruit (Artocarpus integrifolia L. f.).
10 cm.
Fig. 2. Breadfruit (Artocarpus communis Forst.; A. camansi Blanco).
PLATE Ill.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. ] [Puin. Journ. Scer., Vou. VIII, A, No. 1.
Bi infls
Fig. 1. Casoy (Anacardium occidentale L.).
5) (Eli.
Fig. 2. Guayabano (Anona muricata L.).
PLATE IV.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | [Puiu. Journ. Scr., Vou. VIII, A, No. 1.
5) (Cina
Fig. 1. Ates (Anona squamosa L.).
Eels
Fig. 2. Camias (Averrhoa bilimbi L.).
PLATE V.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | [Puiu. Journ. Scr., Vou. VIII, A, No. 1.
5) pits
Fig. 1. Bilimbi (Averrhoa carambola L.).
Fig. 2. Pomelo (Citrus decumana Murr.).
PLATE VI.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | [PHIL. Journ. Scr., Vou. VIII, A, No. 1.
Fig. 1. Papaya (Carica papaya L.).
lo Cm.
Fig. 2. Melon (Cucumis melo L.).
PLATE VII.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. ] [Putn. JouRN. Scr., Vou. VIII, A, No. 1.
io CM.
Fig. 1. Melon espanol (Cucumis melo L.).
10 cm.
Fig. 2. Watermelon (Citrullus vulgaris Schrad.).
PLATE VIII.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | [Pur. Journ. Scr., Vou. VIII, A, No. 1.
|
5 cm.
Fig. 1. Mabolo (Diospyros discolor Willd.).
re ¢
Sci
Fig. 2. Duhat (Eugenia jambolana Lam.).
PLATE IX.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | [Pui. Journ. Scr., Vou. VIII, A, No. 1.
ferme
5 cm.
Fig. 1. Macopa (Eugenia javanica Lam.).
5 ©.
Fig. 2. Mangosteen (Garcini mangostana L.).
PLATE X.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. ] [Pui. Journ. Scr., Vou. VIII, A, No. 1.
ea aes [eee
eee reel Ios]
5 cm.
Fig. 1. Iba (Cicca disticha L.).
3 (hint.
Fig. 2. Guava (Psidium guajava L.).
PLATE Xl.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. ] [Puiu. Journ. Scr., Vou. VIII, A, No. 1.
> Cm.
Fig. 1. Santol (Sandoricum koetjape (Burm.) Merr.
{o cm.
Fig. 2. Chico mamey (Lucuma mammosa Gaertn.).
PLATE XII.
[Pui. Journ. Scr., Vou. VIII, A, No. 1.
PHILIPPINE FRUITS. |
PRATT AND DEL ROSARIO:
10 CM.
Durian (Durio zibethinus L.).
Fig. 1.
Durian (Durio zibethinus L.).
Fig. 2.
PLATE XIII.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | [PHtm. Journ. Scr., Vou. VIII, A, No. 1.
3) (Cnn.
Fig. 1. Lanzone (Lansium domesticum Jack).
> cm.
Fig. 2. Catmon (Dillenia philippinensis Rolfe).
PLATE XIV.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | [PHi. Journ. Scr., Vou. VIII, A, No. 1.
10 cm.
Fig. 1. Condol (Benincasa hispida Cogn.).
5 cm.
Fig. 2. Cirihuelas (Spondias purpurea L.).
PLATE XV.
PRATT AND DEL ROSARIO: PHILIPPINE FRUITS. | (Puiu. Journ. Scr., Vou. VIII, A, No. 1.
Fig. 1. Bignay (Antidesma bunius Spreng.).
5 (fn -
Fig. 2. Tamarind (Tamarindus indica L.).
PLATE XVI.
; BOTANY
|. A FLORA OF MANILA
; : * By Eumeg De: Merartt..
Potase No. 419. Paper, oe pages, $2.50,
\ postpaid.
. Practioally a coripletes flora of the oul-
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Glossary of technical terms, etc.
~ ‘SHE COCONUT PALM IN THE PHIL-
- IPPINE ISLANDS
re Order No. 37. Pansr, 149 pages, 30 plates,
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reprint contains ‘the following . artt-
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ee as
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; te INDO-MALAY AN woona
or By ies W. Foxwortny
Sanh ‘Ind Wee ‘Woods; Dootor . Fox-
Mabe tought, ee large amount
eesagooas in pe lil aaar Ktrien trees
ng. Soess:of if eporiomie value.
/ LOOLOGY
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CONTENTS
GIBBS, H. D., WILLIAMS, R. R., and GALAJIKIAN, “A. S.
Methyl Salicylate 1V. The Saponification of Methyl. Sali- —
cylate, Methyl Benzoate, and the Bo ss Ether ‘of Methyl
Salicylate 2.4... ie et cc Se kA eee a4 eats ce OS
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Hydroxy! and Carboxyl and some Related Groups. in the
Ortho Position. A Study of the Absorption Spectra of.
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~ gover; eae piace: Ele 0. Ae yee eee ps
“TRE ‘SUBANUNS, OF SINDANGAN Bar ow
Order No. alo. Pap ; gig ager
map, 29 plates, $125, pianalt. Race Vale
-Sindangan Bay is situated onthe north: ~~
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-banuns of this region were, studied ‘by Mr, \-
> Christie during two periods of five. and six’
- weeks, respectively. “cit
o- The 29 plates: illustrate. ‘die: sibaiiie: at i
“work. and at play; their. industries, - houses, Orhan
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In the preparation ef his manusoript for’ ge
The’ History of Sulu, Doctor Saleeby spent
much. time and effort in gaining access.
to documents in the possession’ of the Sultan
of Sulu. ‘This ‘book is a history of the
Moros in the Philippines from the . cone x
times to te ‘Amori¢an: Sotupation:
THE PHILIPPINE
JOURNAL OF SCIENCE
A. CHEMICAL AND GEOLOGICAL SCIENCES
AND THE INDUSTRIES
Vou. VIII APRIL, 1913 No. 2
ORE DEPOSITS OF THE PHILIPPINE ISLANDS
By F. T. EDDINGFIELD
(From the Division of Mines, Bureau of Science, Manila, P. I.)
Three plates and 4 text figures
The discussion of the genesis of the ore deposits of the Phil-
ippines is handicapped by the lack of sufficient data in regard
to primary ore. Mining is in its infancy, and most of the
operations of mining and development have been carried on
wholly in the zone of oxidation. This is particularly true of
those deposits which represent the most important gold ores;
that is, those made up of manganese, calcite, and quartz, and
of manganese and quartz alone. However, conditions of a
somewhat exceptional nature are encountered which present
opportunities for discussion. These are, mainly, the compara-
tive youth of the rock formations, the evidence of volcanic
activity throughout the Islands, the abundance of mineral
springs, the unusually large number of veins within a limited
area, and the association of manganese, calcite, and quartz in
many of the mineral deposits.
GEOLOGY
The rocks of the Philippine Islands for the most part are
of Tertiary or post-Tertiary age. Very few have been found
116737——1 81
82 The Philippine Journal of Science 1913
which can be provisionally classed as pre-Tertiary. These are
tabulated by Smith*+ as follows:
Radiolarian chert. Tlocos Norte.
Quartz porphyry Lepanto.
Diorites Benguet.
Gabbros Leyte.
Pyroxenite Ilocos Norte.
Peridotite Near Olongapo.
No definite evidence is advanced to confirm this classification,
and while it seems probable that the majority of these rocks are
pre-Tertiary, it is also probable that some of the intrusions
of quartz diorite were of later geologic age or had suffered indi-
vidual uplifts which thrust the diorite alone through the sedi-
mentaries or igneous rocks which had previously overlain it.
One of the above two conditions may have existed in Cebu as
shown by the geologic section by Smith? where the igneous in-
trusion seems to have folded the sedimentaries, and also in
Batangas as shown by the geologic section by Smith. The quartz
diorite in the Aroroy district, Masbate, has been discussed by
Ferguson.* It is found intrusive in the Kaal series of sedi-
mentaries, which, on account of lack of definite evidence to the
contrary, should be classed as Tertiary, since no pre-Tertiary
sediments have ever been found in the Philippines.
Masses of rock similar in appearance to the diorite, but in
places slightly porphyritic, are found intruded into the andesite
in Gold Creek near the Muyot, Major, and Ascension mines,
and in Bued River Valley, Benguet. This rock megascopically
is quite distinct from the andesite, but is with difficulty differ-
entiated from the diorite intrusions to the east. It is much
lighter in color than the andesite, and the contacts between
it and the andesite are very well marked. Therefore, it would
appear that these intrusions were derived from the diorite
magma, but had cooled more quickly on account of their being
intruded as small masses.
In Paracale and in Suyoc we find granite gneiss and granite
having a relationship to the veins similar to the diorite in
Benguet and Aroroy. The granite and the granite gneiss have
been provisionally located in the Tertiary. Therefore, one would
be inclined to draw an analogy between the two classes of intru-
sives and to place them in the same geologic age.
*This Journal, Sec. A (1910), 5, 319.
* Loc. cit.
° This Journal (1906), 1, 635.
* Ibid., Sec. A (1911), 6, 405.
a
VII, A, 2 Eddingfield: Ores of the Philippines 838
VOLCANOES
At one time or another volcanoes have been exceedingly
active in all parts of the Philippines as shown by the enormous
deposits of volcanic tuff which in places are found to a depth
of over 200 meters. The influence the volcano has had upon
ore deposits is very uncertain. In examinations of mining
districts throughout the world, we are confronted by numerous
instances where the mineral district is in a section once the seat
of volcanic action. This is true of Cripple Creek, Colorado, and
numerous other prominent localities in Nevada, Utah, Montana,
Arizona, and New Mexico. T. A. Rickard® has discussed the
Cripple Creek Volcano exhaustively, and in a closing paragraph
emphasizes the influence it had upon ore deposits in the district,
principally by producing conditions in the rock favorable to ore
deposition. Francis Church Lincoln * has stated that the min-
eral constituents of volcanic emanations have been shown to
include all the economic metals, with the exception of gold and
silver, and that silver was found in galena in ejected marble
blocks of Monte Somma. It has also been noted that among
the products in the fumaroles ejected are such active agents as
hydrochloric acid, sulphuric acid, sulphurous anhydride, hy-
drogen disulphide, carbon dioxide, sulphur, hydrofluoric acid, and
hydrobromic acid.
If it be considered that the fracturing of the rocks and the
creation of the fissures have resulted directly from the cooling of
the molten rock at, or near, the surface of the earth, or from
the eruptive force of the volcano and the subsequent subsidence
of the nearby areas, it is evident that the most active agent lying
beneath the fracture zone would be the molten or heated magma
which produced the volcanic flows. The fissures would probably
be the easiest means for the escape of the resulting gases or
for the ascension of the solution which might subsequently be
derived from the cooling mass. The neck of the voleano might in
some cases also furnish an easy passage. Such a condition may
have existed in the case cited by Kemp“ of the Bassick mine,
Custer County, Colorado, where the ore occurs in an old vol-
canic neck as a coating on the bowlders. That so few cases of
this kind exist is due probably to the fact that the neck of the
volcano solidifies in a confined space in which practically no
° Trans. Am. Inst. Min. Eng. (1900), 30, 367.
* Econom. Geol. (1907), 2, 265.
™Ore Deposits of the U. S. and Canada. 4th ed. New York and London
(1901), 281.
84 The Philippine Journal of Science 1913
fissuring takes place. It is evident that the active volcano
would have little or no part in ore formation, since the magma
below, in its extremely heated condition, would give off nothing
but gas or molten rock, which would escape from the volcanic
vent. Its chief agency is in the formation of fissures which
are filled later by ascending mineral-bearing solutions, probably
derived from, or influenced by, the same magma at a cooler stage.
MINERAL SPRINGS
Hot springs are abundant throughout the Islands. In some
localities they have been found depositing arsenic, iron, lime,
salt, or sulphur. In the Benguet mineral district, large masses
of silica containing small values of gold have been found, which
were undoubtedly deposited by springs. Silicification of certain
rocks has taken place to a marked extent in this region, and has
led to the name “Benguet formation” for this class of rock. It
would appear that vein formation is still going on and that gold
has recently been, or is at present being, deposited in the fissures
up which the gold-bearing solutions are coming.
GOLD ORE VEINS
Gold-bearing veins are found filling fissures in andesite, an-
desite agglomerate, diorite, and granite gneiss, and also along the
contacts between two classes of igneous and between igneous
and sedimentary rocks. By far the greatest number of veins
are found in the andesite. These fissures seem to have been
formed without appreciable movement or vertical displacement,
as shown by the absence of slickensides on the walls of the fis-
sures and the comparative absence of faults in a region which
must have undergone more than one period of fissuring.
The faulting of a quartz vein is seen in the “Tejon dike” on
the Ascension group, Baguio, Benguet. This dike, or vein, and
another or possibly the same vein in Emerald Creek have been
faulted twice, as shown in fig. 1. One section of the vein has
been entirely displaced, and the direction of strike of the western
portion changed by about 30°. This faulting may have been due
to a local shifting of the rock comparatively near the surface.
The only other example, so far recorded, is on the HKastern
property, Aroroy, where only one of a series of six or eight paral-
lel veins is faulted and has a lateral displacement of about 3
meters. The fault line was perpendicular to the vein. It showed
well-marked slickensides, and contained drag material from the
VII, A, 2 Eddingfield: Ores of the Philippines 85
Faults found onthe Ascension
Tejon Dike
Fig. 1—Showing faulting of the “Tejon dike’ on the Ascension group.
vein. This case shows conclusively that at least two periods
of fissuring occurred in this region.
The tendency toward parallel arrangement of fissuring is very
marked in Aroroy and Paracale, but in Benguet there is little
evidence of any regularity, except for a tendency toward east
and west directions rather than north and south. A large num-
ber of long, strong veins strike almost due east and west, but the
most promising veins, so far exploited, strike either northeast-
southwest or northwest-southeast. In Aroroy the veins strike
almost uniformly northwest-southeast, and in Paracale they
strike northeast-southwest. This arrangement of fissures may
have been produced by some force acting upon one portion only
of the fracture zone. The simplest case would be the subsidence
of one side or the elevation of the central portion of the area,
thereby producing fissuring on a large scale similar to those on
the crest of an anticline. However, in Baguio is found much
more pronounced and irregular shattering of the rock, producing
86 : The Philippine Journal of Science 1913
in some places cross fissuring, which strongly suggests pressure
fracturing.
In as much as mining has been done only comparatively near
the surface, it is impossible to tell how deep the ore deposits
can be expected to go. Depths from 30 to 100 meters have been
explored, and at this depth no apparent decrease in width has
been found. The fissures in general are strong, and can be traced
for over 500 meters along the strike. In Mambulao it was noted
that the veins in the granite gneiss were wide and strong, but
where they passed from the gneiss to the schist they became
very irregular, splitting into stringers, and finally pinched
out entirely. In the San Mauricio mine the veins near the shaft
in the schist, which overlies the gneiss at that point, are very
irregular in dip and strike, but when the gneiss is reached with
depth these veins are united into one uniform vein. This is
probably due more to the physical condition of the schist than
to chemical action. The schist offers great resistance to fis-
suring, except parallel to the planes of compression. This has
resulted in a resistance to transverse fissuring and a tendency
to change the fissure parallel to the schistosity.
In Benguet, the Fianza vein is either cut off at the diorite or
the fissuring in the andesite does not extend into the diorite.
In another section of Benguet on the Ascension group, a vein
was found varying in width from 1 to 5 meters in a distance
of 1 kilometer along the strike. These cases are the only ones
so far found where marked irregularities occur, except in cases
of lateral enrichment or in contact deposits between igneous
and sedimentary rocks. These veins are small, unimportant,
and presumably limited in extent. No veins are found cut-
ting across sedimentaries.
VEIN FILLING
The difference in the mineralization of the veins of any one
district is very marked, and indicates clearly that the ascending
solutions must have taken up minerals from different formations
in their path. It is apparent.in Suyoc, Benguet, and in Aroroy
that solutions from at least two different sources have produced
most of the vein matter, each one dissolving different minerals
in its ascent. At one period, solutions deposited silica, silica
and manganese, silica and copper, or silica and lead, depending
upon the minerals encountered in their passage. At another
period, they deposited calcite and calcite and manganese. In
VII, A, 2 Eddingfield: Ores of the Philippines 87
one case alternations of these two classes of solutions have taken
place, producing banding of calcite and quartz. The country
rock seems to have had but little chemical effect upon these
deposits, and the predominance of veins in the andesite is due
entirely to its more fractured condition.
The most characteristic feature in regard to the ore deposits
of the Philippines is the abundance of quartz-calcite-manga-
nese veins. Quartz-manganese veins are very common in Ter-
fiary deposits of the United States, some of which also contain
calcite, but the occurrence of large amounts of calcite associated
with the quartz and manganese is unusual.
The primary manganese ore is probably either manganiferous
calcite or rhodonite; in one mine rhodochrosite was found. It
is probable that, where the manganese and quartz were deposited
together, the primary ore would contain some alabandite. In
the zone of oxidation are found the oxides, manganite, and wad.
These oxides are found in streaks in the veins, and usually
contain the highest gold values found in the deposit.
The characteristic section of this type of vein in the zone
of oxidation consists of: (1) A band of solid compact calcite,
varying in width from 0.5 to 6 meters, often lying next to the
foot wall; (2) bands of black, soft manganese, usually mixed
with quartz fragments or honeycomb quartz, and often con-
taining pockets of white quartz crystals which in some mines
indicate high values; these bands are found in some cases next
to the calcite, in some cases next to the foot wall, and almost
always next to the hanging wall; they vary in width from 0.2 to
4 meters; (3) a band of massive quartz, carrying sulphides and
varying in width from 0.1 to 4 meters, usually separated from
the calcite by a manganese band.
ALTERATION IN THE VEINS
Alteration has taken place in the veins due to oxidation, leach-
ing, and enrichment. These elements have in some cases entirely
changed the character of the ore above the lowest level of ground
water, so that very little remains to indicate the true character
of the primary ore.
The zone of oxidation in the veins in many cases is deep on
account of the mountainous condition of the regions and the
resulting low limit of ground-water level. The ground-water
level varies from a plane near the surface during the rainy
season to a plane near or possibly below the level of the bottom
88 The Philippine Journal of Science 1918
of the valley, which drains the ore body, during the dry season.
The variation is more than 100 meters in some cases. This
tends to retard oxidation slightly during the rainy season, when
the vein matter is so filled with water as to be protected from
atmospheric influences, and also during the dry season, when
the chemical activity of water is lacking. These extreme periods
exist for only three or four months each year. During the re-
maining months there is moderate rainfall, which creates very
favorable conditions for oxidation. The net result is probably
much greater than in colder countries where surface waters are
frozen for six or seven months.
The Philippines escape the destructive action of great changes
in temperature, but since such action only affects the surface rock
it has little bearing upon ore bodies in general. This is more
than offset by the heavy rainfall, the humidity of the atmos-
phere, and, in veins, by the shattering due to earthquakes and
earth movements. The temperature of the percolating waters,
also, plays an important part in oxidation and hydrations, and
the greater average temperature of the surface waters causes
greater chemical activity.
The zone of oxidation extends from the surface to below the
extreme lowest limit of ground-water level. Some of the veins
are so shattered as to permit easy circulation of surface water,
which causes almost complete oxidation throughout. This is
also true of several veins in Baguio which, though but little
shattered, are formed of granular, porous, or crystalline quartz
which permits extensive circulation. Other veins made up of
compact and shattered material or those in which channels are
found along one or both walls, or through the veins, often con-
tain unoxidized material even near the surface. The majority
of the veins in Paracale are but little oxidized, due in part to
the unshattered condition of the ore body, in part to the low
relief of the district and to the consequent nearness to the sur-
face of the permanent ground-water level. In Baguio, also,
there are a few cases where unshattered quartz or calcite veins
have resisted oxidizing agents.
Leaching has played an important part in the gold veins, but
its effect has been one of enrichment rather than impoverish-
ment. In practically all cases the richest ore is at or near the
outcrop, and values decrease almost uniformly with depth. This
is caused by: (1) Rapid erosion of impoverished material, (2)
VIM, A, 2 Eddingfield: Ores of the Philippines 89
leaching out of valueless minerals, (8) mechanical concentra-
tion of valuable minerals, and (4) chemical concentration of
valuable minerals.
Owing to the steep slopes characteristic of most of the dis-
tricts, the erosion of the outcrops of the veins is very rapid.
During the rainy season, with its high ground-water level, only
a small part of the vein is subject to rapid leaching. At the
water level the leached values tend to be redeposited, forming
a zone near the surface. A large part of the partially leached
material above this level is washed away, and the gold content
may eventually form placers. With the descending of the
ground-water level, leaching action takes place extensively, and
calcite, copper, iron, manganese, and other minerals are dis-
solved, and either flow away in solution or are redéposited lower
down in the waterways.
The solubility of calcite is very great on account of the large
amount of carbonic acid in the surface waters. This has been
found to vary from 0.22 to 0.45 per cent by volume. Roth ®
states that 1 liter of pure water, either cold or boiling, will
dissolve about 18 milligrams of calcium carbonate. Water
saturated with carbonic acid will dissolve from 700 to 880
milligrams at 10°C.,° or about fifty times as much as pure
water. This has proved an important factor in the leaching
of the numerous calcite-bearing veins in the Philippines.
In the upper workings of the Colorado mine the ore is honey-
comb quartz stained with iron and manganese, but no calcite has
been found. However, the quartz in the vein shows perfect
mold forms for calcite crystals of characteristic shape, and
proves that at one time the vein contained a large percentage
of calcite which was afterwards leached from most of the vein
in the zone above average ground-water level.
In the Eastern mine, Aroroy, honeycomb quartz is also found,
but in this mine calcite can be found very near the surface.
The leaching has taken place only along certain channels and to
a much more limited extent than in the Colorado mine.
Calcite leaching is the only instance where marked impoverish-
ment of any one constitutent occurs, except in copper-bearing
* Allgemeine und chemische Geologie. Wilhelm Hertz, Berlin (1879),
1, 48.
® Geike, Textbook on Geology. 4th ed. New York (1908), 471.
90 The Philippine Journal of Science 1913
veins or in the case of leaching the sulphur constituent of sul-
phides, in which cases the usual conditions are encountered.
Enrichment of vein matter has resulted from the leaching
out of barren material, from the solution and reprecipitation of
valuable minerals, and from mechanical concentration of valuable
minerals by water. The leaching of the calcite from a vein
reduces the density of the vein, but does not carry with it any
appreciable minerals of value. Therefore, the leached portion
contains a much greater value per ton than the primary ore.
This is very pronounced in the Colorado and Eastern mines,
where it can be shown that this leaching alone has increased the
value per ton about 100 per cent. The leaching of iron and
manganese, while affecting the ore value to some extent, is
relatively unimportant. ©
In all the veins some solution of gold has taken place. In
copper-bearing veins and in manganese-quartz veins this has no
doubt been an important factor, but the rapid erosion of the sur-
face has washed away most of the leached material and has
left exposed on the surface the enriched portion of the vein
where precipitation has taken place. In veins of quartz, manga-
nese, and calcite, the typical veins of the Philippines, the solution
of gold appears to have been very slight and the leaching effect
of manganese-bearing veins discussed by Emmons’ appears
to be lacking, but only observations in shallow workings are
available. This condition will be discussed in a separate paper.
The highest values have been due to mechanical concentration
of valuable minerals in crevices, streaks, and waterways within
the vein or next to one of the walls. These are of common
occurrence. In manganese-bearing veins soft streaks of black
oxides of manganese are found, frequently extending from the
surface to almost a hundred meters in depth, which carry ex-
ceptionally high values in gold. It is probable that part of this
gold was precipitated from solution, but the greatest part seems
to have resulted from mechanical concentration. In manganese-
free veins rich streaks, carrying large amounts of iron oxide or
iron and copper oxides, are common. The large volumes of water
that flow through the veins during each rainy season must of
necessity carry with them valuable particles which are filtered
out at a lower depth as the fissure or waterway fills with
sediment.
2 Bull. Am. Inst. Min. Eng. for 1910 (1910), No. 47, 767.
VII, A, 2 Eddingfield: Ores of the Philippines 91
So far as development has gone at the present time, no second-
ary zone of secondary enrichment has been found in copper-free
veins, which tends to strengthen the assumption that enrichment
has been accomplished mechanically. In practically all cases the
richest ore is found near the surface, and the values found so
far appear to decrease with depth until the unaltered ore is
reached.
The following table gives the principal gold-bearing veins in
the Philippines with their chief characteristics.
1913
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VIII, A, 2 Eddingfield: Ores of the Philippines 95
NOS. PROVINCES.
4 ILOCOS NORTE.
2. CAGAYAN.
3. ABRA, SUB. PROV. /LOCOS SUR. LEGEND
4. ILOCOS SUR. Q Babuyanes Is. Ee)
5. MOUNTAIN PROVINCE, = fp
6. UNION. = Wie
7. NUEVA VIZCAYA. Z
8. ISABELA.
9, PANGASINAN.
10. TARLAC.
th, NUEVA ECIJAc
42. ZAMBALES.
13. PAMPANGA,
44. BULACAN.
45. TAYABAS.
16. BATAAN,
(7. RIZAL.
48. CAVITE.
19. LA LAGUNA.
20. BATANGAS.
21. AMBOS CAMARINES.
22. ALBAY.
23. SORSOGON.
24. CAPIZ.
25, ANTIQUE.
26 ILOILO.
27. OCCIDENTAL.
28. ORIENTAL.
29. ZAMBOANGA DIST., MORO.
30. LANAO DIST, MORO:
3%. MISAMIS. =
32. AGUSAN.
33. SURIGAO.
34. COTABATO DIST,MORO.C)
35. DAVAO DIST., MORO.
Vein Gold Deposits
=Cuyos Is.*°
2°
Kagayanes Is.
Kavilli |.
Fic. 2.—Showing localities where gold-bearing veins have been found.
Fig. 2 shows the localities in the Philippines where gold-
bearing veins have been found.
96 The Philippine Journal of Science 1913
VEIN GOLD DEPOSITS
SUYOC
The Suyoc mineral district, located in the Mountain Province,
about 65 kilometers north of Baguio, contains a number of gold-
bearing veins, varying from 1 to 4 meters in width. The vein-
filling is mostly quartz, but occasionally stringers of calcite are
found along the walls. Manganese is very subordinate, and was
found in noticeable amounts in only one vein. Several veins
carry tellurides, but in the majority of cases the gold was found
free or associated with zinc, lead, copper, and pyrites.
The veins are found in conglomerate, diorite, andesite, andesite
breccia, and along the contacts between igneous and sedimentary
formations. The fissuring seems to have occurred after the for-
mation of the sedimentaries, and was probably influenced by the
intrusion of the Bagan granite, which lies west of the district.
BAGUIO DISTRICT
The Baguio district is located near Baguio, Benguet, and
occupies an area of about 100 square kilometers. This district
was profoundly shattered, and probably contains as many mineral
veins as any district of its size in the world. Some of the veins
are shown in Plate I. It can be divided according to the class
of veins into four distinct sections:
1. The Antamok Valley: The characteristic vein matter is
quartz, manganese, and, in a large number of cases, cal-
cite. The gold occurs in the metallic state, but is also
associated with iron pyrites, insignificant amounts of
copper, and, in some cases, with galena and silver.
2. Itogon River: Calcite predominates in fissure veins in the
diorite. A few quartz stringers were found carrying
copper. Gold values are low.
3. Gold Creek: Calcite is almost entirely absent. Numerous
quartz veins are found carrying free gold values and
varying amounts of iron pyrites. Quartz veins carrying
tellurides were found in the northern part of this group.
Toward the south, copper values increase, and veins con-
taining appreciable amounts of copper and lead are notice-
able. Two veins carrying cinnabar were also discovered.
4. Bued River: A large percentage of copper is found in the
majority of the veins, usually accompanied by high gold
values. Calcite is absent.
(
VIII, A, 2 Eddingfield: Ores of the Philippines O7
Antamok Valley veins.—The characteristic veins of this sec-
tion are represented by the Headwaters, Camote-Clayton, Gomok,
and Hileen. These are made up of compact calcite, manganese,
and varying amounts of quartz. In general the manganese bands
representing secondary ore contain the highest values, but high
assays are also obtained from the quartz and calcite. However,
the last two are very irregular in the distribution of values, and
are barren in many places.
No honeycomb quartz was found in this region. This circum-
stance, together with the regularity of the calcite content of the
veins, leads to the conclusion that in certain instances the quartz
was deposited in the fissure first, and that a second fissuring took
place, after which the calcite was deposited. Veins are found
containing quartz and manganese without any calcite, as in the
Benguet Consolidated and the Madison; and of veins of calcite
without manganese, as in the Capitalist. Veins are also found
in this section without calcite or manganese, but they have not
been developed, although some of them are worthy of exploita-
tion. ‘The most prominent are the Otek, Emma, and the Sunrise
Fraction.
The gold is about 30 per cent free-milling (80-mesh), and is
occasionally found as small specks or plates that can readily be
seen in the ore; iron pyrite is abundant in the quartz veins, but
is subordinate in the calcite-bearing veins. Several mines have
been successfully operated in this section.
Itogon River.—iIn this section calcite veins predominate,
although one large vein, the Lincoln Fraction, was found con-
taining quartz and calcite. The main calcite veins are the
Capitalist, Hamilton, Wheeler, and Jefferson. These veins carry
small values in gold, and have never been properly prospected.
Gold Creek.—The principal veins are large, strong, quartz
veins, striking nearly east and west. Among these are Kelly
No. 3, Keily South Slope, Muyot, Midas, Lorenzo Pao, and Tejon
Dike. Several veins striking northeast and southwest are found
on the Kelly, Mayon, and Ascension groups.
An irregular arrangement of veins occurs in the Kelly North
Slope group. Here four veins are found having different strikes,
which results in several intersections within the property (fig.
3), each vein cutting at least one other group. Another feature
peculiar to this group is the occurrence of telluride ore in the
veins, and the comparative absence of free gold.
In the Major group are a large number of veins striking
northeast-southwest. Many of them are contact deposits be-
116737——2
98 The Philippine Journal of Science 1913
tween sedimentary and igneous rock. The vein matter is chiefly
clear, white quartz carrying free gold. One vein in Major
Creek was found containing beautifully crystalline wire gold.
Y
N.
SCALE
te} 10 20 30 40 50 METERS.
SS
Fic. 3.—Veins on the Kelly group, north slope.
The east and west veins south of the Kelly group are very
wide, and can be traced for several hundred meters on the sur-
face. They are generally low in gold value, and carry varying
amounts of iron pyrites and copper.
Bued River.—In this section the veins are characterized by
high values in copper, sufficient in some cases to warrant their
being classed as copper veins. In the zone of enrichment, gold
values as high as 90 pesos (45 dollars United States currency)
per ton have been found. The principal veins are the Copper
King, Gray Horse, Union Jack, and Confederate. One vein
carrying calcite and manganese was found in the Copper King
group.
Evidence as already given points to the fact that two or more
periods of fissuring had taken place; one period when quartz
VIII, A, 2 Eddingfield: Ores of the Philippines 99
and siliceous gold-bearing solution alone filled the fissures. This
was followed by a second fissuring, probably produced by the in-
trusion of the diorite, when calcite manganese gold-bearing so-
lutions ascended in the Antamok Valley section. This was later
followed by the fracturing of the diorite, from cooling, and the
deposition of calcite, free from manganese. The copper, tel-
luride, and lead veins probably were derived from local deposits,
through which the ascending solutions passed, dissolving in their
course the characteristic minerals.
PARACALE DISTRICT
The Paracale district is located in Ambos Camarines, Luzon,
and occupies an area of about 200 square kilometers. Some of
the veins are shown in Plate II. With the exceptions of the Tum-
baga, Nalisvetan, and Navotas groups, the veins are compact
quartz containing large amounts of iron pyrites with varying
amounts of copper. Among these are the San Antonio, Longos
Point, and California, of Dinaanan Ridge, and the San Mauricio
on May Cruz Mountain. Most of these veins show visible gold
in the oxidized zone.
The Navotas veins are narrow stringers of quartz with galena,
sphalerite, iron pyrites, and gold.
The Nalisvetan deposit is a pockety, silicified mass of ore
carrying free gold and some pyrites.
The Tumbaga deposit is a marked exception to the ores in
the district. It is a contact deposit, between shales and igneous
rock. The ore occurs as quartz and calcite stringers carrying
galena, sphalerite, copper and iron pyrites, tellurides, and large
amounts of visible wire gold. It is very irregular and limited
in extent.
AROROY DISTRICT
This district is located south of Aroroy, Masbate. It com-
prises an area of about 80 square kilometers. The principal
veins are shown in Plate III. Calcite, quartz, and manganese
veins are characteristic of this district. Of these the Colorado,
Eastern, and Keystone are the most important. It is evident that
the quartz was deposited after the calcite, as shown in the
leached ore where only a skeleton of quartz is left outlining the
spaces formerly occupied by calcite crystals.
Colorado veins.—This deposit is found in igneous rock. The
hanging wall is andesite. The footwall for a portion of the
vein at least is decidedly different, and appears to be a separate
intrusion. In the places opened up, the ore is quartz (partly
100 The Philippine Journal of Science 1918
honeycomb), manganese, and iron oxide. It presents a marked
ribbon or banded appearance from the alternating layers of
different classes of ore. This banding is generally parallel to
the walls, but occasionally is seen in concentric rings. Numer-
ous irregularities occur in the dip and strike of the vein, and
horses are frequently encountered. The vein is from 3 to 6
meters wide, and can be traced for several hundred meters along
the outcrop.
Eastern group.—There are several parallel veins in this
group. The two principal ones are the Nancy No. 1 and the
Nancy No. 2.
The Nancy No. 1 is a quartz-calcite-manganese vein from 4 to
6 meters wide. In the upper workings massive quartz predom-
inates, but in depth practically the whole vein is calcite.
The Nancy No. 2 vein is in places only 3 meters from the
Nancy No. 1. This distance varies greatly, owing to the varia-
tions in dip and strike in sections of the two veins. The vein
is practically all calcite, although in places it contains a little
quartz and manganese. It varies in width from 6 to 20 meters.
It is low grade except along certain lines of enrichment 1 to 3
meters wide.
Keystone mine.—This property is located on Aroroy Mountain
at the northern part of the district. The vein-filling is quartz
(somewhat honeycomb), iron oxide, and small amounts of
manganese. The quartz is much shattered, and is cut by numer-
ous stringers of quartz deposited at a later period.
PLACER DEPOSITS
The natural result of the weathering and erosion of a country
containing numerous gold-bearing veins, as represented by
Suyoc, Baguio, Lubang, Paracale, and Masbate, is the formation
of placer deposits. Beside these localities, gold-bearing placers
have been found in several regions where quartz prospecting has
been carried on to a very limited extent and consequently com-
paratively few veins have been discovered, as in Nueva Ecija,
Tayabas, Catanduanes, Mindoro, Mindanao, and other places.
The localities from which placer gold has been reported are
shown in fig. 4. i
For the most part, placers are found in the valleys of the
modern drainage system, but at least two cases have been discov-
ered where the deposit was the result of ancient erosion. The
best example of the latter class is the Cansuran deposit, Surigao,
Mindanao.
VII, A, 2 Eddingfield: Ores of the Philippines 101
} Batanes ts.
PROVINCES.
/LOCOS NORTE, |
CAGAYAN. 5
ABRA, SUB. PROV, ILOCOS SUR. ipa) LEGEND
iLOCOS SUR. : BRS
Q Bebuyenes 's: Definite areas of workable placer
MOUNTAIN PROVINCE.
UNION.
NUEVA VIZCAYA. p EB Areas where placer gold is found.
ISABELA.
PANGASINAN.
TARLAC.
NUEVA ECIJA.
ZAMBALES.
PAMPANGA.
BULACAN.
TAYABAS.
BATAAN.
. RIZAL.
CAVITE.
LA LAGUNA.
BATANGAS.
AMBOS CAMARINES.
ALBAY
SORSOGON.
CAPIZ.
ANTIQUE
1LOILO
OCCIDENTAL
ORIENTAL.
ZAMBOANGA O/ST., MORO.
LANAO DIST, MORO, zx
« MISAMIS,
AGUSAN.
SURIGAO.
COTABATO DIST.,MORO.C)
OAVAO OIST., MORO.
R=)
SSOmpsauneons
csiamianes
Kagayanes Is.g
Kavilli 1 >
Sasijor 1.
Fic. 4—Showing localities from which placer gold has been reported.
Lepanto.—The placer deposit lies in the Comillas Valley of the
Abra River which drains the Suyoc mineral district. The gold
is derived from the erosion of the veins in the Suyoc mineral
district. The amount of workable ground has been estimated
102 The Philippine Journal of Science 1913
to be 27,000,000 cubic meters,* carrying about 50 centavos per
cubic meter (20 cents United States currency per cubic yard).
Pangasinan placer.—The Agno and Tuboy Rivers that drain
the Baguio and Lubang districts are very swift and carry the
gold for great distances before it is deposited. The result has
been the formation of an area of about 100 square kilometers
of gold-bearing gravel in Pangasinan where the country changes
abruptly from a precipitous mountain region to a large rolling
plain. The rivers upon entering this plain have taken mean-
dering courses, frequently changing their channels, and thus
depositing the gold over a large fan-like area. They also very
frequently overflow their banks, filling in large areas with flood
gold. The gold deposited is fine and frequently in the form of
rounded flakes. Coarser gold is found in the mountainous por-
tion, where smaller streams flow into the Agno and Tuboy
Rivers. Many such placers are worked by native miners. The
gravel in Pangasinan is very deep except near the mountains,
and contains many bowlders of all sizes wherever the river
channel has been. This feature has made the testing of the
ground a very difficult operation.
Nueva Ecija.—Gold from the Eastern Cordillera of Luzon has
been distributed irregularly over a larger area than any other
section of the Islands, forming hundreds of square kilometers
of placer in Nueva Ecija, Bulacan, Rizal, and Tayabas. The
most interesting feature is the occurrence of platinum in this
placer. Some flat pieces have been found a centimeter in dia-
meter. Grains weighing a milligram are of common occurrence.
The two largest unbroken areas are found in Nueva Ecija,
extending eastward from the line between Cabanatuan and
Gapan and in Tayabas surrounding Dingalan Bay. The placer
in Bulacan and Rizal is found principally along stream beds.
Ambos Camarines.—There are four sections in this district
where placer gold is found: 1, Mambulao; 2, Gumaus; 3, Para-
cale River; and 4, Maliguit.
The Mambulao placer has not been thoroughly tested. Gold
is found in the gravel surrounding the bay. It is derived from
several large quartz veins in the San Mauricio and Robinson
groups, and from stringers in the schist and gneiss.
The Gumaus placer is very different in character from the
other deposits in the district. The gold is found in rounded
grains of a clear yellow color. Very few crystals or flakes are
found. A large number of rich stringers, many of which con-
* Appendix, Report of the Philippine Commission (1908), 317.
vill A, 2 Eddingfield: Ores of the Philippines 103
tain galena and sphalerite, but no very important quartz veins,
have been found in the immediately surrounding hills. There
is also a smaller percentage of black sand than in the other local-
ities of this district.
The Paracale River placer lies in an elliptical basin covering
an area of several hundred hectares. The bed rock is granite
gneiss, and the alluvium varies from 6 to 14 meters in depth.
The concentrates caught on the tables of the dredge are made
up of about 51 per cent magnetite, 16 per cent limonite, 21 per
cent pyrite, and 12 per cent nonmetallic material. The gold is
mostly angular and crystalline; crystal trees and minute octohe-
drons are of common occurrence. The larger grains of gold are
usually attached to quartz grains. This deposit has been de-
scribed in detail by Fanning and Eddingfield.”
The Maliguit placer is found along various sections and
branches of the Maliguit River. It presents about the same
general characteristics as the Paracale River placer.
Masbate.—The placer deposit lies in the valley of the Guino-
batan River, Aroroy. The gold is very fine and difficult to
recover. It was derived mostly from the numerous large veins
of calcite quartz and manganese and from small quartz veins.
It has been claimed that the presence of manganese in the veins
prevents the formation of placer in accordance with Emmons’
theory of the solution of gold.1? While this may apply to a
limited extent, conditions are such as to justify hesitation in
making its application general.
Mindanao.—Placer deposits are found at Placer, Cansuran,
and Lubangan, Surigao; along several streams on the eastern
side of the Agusan River, Butuan subprovince; and in the valley
of the Pigtao River, Misamis. Of these, the Cansuran deposit
is of the greatest interest. The gold is very coarse and is found
in well-rounded grains. Some pieces have been found weighing
over 30 grams. The alluvium is found on the crests and sides
of the hills as well as in the valleys, and therefore represents
an old deposit which has passed through some geological move-
ments which raised it in part above its old bed. This deposit
has been described in greater detail by Eddingfield."
“This Journal, Sec. A (1912), 7, 218.
“The agency of manganese in the superficial alteration and secondary
enrichment of gold deposits in the United States. Bull. Am. Inst. Min.
Eng. for 1910 (1910), No. 47, 767.
* Min. Resources P. I. for 1911, Bur. Sci., Div. Min. (1912), 27.
104 The Philippine Journal of Science 1913
Other districts——Placer gold has been found in Ilocos Norte,
Polillo, Batangas, Bondoc Peninsula in Tayabas, Mindoro, Catan-
duanes, Sibuyan, Panay, Cebu, Negros, and Bohol. Very little
is known of these deposits. Some are known to be of very limited
extent, while others, particularly in Mindoro, may prove to be
very extensive. The localities where placer gold deposits have
been reported are shown in fig. 4.
ILLUSTRATIONS
PLATE I
Mineral veins in the Baguio mineral district.
PLATE II
Mineral veins in the Paracale mineral district.
PLATE III
Relief map of Aroroy district.
TEXT FIGURES
Fic. 1. Showing faulting of the “Tejon dike” on the Ascension group.
2. Showing localities where gold-bearing veins have been found.
3. Veins on the Kelly North Slope.
4. Showing localities from which placer gold has been reported.
105
4,
eae ORE
ae
EDDINGFIELD: ORES OF THE PHILIPPINES. | (PHL. Journ. Scr., VIII, A, No. 2.
“SCALE
250 590 750 Jo00
1
=r
=o Mineral Veins
PLATE I. MINERAL VEINS IN THE BAGUIO MINERAL DISTRICT.
a
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eae iW
re
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EpDDINGFIELD: ORES OF THE PHILIPPINES. ] [Puiv. Journ. Scr., VIII, A, No. 2.
PLATE Ill. RELIEF MAP OF AROROY DISTRICT.
A BONUS SYSTEM FOR THE PURCHASE OF PORTLAND CEMENT
By W. C. REIBLING
(From the Division of General, Inorganic, and Physical Chemistry, Bureau
of Science, Manila, P. I.)
INTRODUCTION
In the first paper from this Bureau on the subject of Portland
cement, the efficiency of modern cement specifications and
standard methods of testing were discussed. It was made evi-
dent that the ability of a cement to pass even the most approved
specifications did not prove either its real or relative value in
construction work, and that no tests had been devised which
would give definite information about the behavior of cement
both before and after induration. Since then information con-
cerning the physical and chemical properties of Portland cement
has increased, and standard specifications have shown a corre-
sponding improvement; but they still leave much to be desired,
and both the accuracy of standard methods of testing and the
efficiency of standard specifications must undergo considerable
change before they will secure the manufacture and purchase
of Portland cement having the desired constancy in volume,
strength, setting properties, and sand-carrying capacity.
The weakness of all cement specifications is due largely to the
lack of definite knowledge concerning the chemical and physi-
cal properties of Portland cement. In fact, the results obtained
from standard tests are so little understood that they do not
enable us to arrange the various products in their true order of
merit. Consequently:
(1) The chief object of testing is defeated, and it is necessary
to specify minimum requirements which are intended only to
cover the lowest limits which can be allowed on the work and
to provide for lack of uniformity in tests as well as in real
quality.
(2) There is practically no difference between the qualities
and properties of a rejected and of an accepted cement in the
immediate vicinity of the limit set by specifications; and it is
often impossible to avoid the use of inferior material.
(3) As quality is specified, the enforcement of cement speci-
fications usually makes it compulsory to award contracts to the
*Reibling, W. C., and Salinger, L. A., This Journal, Sec. A (1908), 3,
137-185.
107
108 The Philippine Journal of Science 1913
lowest bidder regardless of the advisability of purchasing better
material at a reasonably higher price.
(4) The awarding of contracts to the lowest bidder offers little
incentive to produce a higher grade cement than that which will
meet the specified minimum requirements. In fact, many man-
ufacturers have to cut down their burning and grinding expenses
to the lowest possible figure in order to secure sufficient sales.
The importance of always securing good cement is enhanced
in the Philippines where most of the material comes a long
distance by sea and where the cost of transportation is high;
and many attempts have been made to establish a system of
inspection and purchase which would insure the importation
of nothing but satisfactory cement, and thus eliminate costly
rehandling and troublesome delays which always accompany
rejected cement, and which heretofore have spasmodically
occurred to the detriment of all interests involved. At times,
local officials have bought cement on reputation and personal
experience, irrespective of cheaper brands then available. To
our knowledge none of the cements so purchased were other than
first-class. On the other hand, all cements which have given
questionable or unsatisfactory results were purchased from the
lowest bidder. Nevertheless, accusations of personal motives and
prejudice, or the possibility of such, and the cry of unfair treat-
ment from local agents of other brands ultimately forced officials
to purchase on a basis of quantity rather than quality.
Similar attempts and results have been of common occurrence
in other countries, so that the following brief history of the
local operations of standard cement specifications, and, in fact,
the entire discussion throughout this paper, are general in their
application.
OPERATION OF STANDARD SPECIFICATIONS
Previous to the year 1907 the local standard for Portland
cement was based upon the requirements of the 1902, U. S. Army
specifications. During this time the engineer in charge of the
construction of the water-supply system for Manila purchased
a certain high-grade cement which had an excellent reputation
and always passed well above the specifications in use. It was
well burned, finely ground (about 88 per cent passed the standard
200-mesh sieve), its sand-carrying capacity was large, its pack-
ing was good, and different shipments received from time to
time showed a remarkable uniformity in physical and chemical
properties. However, certain manufacturers objected to the
purchase of this cement on the ground that they were willing
VII, A, 2 Reibling: Portland Cement 109
to furnish cement for less money which would meet all of the
requirements of the specifications; and, finally, the engineer
was forced against his best judgment to use other and cheaper
material. The products then obtained often failed to pass, and
much of the cement barely passed, the specified requirements.
At times, workmen and inspectors complained about their setting
and hardening properties; and, at all times, their use was accom-
panied by considerable controversy, uncertainty, and confusion,
which involved considerable expense and vexatious delays.
In 1908 a special committee was appointed to improve these
conditions. They advised the adoption of specifications similar
to those of the American Society for Testing Materials, but
slightly modified so as to be practicable under tropical conditions.
These specifications went into effect in April, 1908, but they
failed to secure the desired improvement.
About this time another attempt was made to purchase cement
on a basis of quality. The purchasing agent inserted on his
bids the words “selection and award of this contract will be
made on a basis of the quality of the cement offered.” This
brought forth the criticism that a personal equation of opinion
and prejudice had been introduced, which defeated the purpose
of the specifications; and the action of the purchasing agent
was not approved. In 1912, he again inserted the same clause,
and again merchants entered a vigorous protest. The matter
was referred to a special committee, which reported as follows:
After careful consideration, the committee fails to find any just cause for
criticizing the Purchasing Agent for inserting in his request for bids the
words “selection and award of this contract will be made on a basis of
quality of cement offered.” However, as the specifications themselves fix
the minimum requirements, and as it is impossible to determine in advance
the quality of cement which may be delivered, we believe that this clause
should apply to the rejection of cements which have previously proven
unsatisfactory, or, to cements which have not yet established for themselves
a reputation for general reliability and soundness. Interpreted in this
manner, the clause above referred to is neither unusual nor unreasonable.
In support of this conclusion, the committee quoted from
paragraph 11, page 8, of the 1912 Government Specifications,
which reads as follows:
Bids for furnishing cement, or for doing work in which cement is to be
used, shall state the brand 6f cement proposed to be furnished and mill by
which made. The right is reserved to reject any cement which has not
established itself as high-grade Portland cement and has not been made by
the same mill for two years and given satisfaction in use for at least one
year under climatic and other conditions at least equal in severity to those
of the work proposed.
110 The Philippine Journal of Science 1918
The presence of such a proviso fails to eliminate the possibility
of a personal motive or prejudice in selection. Furthermore, the
rejection of all cements except those of established reputation
would practically place the consumer at the mercy of present
manufacturers.
On October 30, 1912, the cement specifications of the Govern-
ment of the Philippine Islands were again changed by Executive
Order No. 75, and now they conform to the 1912 specifications of
the United States Government. As there are no vital differ-
ences between the latter and the specifications of the American
Society for Testing Materials, the change can not be regarded
as beneficial.
During these six years, the quality of the cements received
was equally as unsatisfactory. The records of this Bureau
show that:
(1) The best products received from different manufacturers
varied considerably in character and efficiency.
(2) While in certain instances different shipments from the
same mill showed a remarkable uniformity in quality, in others,
we have met with sound and unsound, slow and quick-setting
cements, and cements which developed both low and high 7-day .
tests, the value of which was no criterion of the ultimate
strength.
(3) At times several shipments showed an apparent inten-
tional decrease in efficiency. New cement factories, especially,
have been known to submit very good material at first, and then,
as soon as their product had gained a suitable reputation, to
cut down grinding and burning expenses and market an inferior
product.
The differences between different brands of high-grade cement
is readily accounted for. I have inspected many large plants in
Asia, Europe, and America, and have found adequate reason
in local conditions for the peculiarities of many products which
laboratory tests had revealed. The quality of the best product
from any mill depends more or less upon the nature of the raw
materials used, the processes of manufacture employed, and the
influences of various factors on the cost of production. For
instance, a uniform shipment, whether good or bad, was always
associated with large storage bins for the ground cement. On
the other hand, the cement received from one factory, where
the storage capacity was so limited that the cement was packed
almost as soon as it left the grinder, usually showed considerable
variation between successive samples taken from the same ship-
ment. It is evident that variations in the product of the grinders
VII, A, 2 Reibling: Portland Cement 111
and kilns become minimized when several hundred tons of cement
become mixed in the same bin. The skill of the workmen, the
kind of kilns and fuel used, the efficiency of grinders and mixers
employed, as well as the hardness, purity, uniformity, and chem-
ical composition of the raw materials are essential factors which
vary more or less at different plants. However, a gradual falling
off in quality is usually the result of deliberate intention. The
manufacturer can control the quality of his product within
reasonable limits; and, as he knows the character of his cement,
no manufacturer unknowingly sends out whole shipments of poor
material.
Manufacturers as a rule are anxious to supply satisfactory
material, but they claim that the policy of purchasing from the
lowest bidder compels them to direct their main efforts toward
cutting down operating expenses rather than toward perfecting
their cement. The manager at one plant made this point very
clear. When asked if he did not think that better burning and
finer grinding would improve his product, he replied: “Certainly,
I could increase its efficiency about 20 per cent, and it would
cost only about 8 cents per barrel to do so, but the Philippine
Government will not pay to have it improved. Our cement passes
the specifications as it is, and in order to get the contract we
have to figure close to the quality specified. At first we bid
only as low as good practice permitted, but, after losing several
contracts because cement inferior to ours sold at a few cen-
tavos, or even one centavo, less, we had to change our policy.”
Our own extensive investigations on the physical and chemical
properties of Portland cement made the truth of this statement
very apparent. For best results, the raw materials must be
carefully proportioned, finely ground, thoroughly mixed, and
hard burned, and the finished product must be ground to extreme
fineness. Therefore, efficiency is obtained only at a correspond-
ing expense to the manufacturer, and the practice of awarding
contracts to the lowest bidder has tended to limit the quality of
the cement and discourage the best manufacturing practices. It
also has failed to obtain the best results from the standpoint of
relative cost and efficiency.
Some time ago the Philippine Division of the United States
Army advertised for bids on 75,000 barrels of Portland cement to
be used for fortification work at Corregidor. The three lowest
bids were as follows:
(a) A Belgian cement at 4.36 pesos per barrel.
(b) An American cement at 4.38 pesos per barrel.
(c) An English cement at 4.38 pesos per barrel.
112 The Philippine Journal of Science 1913
The maximum difference in the cost of the three cements was
only 2 centavos a barrel, or 1,500 pesos on the contract for
327,000 pesos. A low estimate of the total cost of the concrete
construction work is six times that of the cement, or 1,962,000
pesos. Fifteen hundred pesos represent only 0.076 per cent of
the total cost of the concrete; yet, other conditions being equal,
the difference of 1 per cent in the efficiency of the cement
represents, in durability and in strength of the concrete, a value
of 19,620 pesos. That there may be a difference in concrete effi-
ciency of as much as 25 per cent even between two cements of
the same brand, both of which pass the standard specifications, is
illustrated in Table III. The actual difference in representative
samples of two of the above cements is given in Tables I and II,
in which the cements are designated as No. 1 and No. 2.
TABLE I.—Results obtained by subjecting two cements to the tests of the
specification of the American Society for Testing Materials.
Results.
Test.
Sample Sample
No. 1. No. 2.
Specific gravity:
WMriedatO0/CC wet ae eens Neer eee ee ee 8.14 3.08
Teenie! Seo.) nnn ee Beek SE 2s SE Nek Shale 3.19
Composition: Per cent. Per cent.
Lossiby ignibion = 390. eee ee oe eee 1.03 2.94
Content of magnesia (MgO) ________-__-__-_-__________ 1.34 2.83
Content of sulphuric anhydride (SOs) __-_-------___- 1.16 1.19
Fineness: Per cent. Per cent.
Through the 200-mesh sieve _____-------------------- 87.0 717.4
Through the 100-mesh sieve --_---------------------- 97.8 95.2
Time of setting: Hours. Hours.
Initial setvere-= 2s. 5-2 nek Ae ee DN eae se 2.0 1.6
Winall See aon kek. of eo 1 ee a eee A 4.3 3.6
Soundness in steam, air, and water___--_---------------- sound sound
Pounds per | Pounds per
Tensile strength: sq. wnch. sq. inch.
i-day, neat mortar £.0-) 2) ee ee ee ee 739 653
28-day) neat mortars] ocean eee eee eee 745 707
Y=day, Li: 3, Ottawa-saud mortar oo 22 eee enoeenne 310 313
28-day, 1:3, Ottawa-sand mortar__------------------ 422 379
The figures in Table I prove that both cements passed all the
requirements of the specifications. However, sample No. 1 is
VIM, A, 2 Reibling: Portland Cement 113
better burned, finer ground, and contains less free lime than
sample No. 2. Its great superiority to No. 2 is shown by Table II.
TABLE I].—Tests which show the difference in efficiency betweeen cements,
both of which passed all the requirements of standard specifications.
Relative efficiency,
Strength in pounds per square inch. 4 based on the
Sample strength of No. 2.
No.
7 days. | 28 days. |8 months.| 23 years. | 3 months.| 2 years.
Tensile strength of neat
mortar eee et 8 1 739 745 756 b716 105.3 110.0
Dow eee tes 2 653 107 718 e651 100.0 100.0
Compressive strength of
neat mortar_-________- 1 4, 080 6, 030 8, 800 11, 450 116.6 115.8
DG ae 2 7, 050 8, 250 7, 550 9, 890 100.0 100.0
Tensile strength of 1:3,
Ottawa-sand mortar__ 1 310 422 429 418 117.9 150.0
DO ease n a Sea 2 313 379 364 278 100.0 100.0
Compressive strength
of 1:3, Ottawa-sand
moONtbare ees = 2 tS 1 2, 580 3, 470 3, 700 4, 860 139.1 137.4
1D Yo) (ae Ss Se ee ae 2 2,080 2, 565 2, 660 3, 537 100. 0 100.0
"Each value represents the average of ten determinations.
b Total change in the length of a bar of neat cement No. 1=0.047 per cent expansion.
¢ Total change in the length of a bar of neat cement No. 2=0.098 per cent expansion.
The above does not represent an unusual or an abnormal
experience. Some Portland cements which pass standard speci-
fications are far inferior to sample No. 2 and some are superior
to sample No. 1. In this case the superiority of sample No. 1
manifests itself in the specified tests, but very often the direct
opposite is true, as the decrease in strength or the change in
volume with age may be very great. In fact, some cements have
given very satisfactory early results, and then, after several
months, have disintegrated entirely.
Contracts awarded to the lowest bidder have not always
secured the poorest cements. The location and operating con-
ditions of some plants are so favorable that in certain markets
they can undersell all other competitors without supplying in-
ferior cement. For example, it is known that one manufacturer
pays only 80 centavos per ton for limestone and 3.10 pesos for
coal, while the same quantity of material costs another plant,
which competes for the same markets, 1.70 pesos for limestone
and 6.50 pesos for coal. Accordingly, in some localities, such
as the Philippines, certain manufacturers can underbid other
competitors and still supply a high-grade cement at a fair margin
116737——3
114 The Philippine Journal of Science 1918
of profit; and, as a result, there are many local officials who
believe that the present system for purchasing cement is the
most economical and that any expenditure in excess of the lowest
bid would be only an unnecessary expense. However, the records
of cement testing show that the manufacturers who secure such
contracts supply cement which tends to meet the minimum
requirements of our specifications rather than those of a high-
grade cement. This is especially true of cements imported into
the Philippine Islands, where standard, 1:3, Ottawa-sand
mortars, showing a strength over 400 pounds per square inch
between the periods of three months and two years, are as rare
as they should be common.
Careful investigation has shown that practically all of the
cements which have been purchased by the local Government
from the lowest bidder could have been considerably improved
at a very small expense by better burning, by proper seasoning,
or by finer grinding. The following instance will serve to show
that the same is true of Portland cements purchased in other
parts of the world. One of the best-known, high-grade, Amer-
ican cements was reground in a tube mill so that 88 instead of
78 per cent passed a 200-mesh sieve. Concrete made with this
cement before and after regrinding was then molded into six-
inch cubes and crushed after three months. In each case the
sand, gravel, water, and the proportions by weight were the
same. The average results obtained are recorded in Table III,
which also includes the tensile and compressive strengths de-
veloped by the ordinary briquettes.
TABLE III.—The strength developed by a high-grade Portland cement before
and after regrinding.
SIX-INCH, CONCRETE CUBES.
| Age in days. Compressive strength. |
Propor-
Genient tions Total in pounds. In pounds Hoes Rauere
RE by In moist Wea- j
volume. ote thered
; outside. First First
iexale. Ultimate. asa. Ultimate.
As received -_.___.---_- 1:2:5 21 70 55, 745 72, 955 1, 550 2, 027
Reeround 23s 1:2:5 21 70 64, 408 92, 135 1, 800 3, 559
VII, A, 2 Reibling: Portland Cement 115
ORDINARY BRIQUETTES OF 1:3, OTTAWA-SAND MORTARS SUBMERGED IN
FRESH WATER AFTER 24 HOURS IN MOIST AIR.
[ Tensile strength in pounds per Relative compressive strength in
square inch, pounds per square inch.
Cement. < :
7 days. | 28 days. ls months.) 1 year. ! 7 days. | 28 days. |3 months.} 1 year.
As received ______--___- 299 357 385 353 | 2,520 3, 159 3,510} 3,200
| Rerround) — 9225-2222 315 | 386 | 424 424 | 2,430 8, 078 3,861 | 4,239 |
When reground, the cement gave 26.3 per cent higher concrete
efficiency. It is estimated that the additional grinding would
have cost the manufacturer less than 10 centavos per barrel.
Computing on the basis of 5.24 pesos per barrel (the price named
in the latest contract of the Bureau of Supply), this additional
efficiency is obtained at an expense of less than 1.9 per cent of
the cost of the cement. When we consider that the total cost
of the concrete is about six times that of the cement, the extra
expense for finer grinding becomes almost insignificant.
However, there are many who attach little importance to such
facts. Portland cement is used in a rather crude manner and
much of it where great strength is not of practical importance.
This, and the somewhat general belief that a cement which meets
the requirements of our specifications is good enough for all
ordinary purposes, has induced many to belittle the importance
of obtaining a more uniform and efficient product. Also, many
claim that it would-be useless to use better cement with poor
aggregates such as are usually the only ones available for local
construction work. This attitude is founded on a basis which is
neither economical nor progressive.
If weak concrete meets the requirements, then cheaper material
such as “adobe” stone, hydraulic lime, or natural cement should
be used. On the other hand, for important permanent struc-
tures, the greatest economy and efficiency result from the intel-
ligent use of the best cement obtainable at a reasonable cost.
This is especially true in the Philippines where most of our
sewers, retaining walls, bridges, buildings, etc., are frequently
subjected to severe destructive influences such as typhoons,
earthquakes, and floods. Structures must be built to withstand
extraordinary rather than ordinary demands upon their strength
116 The Philippine Journal of Science 1913
and durability, and the very best cement has proved none too
good. The fact that the available aggregates are poor in quality
or that cement is used in a crude manner serves only to increase
the responsibility upon the cement; and, although a second-
grade cement may be good enough for some purposes, usually
a longer and a more satisfactory service will more than com-
pensate for the greater initial expense of securing better material.
Furthermore, if we purchase mediocre cement, and thus promote
its manufacture, we can not hope to obtain uniformity in quality,
without which the architect and builder are unable to figure
on close margins. Structures are small now as compared to
those which are likely to be erected in the future, but, even at
the present time, the lack of certainty of securing cement which
will retain a definite strength and not change in volume suffi-
ciently to develop dangerous internal stresses is a source of
great expense.
The most commendable feature of the present method of pur-
chasing cement is the promotion of competition, which is a
leading factor in keeping down market prices, and eliminating
the possibility of personal motive or prejudice. Competition for
our contracts has been fairly keen, but it has not been a com-
petition which has induced the best manufacturing practices,
supplied a uniformly high-grade product, or prevented the
necessity of expensive rejections. In short, it has been a com-
petition involving price rather than quality; and, unfortunately,
it is impossible to correct the faults of a poor cement by in-
creasing the amount used.
REQUIREMENTS FOR IMPROVED EFFICIENCY
Desirable results can be obtained only by establishing a
reasonable standard for the purchase and use of the Portland
cement which will be fair to the manufacturer and take into con-
sideration the work capable of being done as well as the quantity
of cement used. At the same time, the significance of inducing
and fostering competition should not be overlooked because we
must depend largely upon a condition of vigorous competition
to keep the cost within reasonable limits.’
*In 1909, I officially reported an instance where a cement manufacturer
shipped his best product hundreds of miles by sea and then sold it for less
than 4.50 pesos per barrel, while the community where the factory was
located often paid from 7 to 9 pesos for inferior material. This practice was
made possible by a heavy duty on all imported cements which enabled the
only home factory to eliminate competition.
VIL, A, 2 Reibling: Portland Cement Aire
How, then, can manufacturers be induced to compete on a basis
which demands the best product at a reasonably profitable price?
The most noteworthy attempt to solve this problem was in-
stituted by the New York Rapid Transit Company when it
contracted for cement manufactured according to certain stip-
ulations. An expert was stationed at the mill at all times to
inspect the process of manufacture, to reject any inferior mate-
rial, to insist upon proper burning, grinding, and seasoning, and
to test the cement before it was shipped. Such an inspection
at the place of manufacture can be conducted to the advantage
of the manufacturer and the consumer, but it is only practicable
when the contract involved calls for the purchase of a very
large quantity of material. Many cement manufacturers are
willing to codperate with such a plan provided the inspector
is a person of good judgment and experience. On the other
hand, the purchaser would need to have extreme confidence in
the inspector’s honesty and ability. The difficulty of finding
cement experts who would be acceptable to both parties is suffi-
cient to prevent the general application of this system.
A practicable method would be to buy cement which will pass
the minimum requirements of a standard specification as hereto-
fore, and in addition offer for superior quality a bonus which
will be a benefit to both manufacturer and consumer and induce
nothing but the best manufacturing practices. Such a bonus
system would promote a greater and a more desirable competition
than the present system, because the manufacturers could furnish
their best products at a lower price than heretofore and enter
into fair competition with inferior cements from which little or
no additional revenue could be expected.
None of the numerous attempts to establish such a system
have proved satisfactory. Years ago it was the common practice
to offer a bonus for cements which would give exceedingly high
7-day tests, but this practice was abandoned as soon as it became
generally known that the quick-hardening, rotary cements usually
develop such an abnormal decrease in strength that the slower
* Cement Age (1905), 1, 75.
In this instance the manufacturer complied with the suggestions offered
by the chief inspector, and tests carried on for five years showed a remark-
able regularity in the accepted product. There also was a continued im-
provement in the quality of the cement which corroborated the original as-
sumption that “an early stage, low pulling cement, which undoubtedly will
show best results in the long run can be made in rotary kilns notwithstand-
ing the general tendency of such commercial products to show abnormally
high early results with a consequent retrograde movement later on.”
118 The Philippine Journal of Science 1918
hardening, set-kiln products often gave better results in time.
Recently engineers have begun to realize that ordinary cement
contains only about two-thirds of its weight of actual cement,
and that the remainder is about as inert as ordinary sand because
it has not been sufficiently pulverized, and there has been a grow-
ing tendency to award a bonus for extreme fineness.4 This is a
step in the right direction, but many comprehensive tests show
that the strength developed by different cements does not depend
upon the degree of fineness.
Other conditions being the same, the degree of fineness affects
the quantity of active material in a given bulk rather than the
quality; and as an underburned Portland cement is easier to pul-
verize than a hard-burned product, the manufacturer can supply
a more finely ground cement without a corresponding increase in
strength. The strength developed and maintained by Port-
land cement is the net result of many factors including, besides
fineness, the influences of chemical composition, burning, and
seasoning.
The present state of our knowledge does not enable us to
specify either the conditions of manufacture or the properties of
a cement having the greatest possible value; and, even if other-
wise, manufacturing conditions, the nature of the available raw
materials, and the bulkiness of the product are such that it would
be impracticable to demand an ideal product. On the other hand,
our present knowledge is sufficient to enable us to specify and
identify the characteristics of Portland cements which give the
greatest efficiency which modern improvements for burning and
grinding have made practicable, to promote and support the
best manufacturing practices, and, accordingly, to secure Port-
land cement having the greatest uniformity and efficiency con-
sistent with the principles of true economy.
The efficiency of Portland cement depends primarily upon the
thorough sintering or fusing of the raw materials, and for
best results it is very essential to burn at a high temperature
and eliminate free lime. The strongest cements require the
highest burning temperatures because the formation of the high-
calcium silicates and the low-calcium aluminates requires greater
heat than is necessary to form the much weaker low-limed
silicates and high-limed aluminates.> The effects of the different
“Eng. News (1909), 62, 105, 179, 230, 358.
® Schott, Cement & Eng. News (1910), 22, Nos. 9 to 12.
VIII, A, 2 Reibling: Portland Cement 119
kinds of free lime were thoroughly pointed out in previous papers
from this laboratory.°®
It is sufficient to state here that free lime tends to cause dan-
gerous changes in the setting and hardening properties of Port-
land cement, and that the endurance of the early strength, the
increase in strength with age, and the constancy in volume will
be the greater the less free lime (or magnesia) the indurated
cement contains. Therefore, we can not hope to secure the de-
sired efficiency and uniformity in quality unless the quantity of
free lime is reduced to a very low figure. The best burning
and proper seasoning and storing produce a sound product
which has a high specific gravity and a low loss by ignition; and,
while it is impossible to obtain Portland cement which contains
no free lime, the manufacturer should burn his materials so that
no seasoning is required to produce a perfectly sound cement.
It is essential to increase rather than decrease the severity of
the requirements for constancy of volume.
While the large use of concrete demonstrates beyond question its value
as structural material, there are too many concrete structures now showing
signs of incipient failure to permit us to relax in any way the demands of
the standard specifications or our efforts to secure improvement in the
quality of the cement. If the use of Portland-cement concrete is to continue
to increase, or even remain as great as at present, the engineer must be
assured of its durability. It is unfortunate, perhaps, that the present low
prices of cement offer little inducement to the manufacturer to spend more
money to improve quality, or to assume the additional cost involved in the
storage of the clinker and the finer grinding demanded by Mr. Force. It is
an old axiom “that we get only what we pay for,” and if the engineer is going
to insist, as it seems proper he should, on the furnishing by the manu-
facturer, for important structures, of a cement which will pass the autoclave
test, he should be prepared to offer an advanced price for such a cement.
It is universally recognized that neat Portland cement is not durable,
and it is for this reason, and not from motives of economy only, that cement
is used mixed with sand or other aggregates. Until the cement manufac-
turers can produce a cement which will be durable when used neat, they
should not relax their efforts toward the improvement of their product, and
the engineer should not hesitate to adopt, and to insist that the cement shall
pass, any test, no matter how severe, that will develop any latent unsound-
ness or tendency to expand in time after the concrete made from it has been
hardened on the work. Even though one must pay more for a cement that
will meet such special tests than for one that will meet only those required
° Reibling, W. C. and Reyes, F. D., The chemical and physical properties
of Portland cement: Parts I and II, This Journal, Sec. A (1910), 5, 367-418.
Part III, ibid. (1911), 6, 207-252.
Parts IV and V, zbid. (1912), 7, 185-195.
Abstract and summary, 8th Int. Cong. Applied Chemistry, III ec. (1912),
5, 91-116.
120 The Philippine Journal of Science 1918
by the standard specifications, the increased cost of the work as a whole
will be small, and can be well afforded if it is an insurance against failure
or renders it less likely."
As already stated, the degree of final pulverization is another
important consideration. The particles of Portland cement
which are too coarse to pass a 150-mesh sieve may be considered
as inactive clinkers, the finer grinding of which produces a
cement whose efficiency depends upon the same conditions of com-
position, burning, seasoning, etc., as that of the impalpable
power obtained from large clinkers. The only other consider-
ation which the subject of fineness introduces is concerned with
the permanency of the strength developed by the finest and most
active particles. The durable nature of the indurated impal-
pable powder has been proved, and, considering that free lime hy-
drates more readily the finer its state of subdivision, the great
benefits derived from fine commercial grinding are apparent.
The ultimate chemical composition may vary within wide
limits, and Portland cements of the desired quality can be ob-
tained from most of the mixtures now used. Nevertheless, a
careful study of the available raw materials will show in each
instance that some combinations are capable of giving better
results than others, and usually one combination the best of all.
Therefore, each manufacturer should be induced to study his raw
materials until the most efficient mixture has been ascertained.
Also, he must carefully regulate the raw mixture at all times.
Otherwise it will be impossible to obtain a uniform product.
For best results the raw materials must be carefully selected
and regulated, finely ground, very thoroughly mixed and hard
burned, and the finished product must be of extreme fineness and
properly packed. All of these factors are so important that we
can not afford to neglect any one of them.
I do not believe that it would be advisable to formulate a bonus
system on the present requirements of the American specifi-
cations asastandard. The clauses which permit a determination
of the specific gravity after the sample has been ignited at a low
red heat, a loss by ignition of 4 per cent, unsoundness in accel-
erated tests, and a 25 per cent residue on a 200-mesh sieve
make it possible for rather poor grinding and burning to fulfill
these requirements. A much more efficient standard is outlined
7™Spackman, Henry S., The need of a more severe soundness test for
cement, Hing. News (1912), 68, 80.
VII, A, 2 Reibling: Portland Cement 121
in the recommendations for improving the present specifications
which were given in a previous paper.®
PROPOSED BONUS SYSTEM
In view of the foregoing, I suggest that Portland cement be
purchased as heretofore from the lowest bidder who guarantees
to fulfill the requirement of specifications, and that the following
provisions be made for bonuses to be awarded for superior
. quality: ¥
1. No bonus will be awarded unless the cement passes all of ~
the specified requirements including perfect soundness after the
steaming test and unless the cement is reasonably uniform in
quality and suitably packed.
2. A bonus of 10 centavos per barrel will be awarded if the
specific gravity is consistently above 3.10 (or the loss by ignition
not greater than 2 per cent).
3. A bonus of 10 centavos per barrel will be awarded if the
residue on the number 200 sieve is less than 15 per cent, and
that on the number 100 sieve less than 3 per cent.
4. Provided the gravity is not less than 3.10 (or the loss by
ignition not greater than 2 per cent), a bonus of 10 centavos
per barrel will be awarded if the 28-day, 1: 3, standard Ottawa-
sand briquettes show consistently an average tensile strength
above 400 pounds per square inch.°®
The above would provide bonuses for superior mixing, grind-
ing, and burning, and would permit the manufacturer to earn
30 centavos (15 cents United States currency) per barrel in
excess of the selling price. In Manila, 30 centavos is about 5.7
per cent of the usual cost of Portland cement and less than 1
per cent of the cost of concrete. On the other hand, such a
system properly enforced ought to secure at least 10 per cent
better concrete, eliminate the necessity of rejecting cement, and
secure greater certainty in its use.
Owing to the varying influences of local conditions in different
localities on the cost of manufacture, the values given in this
proposed system are not arbitrary. However, the principles
constitute the essential features, and they must remain fixed.
*This Journal, Sec. A (1912), 7, 189-191; also, Met. & Chem. Eng.
Special number (Sept., 1912), 10, 612; Hng. News (1918), 69, 298, and
Cem. & Eng. News (1913), 25, 91.
* The above recommendations provide for the possibility of a well-burned
cement with a lower specific gravity than 3.10, if the low gravity is not due
to an absorption of volatile constituent, but our experience does not include
such a possibility.
122 The Philippine Journal of Science 1918
Good packing is insisted upon in order to prevent properly
stored cement from serious deterioration. Perfect soundness
(no warping, checking, cracking, or disintegrating after the
hot test) is also essential, and it might be advisable, as recom-
mended by H. J. Farce,’° even to substitute the more severe auto-
clave test for steaming or boiling under ordinary pressure.
It is useless to insist upon soundness unless we also take into
consideration the specific gravity (or the loss by ignition). We
can season an underburned cement, or a cement made from
poorly mixed or coarsely ground raw materials, until it passes
the accelerated tests for soundness; not, however, without a cor-
responding reduction in the specific gravity and increase in the
loss by ignition. Likewise, we can not rely upon the specific
gravity or loss by ignition without taking into consideration the
soundness. A nonseasoned Portland cement usually has a high
specific gravity regardless of whether it is underburned or hard
burned and regardless of the amount of free lime present.
Therefore, a bonus is provided for perfect soundness in conjunc-
tion with a high specific gravity (or a low loss by ignition)
for the purpose of securing a well-burned product.
Another bonus is provided for superiority in strength in order
to induce a careful selection and regulation of the raw materials.
Ordinarily it would not be advisable to base a bonus on the
strength developed in twenty-eight days. If a cement contains
more than a very small quantity of hard-burned free lime, then
no reliance can be placed on the results of the early tests for
strength. However, well-burned cements show little or no de-
crease in strength with age; and, since it is specified that no
bonus will be awarded unless the cement is well burned; that is,
unless it has a high gravity (or low volatile constituents) and
is perfectly sound, no bonus would be granted except for superior
permanent strength.
In conclusion, it may be stated that certain manufacturers, to
whom the proposed bonus system has been submitted, have ex-
pressed their willingness to codperate on such a basis. The
agent of one company has written as follows:
The advantages to be secured from such a system as suggested are of
so pronounced a nature to both the purchaser and to the contractor that it
is not necessary to enlarge on them. The manufacturers would have every
inducement to produce cement above the minimum requirements set by the
specifications, and the bonus would undoubtedly cover the extra cost in-
curred for special care in packing, burning, and grinding. In the majority
“Hing. News (1911), 67, 1111.
VIII, A, 2 Reibling: Portland Cement 123
of cases, the manufacturer and his agent are very desirous to execute their
contracts to the satisfaction of all parties, and where financial conditions
permit, would prefer to supply material above the specifications in order
to avoid any risk of loss through rejection and consequent dissatisfaction.
The above expression of opinion has behind it the result of ten years’
trading in cement and business here amounting to over 100,000 barrels since
the beginning of the year. We shall be glad if it is possible to handle
cement for the Government on the bonus system mentioned above, and
shall be pleased to let you have any information from the factory that may
assist in the furthering of this system. ’
SUMMARY
1. A résumé of the operation of standard specification for
Portland cement shows the need of improving our contracting
methods for the purchase of this material.
2. At present there is little incentive to induce the manufac-
turer to grind and burn to the degree of perfection that modern
improvements have made practicable.
3. In order to secure the desired constancy in volume, strength,
setting properties, and sand-carrying capacity, the raw materials
must be carefully selected and regulated, finely ground, very
thoroughly mixed, and hard burned, and the finished product
must be of extreme fineness and properly packed. None of these
factors can be neglected.
4. Increased efficiency can be obtained only at a correspond-
ingly greater expense to the manufacturer, and Portland cement
should be purchased on a basis of quality as well as quantity.
5. Desirable results can be obtained only by establishing a
reasonable standard for the purchase and use of Portland cement
which will be fair to the manufacturer and take into considera-
_tion the work capable of being done, as well as the quantity of
cement used.
6. This standard must be applicable to a system which will
induce and foster competition.
7. In view of the foregoing, it is suggested that Portland
cement be purchased as heretofore from the lowest bidder who
guarantees to fulfill the requirements of an improved specifica-
tion, and that, in addition, bonuses be awarded for superior
quality.
8. A bonus system is described, the enforcement of which, it
is believed, would secure the desired results.
9. The bonuses specified permit the manufacturer to earn 30
centavos (15 cents United States currency) per barrel in excess
of the selling price provided he supplies a well-burned, finely
ground product and the standard, 1:3, Ottawa-sand mortars
124 The Philippine Journal of Science ath
show consistently an average reliable strength of over 400 pounds
per square inch.
10. In Manila the total bonus would average about 1 per cent
of the cost of concrete. It would secure at least 10 per cent
greater concrete efficiency, and practically eliminate the necessity
of rejecting cements.
11. Cement manufacturers have expressed their willingness to
codperate on such a basis.
ALTERATION AND ENRICHMENT IN CALCITE-QUARTZ-MAN-
GANESE GOLD DEPOSITS IN THE PHILIPPINE ISLANDS
By F. T. EDDINGFIELD
(From the Division of Mines, Bureau of Science, Manila, P. I.)
The agency of manganese in the production of secondary al-
teration has been discussed by W. H. Emmons.' He states:?
Since there are no data which show the effect of highly carbonated
waters on these reactions, I have so far as possible eliminated examples
of gold deposits in limestone, and the discussion is confined mainly to de-
posits in noncalcareous rock.
From this statement and particularly from the discussion
which follows, it appears that the case, where the ore deposit
itself contains calcite, had not been separately considered. It
is my belief that the majority of cases of manganiferous gold
deposits which do not conform to the theories of secondary en-
richment advanced by Emmons are calcite-bearing veins. An
examination of the descriptions of the ore deposits in the last;
section of the article mentioned above will show that the major-
ity of deposits which do not show impoverishment in the upper
level nor enrichment near ground-water level, are calcite-bear-
ing. These cases will be cited later.
Many ore deposits of the Philippine Islands are made up
of quartz and manganese with large amounts of calcite. Veins
of this character are so numerous that they may be said to rep-
resent an important type of Philippine deposits. Attempts have
been made to apply Emmons’ hypothesis to these ores; but in-
vestigations in the laboratory and in the field seem to indicate
that the reactions which take place in this class of deposits are of
such a character as to produce entirely different results.
These ores contain practically no copper. While I believe
that, if the copper content is relatively small compared with
* Bull. Am. Inst. Min. Eng. for 1910 (1910), No. 47, 767.
? Loc. cit., 772.
125
126 The Philippine Journal of Science 1913
the calcite content, the results would be the same, I have not
considered copper reactions in this discussion.
The principal characteristics of this class of deposits due ap-
parently to the presence of the calcite are: 1, The mine waters
are neutral or alkaline at practically all horizons above ground-
water. level; 2, owing to this fact no free chlorine can be formed;
3, should nascent chlorine be formed, it would readily attack
the moist calcite, so that little or no chlorine would remain un-
combined and free to attack the gold; 4, should gold chloride be
formed, some of the gold at least would be precipitated at ap-
proximately the same horizon by ferrous sulphate produced by
the oxidation of the iron pyrites.
In the Philippine calcite-bearing ore deposits the manganese
seems to be associated with the calcite in the primary ore.* All
the evidence available confirms this conclusion. Therefore,
wherever manganese is found, either calcite or calcium carbon-
ate in solution is present and would neutralize any acids,
or has been present and has already neutralized the acids. If
any acids are formed, it is evident that where they are formed
there is no calcite or calcium carbonate in solution and conse-
quently no manganese. Under such conditions, ferrous sulphate
would be formed, and it would appear that if there is insufficient
calcium carbonate to neutralize the acid there would also be
insufficient manganese oxide to oxidize the ferrous sulphate.
This condition would leave active an agent which precipitates
gold. .
ANALYSES OF MINE WATERS
In the analyses of mine waters‘ it is noted that acid hydrogen
was determined or found to be present in only 10 out of 29 cases.
The facts that in the general average of mine waters 295 parts
per million are calcium and 77 parts per million are the carbonic-
acid radicle might account for some of the 19 cases where acid
hydrogen was not reported and in which the mine waters were
neutral.
Analyses were made of mine waters of the calcite-gold deposits
of the Philippines to determine, primarily, free chlorine and
acidity.
° Fanning, Min. Resources P. I. for 1911, Bur. Sci., Div. Min. (1912), 44.
*Emmons, opus. cit., 778.
vil, A,z Eddingfield: Calcite-quartz-manganese Gold 127
TABLE I.—Mine-water analyses."
[Parts per million.]
Constituent. No, 1.6 No. 2.¢ No. 3.4
@hlorine (Cle) nee) ase ene nil nil nil
Chlorine (Cl) (combined) -__-__-_--_-------- ’ slight trace Slight trace 16.8
Sulphuric-acid radiele (SQ4) -.--..--------1 Zope) 283. 4 trace
Bicarbonic-acid radicle (HCO3) -______----_- 136.6 190.19) teh oe ee
Carbonic diexidel(COs)e (combined) te epee eee oe ere EY ey eee 13.2
E@arhonicdioxidel(CO2) merce) ee ee eee ee ton ece ean ae tase 12.0
Iron and aluminum oxides (Fe203, Al2Os) _- 1.2 OSB) at hee eh ea
raya (WRED) wae icine Seen lt aE OS 2 SI | ae es Hee ere re Ques
Manganese, (Mi) 9 se slight trace nil nil
@alerimi (Ga) pees eee ee AE a 186.5 123.3 2.8
Sodium (Na) not determined.
Mores (vier) 322 a ee Se 9.3 FLIPS | eee ee
LEGS: COP os SS See er 1.6 ce. per liter | 5.0 ce. per liter |_---------------
* All analyses by V. Q. Gana, Bureau of Science.
b No. 1. Headquarters mine, Baguio. Upper workings 20 meters from the surface. Solution
neutral to litmus.
© No. 2. Headwaters mine, Baguio.
litmus.
4 No. 3. Colorado mine, Masbate.
Forty meters from the surface. Solution neutral to
Solution reaction alkaline.
The ore above the point where the first two samples of water
were taken is calcite and quartz carrying manganese in large
amounts, about 1 per cent iron pyrites, and in places some galena.
In the analyses of these samples the large amounts of calcium,
sulphuric-acid radicle, and bicarbonic-acid radicle, the small
amounts of iron and manganese, and the absence of free chlorine
are noteworthy features.
The Colorado water sample was obtained where the leached
ore had had most of the calcite removed by surface waters and
the sulphides had been mostly oxidized. This analysis is char-
acterized by the alkaline reaction, the large amount of combined
chlorine, combined carbon dioxide, and relatively high iron, as
well as by the absence of free chlorine. In all three samples
there is no agent present which could dissolve gold.
LABORATORY EXPERIMENTS
A mixture was made of finely ground material representing as
nearly as possible the active constituents of the ore bodies. This
128 The Philippine Journal of Science 1918
consisted of 45 parts calcite, 45 parts manganese dioxide, 5 parts
ferrous sulphate, and 5 parts ferric sulphate.
Experiment No. 1.—Samples of this mixture were placed in
vessels with filter bottoms. Through these a solution, consisting
of about 10 per cent by weight of sulphuric acid and 10 per
cent sodium chloride in 80 per cent water, was allowed to leach
continuously, and the following analyses show the composition
of the filtrate after given periods of time.
TABLE II.—Analyses of water showing composition after given periods.
Constituent. Per cent. /} Per cent.» | Per cent.¢
Chiorines(free))2 siesta ee eee nil nil nil
Ghlorinel(C))k(combin ed) eee bb 1.89 1.3
Sulphuric-acid radicle (SQ4) ---___-_---_------_---_---------__ 0.4 0.733 4.27
Carbon dioxide (COz) (combined) ___________---___-_------_--- 0. 0004 0. 0004 nil
Carbon dioxide (CQz) (free) .------- === nil nil nil
Tron (He) gas =~ SRNR Bei NG ns IE ee AAO eee, Oe ee ee little 0. 034 0.24
Manganese) (Vin) bee 3 ae oe nee ee ae ene 6 eee ee nil 0. 124 little
Galeium (Ca) 20822 eee ee Se ee ae 0.13 0. 067 0. 105
Sodiumt(Na) 22 Sees es ieee a Eee ee oe 0.92 1.18 0.95
8 Solution neutral to litmus after 48 hours.
b Became neutral to litmus after 72 hours. An iron salt precipitated immediately after
passing the filter bed. Solution slightly acid.
¢ Solution acid after 75 hours.
After seventy-five hours the filtrate became decidedly acid and
contained a large amount of ferric chloride. At this stage it
was evident that the leaching solutions had formed channels in
the ore and were reacting only upon the walls of the channels.
The results of Table II indicate that no free chlorine would be
formed in a vein so long as the oxidizing waters were neutral,
alkaline, or only slightly acid, and that free chlorine is formed
only when the solutions are decidedly acid and iron is absent.
When iron is present, ferric chloride is formed which acts as a
solvent of gold in the presence of manganese dioxide. Experi-
ments 14, 15, 16, and 17 in Emmons’ paper® show that gold
is dissolved when hydrochloric acid and manganese dioxide or
ferric chloride and manganese dioxide are present.
Experiment No. 2.—A sample of the ore mixture was placed
in a bottle with 0.5 gram of finely divided gold, 50 cubic centi-
meters of saturated sodium-chloride solution, and 400 cubic cen-
timeters of 10 per cent sulphuric acid and agitated for eight
°Opus cit., 782.
viu, A,2 Hddingfield: Calcite-quartz-manganese Gold 129
hours. No free chlorine was found in the solution, and no gold
was dissolved.
Experiment No. 3.—A sample of the ore mixture was placed
in a bottle, with 0.5 gram of finely divided gold and freshly made
chlorine water, and agitated for eight hours. The resulting solu-
tion gave a strong test for free chlorine, but contained only a
trace of gold.
Experiment. No. 4.—Two parallel chlorination tests were run.
No. 1 was made up of finely ground calcium carbonate, 0.5 gram
of finely divided gold, and freshly made chlorine water. No. 2
was made up of finely ground quartz, 0.5 gram of finely divided
gold, and freshly made chlorine solution. These were agitated
for one hour. No. 1 solution gave a strong test for chlorine and
calcium, and showed. a trace of gold. The calcium was dissolved
to form CaOCl, and possibly CaCl,. No. 2 gave a strong test
for chlorine, and showed a large percentage of gold dissolved.
In the case of No. 1 the chlorine attacked the calcium carbon-
ate first, but the great excess of chlorine gave it an opportunity
to dissolve some gold as well. Another test, in which the chlorine
was in contact with the gold and calcite for forty-eight hours,
showed that a very large percentage of the gold had been dis-
solved. The reaction of chlorine with calcite would be more
important in an ore deposit where there is relatively so small an
amount of chlorine.
Experiment No. 5.—Calcium carbonate was added to gold-
chloride solution, boiled for five minutes, and filtered. No gold
was precipitated. The filtrate was almost colorless. It con-
tained a large amount of calcium, probably as a complex salt of
calcium and gold.
These experiments demonstrate that no acid could be formed
in veins containing calcite, except in waterways in the parts of
the vein where calcium carbonate is not encountered. It is prob-
able that even in such cases the acid would travel but a short
distance before coming in contact with, and being neutralized
by, calcite or calcium carbonate in solution. Chlorine cannot be
liberated except in the presence of acid, and consequently no
free chlorine or very small amounts only would be formed in
the type of vein under discussion.
If the gold were ever dissolved as gold chloride, it could be
precipitated by ferrous sulphate, metallic sulphides, calcite,
organic material, or bacilli at or near the same horizon.
°W. H. Emmons recently has found that gold is precipitated from cold
dilute solutions by calcite. I have not yet seen this in a publication.
1167374
130 The Philippine Journal of Science 1913
Philippine calcite ores.—The ore deposits of this type in the
Philippines are found in the Headwaters, Camote-Clayton, and
Bua mines of the Benguet mineral district; and in the Colorado
and Eastern mines of Aroroy mineral district, Masbate.
The Headwaters deposit is a fissure vein in the andesite made
up of bands of calcite, quartz, and manganese oxide carrying
about 1 per cent iron pyrites and traces of lead and copper.
The calcite in places is about 6 meters wide, while in others it
is very narrow and entirely disappears near the outcrop and
in the vein where leaching has been extremely active. The man-
ganese oxides are found in bands varying from 0.3 to 1.5 meters
in width; these bands are irregular, and vary from 2 to 6 meters
in width. The quartz is much fractured, and its sulphide con-
tents have been mostly oxidized in the upper levels. The calcite
in depth is compact and generally retains its sulphides unaltered,
but near the surface it is fractured, channeled, and contains
numerous stringers of manganese. The highest values are found
in the manganese bands. With depth the manganese oxide seems
to decrease and the calcite to increase. At and near the outcrop,
high values are found. These seem to decrease more or less
uniformly with depth.
The Camote-Clayton deposit is at least in part a fissure in
andesite, but appears to follow the contact between andesite and
diorite for a short distance. The gangue is calcite and quartz
with large amounts of manganese oxides and some iron pyrites.
In the upper workings the calcite bands are small; quartz bands
are also subordinate. The main portion of the vein is manga-
nese oxides (wad) including fragments of quartz and pockets
of crystallized quartz, which are said to contain high values.
The manganese bands vary in width from 4 to 12 meters. The
calcite increases and the manganese decreases with depth. The
gold values which are highest near the outcrop decrease with
depth.
The Bua vein is a fissure in andesite. It is from 1 to 1.5
meters in width. Bands of manganese oxide make up the greater
part of the vein in the upper workings, but in places solid com-
pact bands of calcite are found. With depth, the manganese
decreases, while the calcite increases until it makes up the major
portion of the vein. The ore contains some rhodochrosite and
from 2 to 6 per cent iron pyrite. The highest values are near
the outcrop, and are usually found in the manganese bands.
These values decrease with depth.
4
ee a ee ee
vin, a.2 Hddingfield: Calcite-quartz-manganese Gold 131
The Eastern mine, Aroroy, Masbate, has a very wide vein
with large amounts of quartz, stained with iron oxide and man-
ganese oxide in the upper workings. In places it appears honey-
combed, and stained with black manganese. Very little calcite
is found in the upper level, but it increases with depth until
on the 60-meter level the vein is composed almost entirely of
calcite. On the 30-meter level the vein is about half calcite and
half quartz, and contains from 3 to 8 per cent iron pyrites. The
gold values are highest near the outcrop, and are found in iron-
and manganese-stained quartz.
The Colorado deposit is made up of honeycombed quartz
stained with iron and manganese, crossed irregularly by bands
of hard, flinty quartz and-bands of soft manganese. The band-
ing is very pronounced and in places is very much twisted as
if movement had taken place in the vein producing lines of weak-
ness, but generally it is parallel to the walls. The honeycombed
quartz has formed molds representing perfect calcite crystals
and cleavage, as if at one time calcite had formed the major
portion of the gangue. In the lowest workings some calcite has
been encountered. The gold values are highest near the outcrop,
and decrease with depth.
In all of these examples the richest ore is at or near the surface,
and the values found so far appear to decrease with depth. This
condition would tend to indicate that no solution, or only an insig-
nificant amount of solution, had taken place due to the chlorine
reaction. All of these deposits are*in regions of rugged relief
and heavy rainfall, so that erosion would naturally be very rapid,
and placer deposits would be expected in all cases. In most of
these veins where the values are highest, from 20 to 30 per
cent of the gold can be recovered by amalgamation. The char-
acteristics of deposits where leaching by the solution of gold
with free chlorine has taken place are a barren zone near the
surface and a zone of enrichment near the water level. Neither
of these features is present in the deposits cited. It is probable
that a slight impoverishment occurs at the outcrop, due to the
mechanical transportation of the fine gold along the numerous
cavities and passages left by the leaching of the calcite.
ENRICHMENT IN CALCITE VEINS
While chemical concentration has apparently not taken place,
it is evident that concentration of some character has occurred
extensively, possibly to a greater extent than in a calcite-free
ore deposit. This is due to the great solubility of calcite in
leaching waters and particularly those containing carbon dioxide.
132 The Philippine Journal of Science 1913
Enrichment, therefore, is caused by two conditions: (1) By
the leaching of the calcite, which causes a removal of a value-
less element, leaving a smaller mass of richer ore; and (2) by
mechanical concentration of fine gold along channels caused by
fracturing and by the removal of the calcite.
The removal of the calcite reduces the mass of the ore carrying
the gold from 30 to 75 per cent. This alone would increase the
value of the ore from 50 to 300 per cent. Certain portions of
the veins in the Eastern and Colorado mines have been so thor-
oughly leached of calcite that the network of quartz remaining
has the appearance of a sponge. The removal of the calcite
and the oxidation of the pyrite in the quartz and the pyrite
originally with the calcite but left behind in the leaching process
creates an ideal condition for mechanical concentration of the fine
gold in the primary ore. The gold is carried down with the
manganese and iron oxides by water, and deposited along the
cracks and fissures in the vein. The manganese being difficultly
soluble and being so abundant in the ore is concentrated in
large amounts simultaneously with the gold, forming soft black
bands. This would account for the association of high gold
values with the manganese.
Some of the examples of deposits in the United States cited
by Emmons,’ which seem'to bear directly on points under dis-
cussion and to confirm these conclusions, are given below.
II. Black Hills, S. D—The principal minerals are quartz, dolomite, cal-
cite, pyrite, arsenopyrite, and gold * * *, Some of the ores at the
surface were below the average tenor, while other surface-ores were two
or three times as rich as the average * * *. In general, according
to S. F. Emmons, secondary enrichment by surface-leaching has had rela-
tively small importance.
Ill. Treadwell Mines, Alaska.—The minerals include quartz, albite, rutile,
chlorite, * * * epidote, * * * chalcopyrite, and molybdenite.
Manganese-minerals are not reported. * * * Nothing in the character
of the ore indicates any important concentration of values by oxidizing
waters.
VII. Ophir District, California.—The gangue is mainly quartz with a
little calcite. * * * The extensive development of placers, the value
of the ore near the surface, and the occurrence of valuable ore-shoots just
below the surface are opposed to the notion of extensive migration of gold
in these deposits.
IX. Phillipsburg, Mont.—At the Cable mine the deposits are included
in a long, thin block of limestone in contact on either side with quartz-
monzonite. The principal minerals are calcite, quartz, pyrrhotite, pyrite,
magnetite, and chalcopyrite, with chlorite, muscovite, and other silicates.
At one or two places small traces of manganese dioxide have been noted
"Opus cit., 818 to 836.
viu, 4,2 EHddingfield: Calcite-quartz-manganese Gold 1338
in the oxidized ore, * * *. This deposit yielded important placers.
Good ore was found at or very near the surface; and, according to the
best obtainable data, the values increased somewhat for a short distance
below the surface. Some concentration has taken place by the removal
of calcite and other valueless material more rapidly than gold; but there
is no evidence of secondary enrichment in gold below the water-table. The
indications are that the gold has not been extensively transported since
the deposit was formed. .
XIII. Georgetown, Colo., silver-lead deposits—The principal metallic
minerals are argentiferous galena and blende, with pyrite and chalcopyrite;
the ores usually carry about $2 gold per ton. * * * The gangue is
quartz, chalcedony, barite, with carbonates of lime, iron, manganese, and
magnesia. * * * The zone of complete oxidation extends from 5 to
40 ft. below the surface. The oxidized ore often contains several hundred
ounces of silver per ton. Below this ore are friable black sulphides and
secondary galena. This secondary ore, according to Spurr and Garrey, is
rich in silver and lead, and carries more gold than occurs at greater
depth.— Quoting from Spurr and Garrey:
* * * These richer ores diminish in quantity as depth increases,
though gradually and irregularly, so that the lower portion of the veins
contains relatively less silver and lead. The best ore in most veins has
‘been found in the uppermost 500 feet, * * *,
XIV. Auwriferous deposits of the Georgetown Quadrangle, Colorado.—
They carry pyrite, chalcopyrite, * * * quartz, adularia, and gold, with
minor amounts of barite, fluorite, telluride, ete. Carbonates of iron, mag-
nesium, lime, and manganese occur, but are relatively rare. * * * They
have yielded some moderately-productive placers. In several mines, the
oxidized is much richer than the average ore.
XVI. Cripple Creek, Colo—* * * Calaverite is the chief primary
constituent; native gold is rarely present in the unoxidized ores. Pyrite
is widely distributed; tetrahedrite, * * * and molybdenite are spar-
ingly present. The gangue is quartz, fluorite, adularia, carbonates (in-
cluding rhodochrosite), some sulphates, etc. Some of the deposits were
workable at the surface, but the placers which have formed are relatively
unimportant. * * * Manganese oxides are often present in the oxidized
zone, and, according to Penrose, form nodules in the Pharmacist and
Summit mines. They result from the alteration of rhodochrosite, manga-
niferous calcite, or other minerals, and are generally distributed in the
oxidized zone as stains filling cracks and fissures. * * * Whether a
slight enrichment of gold has taken place in the oxidized zone it is not
easy to decide. Lindgren and Ransome are inclined to the belief that the
oxidized zone as a whole is somewhat richer than the corresponding tellu-
ride zone. If this is true, no extensive downward migration of gold can
have taken place. The trivial enrichment in the oxidized zone may have
resulted from the removal of some constituents of the primary ore.
XX. Tonopah, Nev.—The deposits at Tonopah, Nev., are silver-gold
replacement-veins in andesite. * * * Placers are not developed. The
primary ore, according to J. E. Spurr, is composed of quartz, adularia,
sericite, carbonates of lime, magnesia, iron, and manganese, with argen-
tite, stephanite, polybasite, chalcopyrite, pyrite, galena, blende, silver
selenide, and gold in an undetermined form. * * * The waters which
descend through the oxidized zone carry sulphates and chlorides, and “wad”
134 The Philippine Journal of Science 1913
is plentiful; but judging from the fairly constant proportion of gold to
silver (about 1 to 100 by weight) there has been little selective migration
of gold and silver during oxidation, although the vein has been enriched
to some degree by downward penetration of minerals leached from the out-
crop as it was eroded.
XXII. Manhattan, Nev.—Although the schists contain stringers of gold
of uncertain genesis, the principal deposits are steeply-dipping lodes of
quartz and calcite, stained with iron and manganese oxides. Some placers
are developed. Rich ore was found very near the surface, but it was
richer a few feet below the outcrop than at the surface. * * * In
many instances the gold of the pockets of rich ore is intimately associated
with iron and manganese oxides.
XXIV. Bullfrog District, Nevada.—The minerals include pyrite, quartz,
and manganiferous calcite. Enough manganese is present in the calcite
to stain much of the oxidized ore chocolate-brown or black. No placers
are developed. The outcrops are comparatively poor, but within a few
feet of the surface good ore was encountered, and some of the deposits
were worked by open-cut. Some of the deposits decreased in value below
the 400-ft. level, where ore carrying less than $5 per ton is encountered.
Since the ore above this level carried many times this value, it appears
that there has been a secondary concentration by surface-waters, and that
the rich ore is related to the present topographic surface.
GOGO, ENTADA SCANDENS BENTHAM, AND ITS EFFECT ON
GOLD AND GOLD SOLUTIONS
By F. T. EDDINGFIELD
(From the Division of Mines, Bureau of Science, Manila, P. I.)
Since in the Philippines gogo juice has been universally used
by the natives in panning gold-bearing sands, an investigation
of its properties seemed desirable. The native has for panning
a large wooden bowl, batea, which is about 65 centimeters in
diameter, and slopes to a point in the center like a very flat
inverted cone. The panner, usually a woman, has a little gogo
bark at hand which at certain times she squeezes over the pan,
causing the juice to fall on the water in the pan. It is believed
that in this way more gold is recovered, by causing the fine gold
to settle quickly and not float away.
According to Bacon,' gogo is taken from the plant Hntada scan-
dens Bentham. It is called “gogo” by Tagalogs and “bayogo”
and “balogo” by the Visayans and Pampangans. The solution
obtained from gogo is neutral, neither acid nor alkaline. Its
chief constituent is saponin, a complex vegetable poison, which
has a very slight acid reaction, and constitutes one of the groups
of glucosides. These are generally colloids. Bacon further
states that saponin has the quality of holding bodies in suspen-
sion; such as powdered charcoal, lead sulphide, barium sulphate,
and barium carbonate; and that mercury is readily “killed” and
oils emulsified by its aqueous solutions. In the following pages
the aqueous solutions of gogo bark will be referred to as “‘gogo.”
Several tests were made with mercury, and it was noted that
when gogo was added the mercury was easily divided into minute
globules which refused to be reunited. This is caused by a thin
film being formed around each globule which “soils” it and makes
it difficult for fresh faces of mercury to come in contact with
each other. It also robs the mercury of its quality of amalga-
mation with gold, silver, and copper; a condition which has prob-
ably given rise to the belief, held by some, that Paracale gold
will not amalgamate.
*This Journal (1906), 1, 1022.
135
136 The Philippine Journal of Science 1913
In order to obtain finely divided gold, gold chloride solution
was treated with oxalic acid. While this precipitate was still
in suspension, gogo was added. It had apparently no effect upon
the physical condition of the gold, which settled with the same
rapidity and had the same color as gold precipitated by oxalic
acid alone.
Further tests were made to determine if gogo in any way
increased the adhesion between gold and wood or the cohesion
between gold particles, but no change was noted. It also failed
to reduce the surface tension of water to any noticeable extent,
or to clean the gold by cutting the oil upon it.
The above tests show that gogo has no qualities which would
be beneficial to the concentration of gold and it would be actually
harmful where amalgamation is used. Apparently its only
agency is the effect of the spray of solution falling on the float-
ing particles of gold in the pan and causing them to sink. Water
sprayed in the pan would have the same effect. On the other
hand, the tests indicated that gogo is detrimental where amal-
gamation is used, and its only apparent quality is to hold fine
particles in suspension, an effect just opposite to that desired.
In making the test on finely divided, precipitated gold it was
found that if gogo were added to the gold chloride solution before
oxalic acid, or before precipitation had taken place, purple solu-
tions were obtained which appeared to be colloidal gold. While
such an investigation rightly belongs in the field of physical
chemistry, it was decided to make a few tests on the formation
of colloidal gold solutions by means of gogo, with the hope
that they might prove of value as a basis for a more thorough
research.
Zsigmondy ? states in regard to forming colloidal gold, that—
the chief essential is distilled water of sufficient purity, and the absence
of electrolytes is not so essential as the absence of colloids. Traces of
the former will do no harm, seeing that a certain quantity of them is
introduced into the water by the reagents themselves. On the other hand,
traces of colloids, almost always present in all commercial distilled water,
completely prevent formation of bright red gold hydrosols.
Therefore, it was interesting to discover that colloidal gold
solutions could be made in the presence, and by means, of colloids.
The gogo was extracted from the gogo bark, which is obtained
commercially in the Philippine markets, by allowing the bark to
soak thoroughly in distilled water for five or ten minutes and
? Colloids and the Ultra-microscopic. 1st ed., J. Wiley & Sons, N. Y.
(1909), 124.
ae Ave Bddingfcide: Gogo 137
squeezing out the solution. The solution is of a brown to reddish
color, which gradually turns upon standing to a deep reddish
brown. It was found that, if exposed to the air, large numbers
of bacilli belonging to the Bacillus proteus* group were devel-
oped in the solution, and probably acted as reducing agents,
producing different chemical compounds. It was also found that
a mold (Penicillium sp.) grew prolifically on the surface of
the solution. This fungus Bacon‘ states “decomposed the solu-
tion, causing the separation of sapogenin, carbon dioxide at the
same time being given off.” However, sterilized solutions of
gogo undergo certain changes if allowed to stand for a sufficient
length of time, giving results similar to those obtained by solu-
tions in which bacilli have been developed.
The first experiment was made with freshly made gogo juice.
One cubic centimeter of gold chloride solution, obtained by dis-
solving 1 gram of crystallized gold chloride in 100 cubic centi-
meters of distilled water, was placed in a test tube; 1 cubic
centimeter of concentrated oxalic acid and a slight excess of gogo
were added. The solution was thoroughly shaken and heated
over a Bunsen burner. A deep purple solution was formed which
remained practically unchanged upon standing. Freshly made
gogo without the oxalic acid merely caused the formation of a
brown precipitate. Purple solutions were also obtained by first
boiling the gogo or the gold chloride solution with calcium car-
bonate or sodium carbonate, using the same proportions of solu-
tion. Several different colors were produced during these tests
which were probably caused by various other organic compounds
in the gogo. One was a black suspension of fine particles, which
settled out completely at the end of ten days. Another was a
slate-colored suspension which settled after five days. The char-
acteristics of these precipitates were not determined. After the
gogo had been allowed to stand for several days either in a sterile
condition, or exposed to the air and the action of the bacilli
or fungi, beautiful red solutions were obtained by adding from
2 to 6 cubic centimeters of gogo to 1 cubic centimeter of gold
chloride solution and boiling. This solution remained prac-
tically unaltered upon standing, although diminution of the color
was noted in the top of the test tube after a few weeks. The
exact character of these reactions is too complex for so brief an
investigation.
* Determined by Liborio Gomez, Bureau of Science.
* Loe. cit.
1388 The Philippine Journal of Science 1918
Another set of experiments was carried on by using pure sap-
onin powder. A saturated solution of saponin in water was
made. One cubic centimeter of gold chloride was placed in a
test tube with saponin solution and boiled over a Bunsen burner.
By variations in the amount of gold and saponin present, and by
variations in the intensity of the heat applied, colors ranging
from dark blue to purplish red were obtained. All of these sus-
pensions settled out in from twenty-four to seventy-two hours.
It was noted that the colors always changed gradually, through
their various shades, to a dark blue, before settling.
Another test was made by placing 1 cubic centimeter of gold
chloride solution in a beaker, adding 5 cubic centimeters of water,
and boiling. To the boiling solution was added about 0.1 gram of
saponin powder, which, upon further boiling, became a beautiful
clear red. This also, upon standing, changed through the various
purples to dark blue, and finally settled after seventy-two hours.
It was found that if the gold chloride solution contained excess
of acid, none of these reactions occurred. In such case sodium
carbonate had to be added to neutralize the acid. By adding
a few drops of sodium carbonate to 1 cubic centimeter of gold
chloride and then adding saponin powder or gogo, various shades
of red and purple were obtained which remained unchanged
upon standing. The reds were particularly clear and deep. The
application of heat seemed to be essential in all cases.
Microscopic examination was made to determine whether or
not the solutions contained suspended metallic particles. By
concentrating the rays of a strong arc light upon a thin film of
solution placed upon a glass plate, the metallic particles could
easily be distinguished in all of these solutions. It was noted
that all of the purple and violet solutions had the same color by
reflected and transmitted light, but only a few of the red solutions
exhibited this characteristic; others, while showing beautiful
clear colors by transmitted light, gave a brownish, muddy color
by reflected light.
It appears from these experiments that the red hydrosols rep-
resent the finest particles of gold, and the deep blue the largest
particles since the red changed to blue before complete precip-
itation. Whether this is due to a growth of the particle by
continued precipitation or the joining together of particles was
not determined. Furthermore, the finest particles would permit
the passage of longer wave lengths of light than the larger par-
ticles ; this would mean that the largest particles would transmit
ea a eae
VIII, A, 2 Eddingfield: Gogo 139
colors in the violet part of the spectrum and the finest particles
in the red.
The most interesting feature is the formation of colloidal gold
solutions by means of a colloid (saponin) and in the presence
of an electrolyte (oxalic acid), the two factors claimed by Zsig-
mondy to prevent its formation.
SUMMARY
Colloidal gold can be formed by—
Gold chloride, fresh gogo, and oxalic acid, plus heat.
Gold chloride and gogo (after standing), plus heat.
Gold chloride, gogo, and calcium carbonate, plus heat.
Gold chloride, gogo, and sodium carbonate, plus heat.
Gold chloride, saponin solution, and sodium carbonate, plus heat.
Gold chloride, saponin powder, and sodium carbonate, plus heat.
Suspensions which have colors similar to those of colloidal gold
can be made by gold chloride and saponin alone plus heat, but
these settle quickly.
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CONTENTS (4,824 gee
EDDINGFIELD, F. T.. Ore Deposits of ‘de Philippine ‘jalan
REIBLING, W. C.. A Bonus System for the Purchase of Portland —
Cement (0)... 5885 at ce i aie Ses a Ree eM sa
EDDINGFIELD, F. T. Alteration and Enrichment in ‘Calcite.
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EDDINGFIELD, F. T: Gogo, Entada scandens Bentham, and
Effect on Gold and Gold Solutions... :
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THE PHILIPPINE
JOURNAL OF SCIENCE
A. CHEMICAL AND GEOLOGICAL SCIENCES
AND THE INDUSTRIES
Vou. VIII JUNE, 1913 No. 3
THE COMPOSITION OF VARIOUS MILKS AND THEIR ADAPT-
ABILITY FOR INFANT FEEDING
By FRANCISCO AGCAOILI
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
One plate
One of the most important factors responsible for the exces-
sive death rate among Filipino children is found in the quality
of milk frequently employed to nourish small children. The
supply of fresh cow’s milk is very limited throughout the Phil-
ippines generally, and recourse cannot therefore be had to this
common substitute for the natural milk of the mother. The
milk of goats can be obtained in some localities, but the supply
is far too small to alleviate the situation. This is especially un-
fortunate, as the goat has been found of great value in tropical
countries, the child obtaining its food directly from the animal
in many cases, thus avoiding all danger from outside contamina-
tion of the milk (Plate I).
Carabao milk is abundant, but not well suited for young chil-
dren. The fat content is very high, and the milk shows a marked
tendency to form large curds. It is seldom found on the market
in an unadulterated condition, and is rarely collected in a sanitary
manner. It may safely be said that all fresh milks available
at prices within reach of the poorer classes are highly danger-
ous owing to bacterial contamination, and should never be em-
ployed as food, especially for children.
The choice of a substitute for mother’s milk is thus confined
to various canned milks and prepared infant foods which are
available in a satisfactory condition and at a reasonable price.
During the past five years the Bureau of Science has had occasion
119480 141
142 The Philippine Journal of Science 1918
to analyze many hundred samples of these sterilized and con-
densed milks, and the average results thus obtained should be of
considerable utility in aiding both mothers and physicians prop-
erly to adapt the various brands for infant feeding. The pro-
blem of modifying or altering a milk to make it approximate the
composition of mother’s milk is not difficult. The basis of any
scientific modification must rest on the proportions of fat, carbo-
hydrate, and protein present in the original milk as compared
with normal mother’s milk. It, therefore, becomes necessary to
have data concerning the many brands of milk suitable for the
purpose, and this information is recorded in the following tables.
The composition of various fresh milks is shown in Table I.
TABLE J.—Gomposition of fresh milks obtained in Manila.
ij Number
Type of milk. ppecwe Water. Fat. Lactose. | Protein. Ash. ot
lyzed.
Human: Per cent.| Per cent. |Per cent. | Per cent.| Per cent.
Maximum 222-2 1.0360 91. 48 9.97 11.21 2.76 0:72). eee
Minimum _______----_- 1.0260 81. 50 - 88 2.50 13 -01 a 151
Mean i225. = 05.2 1. 0327 87. 58 3.77 7.03 1.48 #20)\|)) 22 cae
Carabao, pure:
Maxaimum=soss=sese=s=> 1.0418 82.39 15.95 bo 15 6.51 91, || 22
Minimum ---_---------- 1. 0307 73.40 5.99 3.22 5.01 -77 7
Meania4i2o cnet: ee 1. 0366 79. 68 9.60 4.60 5. 68 80. /4 255 eeeee
Carabao, high-grade mar-
ket:
Maximum-__---- ----__ 1.0400 89. 43 28. 40 9.95 10.00 1507 ||-2: See
Minimums 2-2 - 9030 61. 04 4,28 -85 1.30 .24 213
Mean: =! #2 Rare 1.0334 80.57 9.56 4. 66 4.74 Py file) Peper:
Carabao, low-grade mar-
ket:
Masaimiim = 2seeee= es 1.0400 97.80 8.90 6.90 5.50 28) | ee
Minimum) ose 1.0100 83.19 1°35 -10 84 -17 125
Means 205) o- aec ee! 1, 0200 89. 57 4.69 2.64 2.75 oA4, |s Sees
Goat
Maximitm 2582s ee 1. 0360 87.97 6.80 5. 87 4.70 ~ 80) |. zeae
Minimum! 226 1.0280 84. 90 8.24 3.31 2.29 -59 ll
Mean’: = 1.225 aie Dee 1.0304 86. 69 5.02 4.34 3.29 (60) |. eee
Cow:
IMeixam tmnt ee eee 1. 0350 90. 59 7.68 6.05 4.55 PY ees ee
Minimum)s 242s eees 1.0170 84. 88° 1.64 2.39 6. 05
Mean 22222226 5 ue eae 1. 0300 87.74 3.79 4.60 3.18
Cream Australian dairy Sear 56. 08 40.65 - 78 2.00
a These extreme variations are due in part to the physical condition of the mother. In
those cases where the calorific values are very low, the abnormal milk is generally due to
insufficient nourishment of the mother. The age of the chilld also affects the composition of
the milk. See Musgrave, This Journal, Sec. B (1907), 2, 380.
The composition of various brands of sterilized natural milk
is shown in Table II.
vuia,3 Agcaoili: Various Milks for Infant Feeding 143
TABLE II.—Composition of sterilized natural milks.
Brand. Analyses.) Water. Fat. Lactose. | Protein.| Ash.
- Per cent.| Per cent. | Per cent. | Per cent. | Per cent.
Mri rricti here tare ace near ee 20 87.29 3.68 5.11 3.24 0. 68
BSE is esl aed ae ae te 9 15 87.14 3.70 5. 22 8.25 -69
ING arb tai Sis Talat See egies 8 87.51 3.68 4.88 3.28 - 65
Fussel’s Green Butterfly ____________ 6 87.20 3.78 4,98 3.37 . 67
LIE ET se = ys ee at eS 4 87. 64 3.71 5.01 3.06 -58
LOPE T aan ERS eee TD ai ee 4 87.49 3.62 5.00 3.31 -58
ONCE SEE OB Ee ne eae 2 87.65 3.39 5. 09 8.24 -63
Divine ipen swe tees ot eee 2 88. 02 3.24 4.89 3.19 - 66
LUG) ee ee Se Se ae er 2 88. 03 3.53 4.75 3.07 - 62
Bib ifaneces ses ues ee 3| 389.29 3.13 4.39 2. 62 BT
Congleton ee. a. wid ae 2 88.19 3.28 4.87 3.04 - 62
BacchusiMarsh sss. 5 02! Tide se 2 87.69 3.81 4,74 8.15 -61
RONDO bse a ere =k LS 1 88. 82 2.97 4.72 2.94 55
SST DEE (Sy meee AGB pe as lr ere Se 2 88.58 3.17 4.80 Pate - 68
Whampiony see ete swe Te a 1 87. 82 3.21 5.26 3.02 -69
Pics ee. SEP eh oe 1 88. 14 3.87 4.36 3.04 .59
BBR te Gri Pleo eee Nt Ne 1 87.77 3.32 5.18 3.07 - 66
PEUTIC HORS soe se 1 88. 08 3.60 4.35 3.33 - 64
LD ES) Se Se el oe 1 87.25 3.43 5.04 3.59 .69
Golden Cow and Calf________________ 1 87. 65 3.56 5.06 3.15 -58
PBR Rryge cee te See op SE 1 86. 46 4,98 4.10 3.77 -69
SUT ty (Ore ope a es 2 87.79 EE ON eee ore ase So Mie Meo
Rictorial ser ees Sab ses 55 oe 1 88. 29 DSO eas ei NS Be
aVcecay Melle oo ee es -t 87.97 S361) 5 Sees eee eee ea ie | cee ee
GoldentHarg so) 5h So Ss 1 87. 60 SW (1).) alee arenes A Es Se ees
SEO D ee ae ee 1 88.15 SNIAN eee ee ee aoe erat omnes ct ek
Mupbiteswpane ss oe ek re 1 87. 60 AES OR a ea | ie
PEROINCHE TOO Go Soe Se ee ft 89.00 Pfs saunas Meo A Pia Sens yok) | em
OTST RHEE pal RUE SSI WBE rat pe SO ae a 1 86.17 SSO We ee eve eee Mee ect eee
MONE Sen yeac uns enungie se he oek 1 89.15 1.94 5.19 3. 04 - 68
(SE TUES ae SPA orale eee ana 1 87. 63 2.82 5.82 3.11 -62
Bocati-Trinlzi' Co. 22 2. 1 86. 40 4.05 4.77 4.08 -70
Rents heer ee tt Ba 1 88. 29 8.35 5.11 2.67 -58
The composition of various brands of unsweetened condensed
milk is shown in Table III.
TABLE III.—Composition of unsweetened condensed milks.
Brand. Analyses.| Water. Fat. Lactose. | Protein.
Per cent.| Per cent.| Per cent.| Per cent.| Per cent.
ae ea ee as ee 10 67. 89 9.70 13.26 7.44 1.71
eke ee a eased 6 67. 26 9.75 12. 86 8.37 1.76
TERE) TEGO [2 lee Sa ot ao SS Or 6 72.75 7.75 10. 45 7.45 1.60
JOS eee ee ey ee oe ES ce 6 72.08 8.55 10. 74 7.21 1.42
Peerless’. 28 eeeee re ee 6 71.99 8.60 10.50 7.36 1.55
(Rib by: Soe eee ae eee 7 73.55 8.34 9. 66 1.21 1.24
very Gay Sateen eek ese ti 6 74,21 8.30 9.54 6. 57 1.38
Fussel’s Silver Butterfly ____________ 6 66.78 9. 48 13.71 8.63 1.40
@aw' shed to. os cee 22) eo ee ae 3 63. 69 10.05 15.07 9.17 2.02
teharlesie 20 se. Bete la See eee 5 71.30 8.17 10. 44 8.381 1.78
iaant Vernon oo 99. 5. =n ee 3 70.25 9. 46 10. 26 8.60 1.43
144
The Philippine Journal of Science
1913
TABLE III.—Composition of unsweetened condensed milks—Continued.
Brand.
St. George--__------ at
Cascade
Silver Cow
Bacchus Marsh=--2¢== = 42-3 bs ee
Milking -=. Qos ee oie ee ae
Rizal Days Aes ee
Domesti¢ == 2222-0 ee eee eae
Harmensi- 22) 2 s~ See e
Carnation
Analyses.
ee Oe
Water. Fat. Lactose. | Protein. Ash.
Per cent.| Per cent. | Per cent.| Per cent.| Per cent.
78.91 6. 67 7.38 5.79 1.25
73.95 8.78 9. 57 6. 50 1.20
70. 72 8.80 11.20 7.98 1.30
69.74 10. 42 10.35 8.49 1.00
71.02 8. 80 10.33 8. 42 1.43
69. 92 9.78 11.68 7.10 1.52
71.50 7.20 10.29 9.51 1.50
71.82 11.44 8.54 6.69 1.51
68. 95 V7. Ue [lected | ate a 1.45
64. 35 TONGA NE eee Ses ae 1.90
73. 62 9:26; \2.= 22.5 | EE
70. 39 9559))|5. 2.82.0 le ee
69.13 8.18 | 2264S S| ee
65. 75 T0885 + 5c) ee
74.32 6.18 |2-22-2----|_--. ee
72.30
67.10
73.89
The composition of various brands of sweetened condensed milk
is shown in Table IV.
TABLE I1V.—Composition of sweetened condensed milks.
Brand. Analyses.
ra
for)
Milkmaid
Gold Seal
Fussel’s Red Butterfly----
Natura
Malkyriels se 522. Fie gi aa8
Silver Churn
H
ge
a
oa
sh
om
f
'
1
'
'
1
1
'
t
1
1
'
'
!
'
'
1
'
1
PORE Re RPE RPP OHPNYONYYHP POAT A
Protein.
Ash.
Sucrose.
Per cent.| Per cent.| Per cent.| Per cent.| Per cent.| Per cent.
Water. Fat. Lactose.
22.30 9.80 14. 87
19. 27 9.94 15. 74
22.01 11.24 12.53
21.80 9.60 15. 90
23.30 9.24 16.04
21.120 7.92 12.19
25. 40 9.85 10. 50
30. 60 8.50 11.91
24.93 9.00 7.86
21.24 9. 18 15. 50
22.17 RES) ee Sek el se
26.59 8.38 15.11
25. 69 9800) eee
26. 65 8.80 9.11
27.38 11300) 2
22.77 12.96 11.13
29.95 9.79 18.51
13.20 GO tL iene Tee = 2
20. 05 7.75 18.62
28. 04 5.04 10.16
23.32 9560) | Sesh eee
29.09 oT a ete eal
28.90 9480) )/38 ses et
22.40 9.11 13.78
21.95 10. 18 15. 94
19.31 10.13 17.20
19. 64 9.25 19.78
8.84
8. 98
9. 45
9.00
9.74
10.29
10.00
8.92
1,92
1.83
1.75
1.70
1.68
42,27
44,24
43. 02
—
vir, 4,3 Agcaoili: Various Milks for Infant Feeding 145
The composition of various brands of sweetened condensed
skimmed milk is shown in Table V.
TABLE V.—Composition of sweetened condensed skimmed milks.
Brand. Analyses.) Water. Fat. Lactose. | Protein. Ash. | Sucrose.
: Per cent. | Per cent. | Per cent. | Per cent. \\Per cent. | Per cent.
a 3 24.18] traces. 17. 40 9.78 2.01 46. 63
. 1 23.16 | traces. 17.17 10.17 2.14 47.36
| 2 21.32 0. 88 16. 86 9. 98 2.41 48.55
1 29.70 | traces. 10. 92 10. 63 2.00 46.75
1 21.70 0.38 17. 68 9.19 1.98 49.07
at Q6nGdn| wee es ee IE. Sees es eee
2 16.85 | traces.
A peer eee eee |e ee soos oe ea ee
2 24.45) traces
1 21.25 | traces.
it 15.02 | traces.
The composition of various brands of cream and dried milk
is shown in Table VI.
TABLE V1I.—Composition of creams and dried milks.
Brand. Analyses.| Water. Fat. | Lactose.| Protein.| Ash.
Per cent. | Per cent. | Per cent.| Per cent. | Per cent.
Tcl eer as See) ee 10 64. 74 23.07 3.52 2.90 0.77
Cae i ee ol a a 6 57. 52 37.61 2.36 2.09 -42
J ee ae 3 69. 49 22.50 4.71 2.76 -54
3 62.38 31. 23 3.54 2.38 -47
1 64. 65 32. 40 -55 2.05 -35
1 63. 04 30. 60 2. 88 2.80 - 68
1 70. 90 21.60 4.12 2.89 .49
1 81.07 11. 90 8.59 2.98 -46
DRIED MILK.
| PERU lores 35 ssa oo eee Seen 2 1.70 31.67 85.05 |° 27.65 3.93
| BOs 2355 353 ee ea ee ee 4 3.07 24. 44 52.05 15. 50 4.94
METHODS FOR MODIFYING MILK
The most convenient method possible for modifying cow’s milk
is to dilute it with the correct amount of pure water, but the
result is never a very close approximation to mother’s milk since
the proportions of the various constituents are not altered by the
addition of water. In many cases a more exact modification is
desirable, though seldom closer than to 0.1 per cent, and numerous
tables have been devised whereby this result may be obtained.
146 The Philippine Journal of Science 1918
The proportion of sugar is greater, and that of protein consider-
ably less, in mother’s milk than in cow’s milk. This may be seen
from Table VII.1
TABLE VII.—Comparative average composition of cow’s milk
and mother’s milk.
eee
Woman's |Gow’s milk,
average. | 2verage.
Per cent. | Per cent.
Mate 2 A aa Nee ee 4.00 4.00
Sugar) <.. 2252.5 Soe. Seen eee 7.00 4.50
WProteidss-2- 4-2-2 — eae eee eee 1.50 3.50
Salits 225. Ee a ae ee een . 20 15
Water 25-2206: 22 see Fee aes 87.30 87. 25
The addition of cream and milk sugar or lactose to diluted
cow’s milk is, therefore, necessary to effect a proper balance.
The amount of each of these constituents may be calculated
from analyses of the original milk and cream by a simple for-
mula. An actual case for which the data are contained in Table
VIII may serve to illustrate the method.
TABLE VIII.—Data for modifying cow’s milk.
| Fat. Sugar. Protein. |
Gram Gram Gram
Per cent.| perce. ;Per cent.| perec. | Per cent.| perce.
WMilked esiredmee <== nasa nares 4.00 0. 040 7.00 0.070 1.00] 0.0100
Originalonilke=: 2 Se See 3. 60 - 036 5.10 -051 3.30 . 033
| QOriginal\cream|--5.- ee See 28. 40 - 284 3.90 - 039 2.90 - 029
The proportion of cream that should be added to the original
milk may be found from two equations based upon their fat and
protein content. Let M@ = number of cubic centimeter milk and
C = number of cubic centimeter cream required. Then the milk
used will contain 0.036 M gram of fat and 0.033 M gram of pro-
tein, and the cream added to it will supply 0.284 C gram of fat
and 0.029 C gram of protein. Therefore, 100 cubic centimeters
of the modified milk containing 4 grams of fat and 1 gram of
1 Holt, L. E., The Diseases of Infancy and Childhood. D. Appleton and
Company, New York and London (1910), 185.
eS a a Se eS Oe OS
vur,a,3 Agcaoili: Various Milks for Infant Feeding 147
protein corresponding to mother’s milk must be made from the
volumes of milk and cream necessary to satisfy the equations:
0.086 M + 0.284 C =4
0.083 M + 0.029 C= 1.
Solving for M and C gives 20.1 cubic centimeters of milk and
11.7 cubic centimeters of cream as the requisite volumes to em-
ploy. The amounts of fat, sugar, and protein contributed by the
milk and cream are shown in Table IX. A chart for the com-
position of these is given by Cox.’ S:
TABLE [X.—Data for modifying cow’s milk, continued.
| Source. Fat. Sugar. | Protein.
Grams. | Grams. | Grams.
2Oeemrikieate cee ea ese ee See 0.72 1.02 0. 66
3.32 -46 34
4.04 1.48 1.00
This mixture contains the proper amounts of fat and protein
when diluted to 100 cubic centimeters, but the total lacks 5.519
grams of sugar that must be added in the form of milk sugar or
lactose. The amounts of the various constituents have been re-
corded to the second decimal place merely to simplify their deri-
vation, although the requirements in practice would naturally
demand less accuracy.
The total amount of the resulting modified milk that should
be allowed a child during twenty-four hours for its nutrition and
proper development may be approximated by considering the
calorific value of the food. This is computed from the fat, pro-
tein, and sugar content with individual calorific values of 9.3, 4.1,
and 4.1 calories per gram, respectively. The value of 1 cubic
centimeter of the modified milk as obtained above would thus
be 0.704 calory. Holt? gives the following data for determining
the volume of milk necessary for a child. Divide the weight
in grams of the child by 10, and the quotient by the food value
in calories of 1 cubic centimeter of the milk. The result gives
the number of grams of milk required to supply the necessary
calories for twenty-four hours. In the case of a child of one
* Musgrave, W. E., This Journal, Sec. B (1907), 2, 382.
* Loe. cit.
148 The Philippine Journal of Science 1913
month, weighing 4 kilograms, and fed ten times a day on the
4000 :
103 0.704— 568.18 cubic
centimeters, or 56.8 cubic centimeters for each meal. This may
be diluted with pure water according to the capacity of the child’s
stomach.
The tables of analyses included in this paper make it possible
to modify properly any of the numerous brands of milk avail-
able, and should assist in encouraging scientific feeding and the
reduction of infant mortality due to ignorance or neglect of a
few simple principles of pediatrics.
above modified milk, the rule gives
_ TLLUSTRATION
owing baby feeding directly from a goat. (By the courtesy of
La Gota de Leche.)
149
“LVOS V WOU DNIGSS4 AsvVa ‘1 ALW1d
ON ‘V ‘IITA “l0S “Nunof “IHg] [‘SUINL 410 NOIWISsodWOD :1l0vODy
_.
THE COMPOSITION OF CARABAO’S MILK
By EH. R. DOovEY
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.) %
With the possible exception of goat’s milk, carabao’s milk is
the principle native dairy product in the Philippine Islands. Its
use is almost wholly restricted to the native population. The
milk has long been known to be very rich as compared with
cow’s milk, resembling the milk of other kinds of buffalo in this
respect, but its composition has been little studied. Although
many analyses of buffalo’s milk have been published from time
to time, it is a regrettable fact that in many cases the species of
animals from which the milk was obtained is unrecorded. The
average results obtained by several workers who have examined
the milk of various species of buffalo are given in Table I.
TABLE I.—Analyses of buffalo’s milk.
Kinds of buffalo. | S4™- Analyst. actal | Fat. |Protein.| Sugar. | Ash.
Per cent. | Per cent.| Per cent.| Per cent.| Per cent.
nko Waly = 2.225. |..2 =... Fleischmann @___-_-_- 17.07 7.46 4.59 4,21 0.81
Egyptian (Ga- 16 | Peppel and Rich- 15.9 5.56 8.86 5.41 1.03
moose). mond.»
Prigiane 8222S 18 | Leathere_______-__- 16. 26 "6.76 3.78 4,80 by
100) 6 oe large | Meggitand Mann 4_ 18.27 8.11 4.33 5.00 . 82
number
Unknown ------- 1 | Strohmere -__--_-_- 18.33 9.02 3.99 4.50 ott
Carabao -__-----. Gill) Soliss Bae Se es Be 22. 09 10. 63 6.31 3.78 -88
4 Blyth, Wynter, Foods, their composition and analysis. C. Griffin and Company, London
(1910). ; j
b Trans. Journ. Chem. Soc. (1890), 51, 754.
© Analyst (1901), 26, 40.
4 Mem. Indian Dept. Agr. (1912), 2, 195.
© Chem. Centralbi. (1888), III, 19, 478.
tThis Journal, Sec. B (1907), 2, 371.
Table II shows the composition of carabao’s milk on the Ma-
nila market, where adulteration is known to be practiced ex-
tensively.
151
152 The Philippine Journal of Science 1913
TABLE II.—Carabao’s milk from Manila markets analyzed at the Bureau
of Science, 1910-1912.
Total Solids not!
Water. Fat. fat.
solids.
Per cent. | Per cent. | Per cent. | Per cent.
Maximum --_-_-------- 97. 80 27.21 16. 02 15.27
1910. 84 samples_---------------- psi ys seen 72.79 2.20 1.78 42,
Average ___--.-------- 87.27 12.73 6.31 6.42
Maximum --_____---_-. i 91. 65 26. 96 19. 40 16. 80
1911. 96 samples_._-....--_------ imam Sa Shs EO 73.04 8.35 1.80 4.07
Average _______.------ 83.16 16. 84 7.77 9. 07
Maximum -__-_---_--- 92. 68 19. 56 10.81 10.17
1912. 18 samples--------.-------- im Rela bey 80.44 7.32 3.51| 3.81
Average'...54.452.-4 86. 89 18.11 6.09 Te a |
The object in view in undertaking the present work was to
collect data to enable the local Board of Food and Drug Inspec-
tion to fix a standard for milk sold for public consumption. For
this purpose it was decided to make complete and accurate anal-
yses of a number of milks.
In obtaining the samples for these analyses, the carabao was
milked dry under our supervision and the complete milking was
thoroughly mixed and its volume measured. The milk was col-
lected directly in a clean graduated glass, and transferred to stop-
pered bottles.
Owing to the high percentage of total solids, if a sample was
allowed to stand overnight it would invariably be found in a
clotted state in the morning. The most effective method for
breaking up such a coagulum for analytical purposes was found
to be shaking vigorously with steel balls.
In making the analyses, the milk fat was estimated by the
Leffmann-Beam centrifugal method using Babcock bottles and
10 cubic centimeters of milk, the result being corrected by the
factor 1.76. This result was confirmed by the Werner-Schmidt
process, extracting five times and using the residue of fat for
determining the butyro-refractometer reading. The total solids
“were determined directly on 10 cubic centimeters of milk, and the
result confirmed by means of the Richmond formula from the
percentage of fat and the specific gravity.
Pr a Pen es ese
: a,
me
VILL, A, 3 Dovey: Composition of Carabao’s Milk 153
In determining the aldehyde figure, in every case after the
second end point had been obtained a further addition of for-
maldehyde was made and a third end point obtained, which thus
measured the acidity of the formalin in each estimation. The
total protein and albumin were estimated in the usual way.
Attempts to measure the albumin and casein separately by a
modification of the process used for the aldehyde figure did not
prove successful. The lactose was in every case estimated polar-
imetrically and checked by subtracting the sum of the fat, protein,
and ash from the total solids.
The complete analyses of 19 authentic samples of pure cara-
bao’s milk are given in Table ITI.
TABLE III.—Analyses of carabao’s milk.
| Sample No.— |
1 2 3 4 5
Age of carabao_____--_-----_- years._| 12 8 “f 12 t
BYP OlOf Cate ese oso 8 months__ 6 5 3 2.5 5
Metal volume e2--- 5 -5-- =) 2s. ec___| 520 900 300 350 750
Specific gravity at 179.5 C ___________ 1. 0362 1.0374 1.0418 1. 0307 1. 0332
WVetherecserers Ie per cent__ 78. 42 82.39 82.39 73. 40 80. 44
Total solids:
DSRS) he ee ee do.-23 21.58 17. 6h 17.61 26. 60 19. 56
Calculated __.... = 20. dove” 21. 64 17. 42 17. 30 29. 98 19. 70
105 |) 2-6 seen: 3 Se ie Brae Oe 10. 44 6.57 5. 62 15. 93 9.42
MOMGnsNObtab. 6s 2 oe! gdG--s 11.17 11.04 12. 02 10. 65 10.18
Proteins: “
@aleulated «2.22/22. do____ 5.16 5.16 5.73 6.27 4,98
Direct (N X 6.25) __________ doe--5 5.16 5.08 5. 83 6.29 5. 91
Rasa erean eeee - i el h ed do____ 4.73 4.77 5. 44 6. 05 4.74
LAT) iT yee eee doe 43 381 .39 24 27
TDD CTE OSes re eT do! 5.17 5.20 5.32 3.55 4.22
Matalin ose se ae dots . 840 . 770 . 865 -914 - 186
poelublewagh 2-02. eo dot . 150 . 053 .170 .140 . 080
LTE 0) eet) 1 SS a dons: . 690 - 723 . 695 . 774 - 706
Alkalinity of ash __-___________ do-=- = . 002 . 004 . 002 - 002 . 004
@hlorides' asi) _. =~ 2-2 22_ do. - 042 . 028 - 052 . 056 - 039
@aleitm.as'CaO --.----_----- do .278 . 250 . 296 . 299 -278
Phosphoric acid -__.___---______ do____ . 280 TSU | te Sas ea 297
Acidity (as lactic) _.___________ do___- . 260 . 260 229 216 - 248
midehydereure!:2o 02 - oo 30. 2 30.2 33.5 36.7 20:1
Serum:
Specific gravity at 20° ___________ 1.0845 1.0831 1. 0323 1. 0321 1.0290
Immersion refractometer at 20° _ 43.8 43.3 43.0 42.8 40.2
Fat butyro-refractometer at 25° _____ 49.2 50.0 49.7 51.1 50.0
a After the formula of Richmond.
154 The Philippine Journal of Science 1918
TABLE III.—Analyses of carabao’s milk—Continued.
Sample No.—
6 7 8 9 10
Age of carabao____-_-________ years__ 12 9 iif 8 2
Age icficalfi eau) ia Sem months-_- 2 5 8 B} 6
Total volume __________ seeeeeened ec_-| 700 680 480 480 820
Specific gravity at 179.5 C____________ 1. 0365 1. 0399 1. 0885 1. 0386 1. 0347 ©
Water :220s Bie eee ee per cent__ 80. 20 80. 50 73.24 79.99 72.15
Total solids: } :
Direct wee Nee. Ler ee eudos ee 19.80 19.50 26.76 20.01 27. 85
Calculateda________________ do____ 19. 97 19. 52 24, 84 20.73 27.55
Fat 22. shes ee ee does 8.96 7.94 12.48 9.15 15. 62
Solids}mottateeoe ss oe do____ 10. 87 11.59 14, 22 10. 87 12.29
Proteins:
Calculated=es eee do____ 6.00 6.01 7.26 5.48 6. 85
Direct (N X 6.25) __________ do___- 5. 88 6.51 979 5.49 7.87
Casein 222.222. Sn eee do____ 5.41 5.69 8.54 5.02 6.94
Al buminse 2-22 ee eee doses 49 - 82 1.25 AT - 93
LACtOS G22 8 a ak ee ee dos 4,40 4.20 3.50 4.50 3.50
Wotaliash\.- =~ --20- EF eee do____ - 798 - 840 - 948 - 875 - 922
Soluble'ash a. =e =e es do____ - 043 024 018 021 . 122
Insoluble ash __________-_______ dol . 755 - 818 930 854 - 800
Alkalinity of ash ______________ do____ . 002 - 002 . 002 - 002 - 002
Chlorides as C] -_----_______-___ do__-- - 000 . 016 -017 - 010 - 028
Calcium as CaO _______________ do___- . 267 - 3804 . 342 . 299 314
Phosphoric acid -_--------_-__- dom 3 - 823 BOL . 372 - 338 847
Acidity (as lactic) _____________ do--_- 272 . 267 315 . 267 . 189
Aldehyde figure —.--=-=--=-2--- 20) 22 35.1 35.1 42.4 31.8 40.1
Serum:
Specific gravity at 20° ___________ 1. 0350 1. 0325 1. 0322 1.0337 1. 0853
Immersion refractometer at 20°__ 44.3 44.0 43.0 47.0 47.8
Fat butyro-refractometer at 25° _____ 48.5 49.8 49.7 48.7 49.2
Sample No.—
11 12 13 14 15
Ag ciohicarabao- = eee years__ 15 10 if 10 11
Ace of cali eee. ees months__ 9 11 2 6 4
Total-volumey= so-so eee ec__| 1,060 350 750 600 600
Specific gravity at 179.5 C 1.0374 1. 0348 1. 0390 - 1.0360 1. 0344
Water 2 Seetaie is See 80. 24 72.55 80. 45 76. 79 75. 98
Total solids:
Directisc 22-22 = asec aan 19. 76 27.45 19.55 - 23.41 24, 02
Calculated a___ 20. 04 27. 62 19.79 23. 82 24. 50
at ese a 1 Re 8.82 15.75 8.20 bea Ary 12. 87
Solidssmotrhate = aaae ese 10. 94 11.72 11. 28 11.14 10. 84
Proteins:
Calculated 2222-32-28 doz 5.07 5.64 5.38 4.85 5. 20
Direck(Ni><6:25) 22 do=— 5. 62 5.43 5. 62 SEPA 5. 66
Caseinersea: ee eee ee dos==s 5. 23 4.81 5.08 4.80 5.19
Album init-220ee- eee ae Goss - 889 - 63 54 -47 47
(hactose@res. eee ee ee dole 4.78 3.58 4.34 4.55 4.40
Dotaltash(zs. 42s seo a se eee es dos2=- . 843 - 903 - 823 . 834 . 755
Solubletash = sea ees see dos - 106 - 100 - 081 . 120 . 056
a After the formula of Richmond.
VIII, A, 3 Dovey: Composition of Carabao’s Milk 155
TABLE IIJ.—Analyses of carabao’s milk—Continued.
Sample No.—
11 12 13 14 15
Insoluble ash ____-_-__---- per cent __ 0.737 0. 803 0. 742 0. 720 0.699
Alkalinity of ash ___.-.._-_-_-- do___- - 005 . 001 . 002 . 000 . 000
Chlorides as C] -__-___________- doz. .018 . 048 - 021 . 042 . 045
@alctum\as!CaQen ee So do____ 311 - 308 -310 - 278 . 252
Phosphoric acid -__-_-----____- dows: .278 . 308 . 283 312 - 827
"Acidity (as lactic) ____-_-______ dozs .151 213 -170 - 165 234
Aldehyde figure ______._____-__-____- 29.7 33.0 31.5 28.4 30.4
Serum:
Specific gravity at 20° ___________ 1. 0353 1. 0380 1.0382 1.0370 1. 0368
Immersion refractometer at 20°__ 46.0 48.8 48.0 48.1 48.2
Fat butyro-refractometer at 25°_____ 48.9 49.7 48.5 50. 4 50.6
Sample No.—
16 17 18 19 Average.
“Age of carabao____.__-___-__ years__- 10 6 5 eS ee see ees
Ase ot calf 2-522) months-__ 5 6 1 BAe wala ree See
tal volume: #2522 5-1 88 ec___| 1,400 550 1,180 T30MI IE 1) | Sastre Lee et
Specific gravity at 179.5 C____________ 1.0377 1. 0370 1.0360 1. 0316 1. 0864
WED Soe eee per cent___ 80.77 80. 25 80. 41 80. 22 78. 46
Total solids:
Dia 7 toe Se aaa aera Fo does. 19. 23 19.75 19.59 19. 78 21.55
aleulateda: 882-8 dow 19. 66 19. 93 20.17 19. 87 21.59
NR eee ook es dora 8.49 8.80 9.01 9.81 10. 35
Solids, not fat. 2-9-2 doz 10.78 10. 98 10.34 9. 92 11.20
Proteins:
G@ateniated =o es ido-ss4 5.12 5.49 4,49 4.57 5. 50
Direct (N X 6.25) -________- dos. = 5.65 5.65 5.18 4.86 5. 88
Waseinbes. = 622 te EL doe! 5.19 5.16 4.66 4,44 5. 35
22 TUN | a does 46 49 .52 -42 -58
Lite iG eS ee nee do=-> 4,15 4.00 4.27 4.45 4,32
GLA AS Remsen te as dow - 896 . 818 . 890 -710 . 844
Polubleash. Vel ee doves . 061 110 067 110 086
Tnsolubleiash 2-222 2602 ce dow== . 885 708 823 610 158
Alkalinity of ash ______________ dow - 006 .001 . 000 . 004 . 002
Chlorides as Cl ________________ dokescc -021 - 024 .021 . 018 - 029
Calcium as CaO____________-__- does . 350 - 261 . 260 . 255 ~274
Phosphoric acid _______________ dou . 331 343 . 334 . 227 .310
Acidity (as lactic) _____________ do___- . 155 . 244 -216 . 146 . 222
Aldehyde hennre ns) 2. 68 5 et 29.9 32.0 26.1 26.7 32.2
Serum:
Specific gravity at 20° ___________ 1. 0342 1.0380 1.0374 1. 0304 1.0345
Immersion refractometer at 20°__ 46.0 47.5 46.8 42.6 45.3
Fat butyro-refractometer at 25°____- 50.4 50.2 50.2 50.3 49.7 |
« After the formula of Richmond.
It will be seen by a consideration of the above figures that
whereas in cow’s milk the fat is approximately 30 per cent of the
total solids, in the case of carabao’s milk, it reaches nearly 50
156 The Philippine Journal of Science 1918
per cent. The ratio of lactose, protein, and ash differs greatly
from cow’s milk, being about 5:7:1. This agrees approxi-
mately with the figures 5 : 6:1 obtained by Meggit and Mann *
for the milk of Indian buffaloes. A very different ratio was
obtained by Peppel and Richmond ? for the milk of the Egyptian
buffalo, their figures being 6:5:1. The percentage of lactose
in carabao’s milk is approximately the same as in cow’s milk.
The protein is much higher, higher in fact than in the milk of
any buffalo.
Again, whereas the ratio of casein to albumin in cow’s milk
is as 1 : 7.5 and in the case of the Egyptian buffalo, 1 : 5.5, in the
case of the carabao, it averages 1:10. However, the amount
present fluctuates considerably as was found by the varying de-
gree of ease with which an albumin-free serum was obtainable
for the serum determinations.
The calculation of total solids by the Richmond formula,
Cs. = 4 als & + 0.14, was found to give accurate results as is
shown above, and is available for use if any large number of
control analyses have to be made at any time. The determination
of the total protein by means of the aldehyde figure using the
common factor 0.171 was not so successful, and it would seem that
better results might be obtained using the factor 0.181.
The total mineral matter shows about the same ratio to the
solids not fat in carabao’s as in cow’s milk, but the ratio of phos-
phoric acid and calcium to ash is greater in the former than in
the latter. As usual, the principal ash constituents are fairly
constant, and a determination of the phosphoric acid * might be
of assistance in examination of samples suspected of being
watered, as confirmation of adulteration.
In order to confirm the above results, an estimation of fat and
total solids was made on samples of genuine milk from 105
animals with the following result:
ie . . - - aaa
Constituent. ee an ee
content. | content. .
Per cent. | Per cent. | Per cent.
Mille fat:=. 0 Se. kee eee 2 oe eee 17. 42 5. 66 10. 44
|) SPotalisolids=o 2-52 2.2225) =e sooo pee 28.70 15. 84 21. 42
Solids not fat by difference__-_____-_ 15.16 8. 68 11. 28
Water 242-35. 2s ee eee 84.16 71.30 78. =|
Mem. Indian Dept. Agr. (1912), 2, 195.
* Trans. Journ. Chem. Soc. (1890), 51, 754..
* A new method of milk testing. Analyst (1908), 33, 278.
ee ae ee al il as ee ag fms
4
VIII, A, 3 Dovey: Composition of Carabao’s Milk 157
These figures show that carabao’s milk varies greatly in com-
position. However, in view of the above results, which are in
close agreement with the more complete analyses given in Table
III, it is recommended that a minimum of 8.5 per cent of solids
not fat and 8.0 per cent of milk fat be adopted as the standard
under the Food and Drugs Act.
CHEESE FROM CARABAO’S MILK
The milk of the carabao is not used for making butter in spite
of its high fat content, owing to lack of knowledge regarding the
use of butter and the difficulty of keeping it without ice in a warm
climate. However, a kind of cheese is made by warming the
milk, then coagulating the fat and protein by adding vinegar and
salt. The whole is poured into bamboo tubes fitted with pistons
by means of which the curd is compressed in the bottom of the
tube and the whey is forced out through small apertures in the
side or through the porous partition of the bamboo. The result
is a small curd cake, about 4 centimeters in diameter, 1 centi-
meter thick, and weighing about 16 grams. It is white in color
and tough in consistency, as might be expected from its mode
of manufacture. It is incorrectly called cheese since no ripening
process is allowed to take place.
The analyses of 3 samples of this cheese are given in Table IV.
TABLE 1V.—Percentage composition of cheese made from carabao’s milk.
Sample No.—
Constituent.
1 2 3
MOIS TUTE res eet eee eee Se ete 51.55 50. 00 56. 00
WRU USS 2 eS Se eee ee ae 27.14 28.91 29.37
Protein (NX 6:25) .2-2-----222- 22-2 15. 52 15.17 15.71
Acetic acidi ss. 2262 hes 2) eee sek 112 O29)! ree oe
Waebic heid. 922s ase re SoS eae 195 AS meee ates
Insolubleiash=-+—+--2+--. --- 2. 1.48 1.64 1.76
Solubletash) 2 $22 22222582 soe ss 8.45 4,27 4.01
Sodium chloride -._---_.-...---__-_-- 43 OFAATs | Ge meee a t
Fat butyro-refractometer reading
ENP AO oS oy eee es Se? eee 50. 6 50.7 49.7
119480——2°
r
Le Sm co be se miei
Pdi ge hs Maal ¥9 ee
Crier saa
nq
:
4
faa ee ot oie
oe 2 Baa eR we
SUGAR-CANE EXPERIMENTS
By CLODOALDO TEMPONGKO *
(From the College of Agriculture, Los Banos, P. I.)
Sugar cane was being cultivated by the natives at the time Ma-
gallanes discovered the Philippine Islands in 1521, and has ever
since supplied an important article of commerce. The yearly
amount exported since 1817 is shown in Table I. ‘
TABLE 1.—Sugar exported from the Philippine Islands.
a Per cent Per cent
Year. Quantity. Value. o6 tolal Year. Quantity. Value. of aek
exports. exports.
Kilos. Dollars. Kilos. Dollars.
ifil( eo a OPO 72, DOONE Seek Ss be eS 18830252 2533 196, 834, 584 | 10, 546, 185 45.88
i159, ae 26. 1>O8 00S) |eseee ees ah cane 198422 sash _ 122, 128,325 | 6,013, 982 30.33
iG) ee 47,704,105 | 2,225,022 88207 |} 1885.2. = 2-5. = 204,222,480 | 8,646,735.) 42.18
PSbboses 35,570,206 | 1,725, 630 26. 83 || 1886 _____-___ 184, 939,549 | 7,016,348 84. 90
9856 =>: = =. 48,157,225 | 3,705, 434 38.61 || 1887 -__-_--_- 171, 752,248 | 6,153,511 31.66
G57 | Rae ean 36, 644,895 | 4,576, 531 36.19 || 1888 ___-._-_- 160, 987,894 | 6,274,385 32.32
See 27,288,687 | 2,249, 195 22.78 || 1889.-...-_-- 228, 468, 873 | 9,098, 543 35. 45
HSpQeoss | 49,799,815 | 4,186,296 40.93 || 1890 ---.-.-__ 144, 841,483 | 7, 266,798 33. 72
E177 et Rede oe 46, 043,438 | 3, 166, 678 SIAL!) TOT See 138, 217, 635 | 5,698,949 | ~ 27.29
PRG2 ouck .= 54 61, 934, 853 | 3,561,289 B00) AS9Dk ae oe ae 252, 798,196 | 17,766,326 40. 54
it) 52,061,920; 3,341,056 31. 44 || 1893 _-__._-_. 261, 522,201 | 10,370,574 46.63
TO (sy. Geese eee * 45,036,305 | 3,513, 603 31.20 || 1894 _________ 210, 646,386 | 5,474, 422 33.11
i fee 46, 831,637 | 6,383, 629 29; OF || 189b:. 222 =~ - 22 341, 469,556 | 6, 068, 485 32. 22
AR GG ieee 41, 288,259 | 6,039, 496 25288),||) 1899 :25-5- 2 85, 827, 565 | 38, 458,370 28.29
RG 56, 080,860 | 6,526,351 23:42 || 1900... --=-- 65,190,951 | 2,397,144 10. 43
EG eel 85, 210, 319 | 13, 970, 248 BBE245 190K == S222 56, 872, 592 | 2,549, 147 10. 40
Isa 101,371,178 | 6,104,729 S510 |\902 2st ee 98,596,473 | 3,342,478 11.66
128, 112,022 | 9,028,775 48.88 || 1908 __..---.- 86,512,179 | 3,324,554 |________-.
130, 547,168 | 6,773,177 AGNOI | 19042 2k 88, 281,892 | 3,092,734 |_________-
122,994,279 | 8,309, 585 BS itn Io oe eee 110, 030,285 | 5,078, 233 |_.--------
122, 023,228 | 17,496,824 47.34 || 1906 -._-_-_-- 131, 281,077 | 4,554,092 |_-_---___-
131, 859,429 | 6,846,510 Ate 21 el907 eee ee 129, 723,495 | 4,195, 671 |----------
181, 190,277 | 10,265, 788 48.65 |) 1908 -...--_. 146, 778, 080 | 5,703,641
208, 805, 946 | 11, 085, 833 60).47°|) 1909. ------_-- 131, 153,472 | 5, 608, 287
150, 422,377 | 7,972,780 43,22
8 El Archipielago Filipino (1900), 1, 278.
The above table shows a recent decline in the volume of export
that is the result of many causes, both internal and external.
One of these may undoubtedly be found in the decreasing fer-
* Graduating thesis No. 1.
159
160 The Philippine Journal of Science 1918
tility of the cane fields naturally resulting from long-continued
planting without replacing the food elements by fertilizer. This
phase of the agricultural problem is considered briefly in the fol-
lowing résumé of experiments carried out during 1910 at the
College of Agriculture, near Los Bafios, Laguna Province, Luzon.
The object of the investigation was to settle the various ques-
tions enumerated below:
1. The effect of prolonged soaking on the cane seed.
2. The effect of late planting.
3. The results obtained by various methods of planting.
4. The influence of various fertilizers on the cane as manifested
by: (a) suckering; (6) growth of cane in length; (c) growth
of cane in circumference; (d) production of leaves; (e€) color of
foliage, and (f) yield of stripped cane per hectare.
The purple variety of cane was employed throughout, as it
appears to be superior to the white.
The experimental plots were located on an old sugar plan-
tation formerly belonging to Mr. Agripino Salva Cruz. The soil
was a sandy clay loam with surface layer about 25 centimeters
deep and clay subsoil. The field was never artificially fertilized,
but had been in continuous use for fifteen years as a sugar ha-
cienda. The land was allowed to lie fallow during the year pre- -
ceding the experiments, and planted with purple cane in the
early part of June, 1910. The tops used for planting were ob-
tained from Negros a month previous, and immediately placed
in running water. Thus the period of soaking was excessive,
and the date of planting very late.
The field was then divided into 6 plots designated as V—A,
V-B, VI-A, VI-B, VII-A, VII-B. Plots V—A, VI-A, and VII-A
were unfertilized and served as checks on the 3 corresponding
fertilized plots designated as B. The rows of all corresponding
plots were continuous from one to the other.
The remaining seed tops were planted in 4 plots, I, II, III, and
IV. All tops were about 30 centimeters long, and bore approxi-
mately 6 buds each. The fertilizers used consisted of dried blood
and compound fertilizer of ammonium sulphate, potassium sul-
phate, and superphosphate of lime in the proportions of 2 :3 : 5.?
Data regarding the amounts of these fertilizers may be found in
the subsequent tables.
Ten plants in each plot were selected from continuous stools in
rows of average condition, and carefully labeled. Weekly obser-
? This fertilizer was furnished gratis by Messrs. Behn, Meyer & Co., Ltd.,
of Manila.
VIII, A, 3 Tempongko: Sugar-cane Experiments 161
vations of these plants were made, and the growth of stalk from
the base to the longest leaf, as well as the stalk circumference,
were carefully noted. The cane from each plot was weighed on
April 21, 1911, and the yield calculated.
The data obtained in the plots where different methods of plant-
ing were followed are shown in Table II.
TABLE II.—Results obtained with various distances between rows of cane.
we Pinion:
| Plot dimen- istance| between Tops per
Plot No. A between | ends of
sions. HGH, weed hectare.
cane.
Meters. Meters. | Meters.
Wieates penne eee a ey Ba See 40 by 15.75 1.75 0.75 7,125
UT eee od iss ee Sap de ete ee 40 by 14 1.75 1.00 4,399
TE ViCAS VLA) sho ae eee ee ees a 2,378 1.20 -50| 10,416
LW (fe ae ES eae ee 40 by 13.2 1.20 -00 | 27,776
VIS oe 2 ee eed ee 83.3 by 30 1.20 -383 | 18,778
& Square meters.
The average growth and condition of the cane in these plots
are shown in Table III.
TABLE IlJl.—Average growth and condition of the cane in the experimental
plots.
Pro-
Growth :
inlength| Length panetion, Per cent TS rarastin
per week |from base} Circum- of har- Yield of
Plot N from jtolongest| ference ier meee vestable . ans) Origi- | stripped
ONG Aug. 30, | leafon | on Apr. | q, Te tO suckers Ba hec-| Bals.> | cane per
1910, to | Apr. 20, | 20, 1911. |“Ioho" to’ | to orig- | PA oes hectare.
Apr. 20,| 1911. oe 90, | inals. me
1911. 1911.
Meter. | Meters. | Meter. Kilos.
1 Ye SER ae 0. 0406 2.3775 0. 0815 0. 939 13 31, 198 42, 750 143.8
1 oe - 0391 2.2121 . 0820 . 996 81 21,379 26, 394 160.8
212.1
III (V-A, VI-A) - 0435 2. 4595 - 0848 - 910 70 43, 565 62, 496 240.8
287.4
) NY fee Sa aera - 0444 2.5417 - 0800 . 894 0 0] 166, 656 216.8
MPI AS ote ool . 0416 2.3094 . 0810 . 875 55 45, 467 82, 668 280. 4
® The number of suckers was calculated he subtracting 6—the number of original buds—
from the total number of harvestable canes in a stool.
b The number of originals was calculated by multiplying 6é—the number of original buds—
by the number of seed tops used.
In general, the rate of growth in length was greatest in the
most thickly planted plots, while the reverse was true in the gain
measured by circumference. The per cent of harvestable suck-
ers was proportionally greater in the thinly planted areas, while
the total yields of cane varied irregularly as may be seen from
the table.
162 The Philippine Journal of Science 1918
EXPERIMENTS WITH FERTILIZER
Data regarding the corresponding plots on which fertilizer was
used are given in Tables IV, V, and VI.
TABLE I1V.—Data showing the planting followed
Plot No. Plot aimess ree
2 rows.
Meters. Meters.
VA ee 8 Se en ee 33.3 by 30 1.20
Wa B ie 8 Se ee ee eee 33.3 by 30 1.20
WAHA fo tee ot ee eee eee 28.3 by 30 1.20
VICB 2 ee ee oe 33.3 by 30 1.20
WITSA 2 2 oe ee ee Ee | Ee 1.20
Wii=B ie 522s te ee eee 33.3 by 30 1.20
TABLE V.—Data showing the fertilizer used
in fertilized plots.
Dittance
etween
ends of | Tectare,
cane.
Meter.
0.50 | 10,416
-50 | 10,416
-50 | 10,416
-50 | 10,416
-33 | 13, 778
-33 | 18,778
on these plots.
Potas- | Calcium |.
Tum: eine De Paper Dried z
nium sul-| phate phos- ost per
Plot No. phate per|percent)| phate blood per hectare.
hectare. | per hec- | per hec-
tare. tare.
hectare.
Kilos. Kilos. Kilos. Kilos. Pesos.
WA oe cea ee US ee eee ee ae SAEs eee le. Se cee ae |
WB tee nae Rl ee ON ee ee ye 80 120 200 ;)| Pee ee 44
WIFA: 22+ ce ess ee ee nn eee | eS ee ee | ee
VISB RE 2.82 0 pon oe ee ae ee 80 120 200 150 62
VA ee ee ar a a ee | ers
WAS Bi ee coe ee ae ee 40 60 Te ee Se 22
TABLE VI.—Average condition of cane in these plots.
Produc-
Growth :
lin length| Length Homer Per cent Fa -vest |
per week|from base} Circum- ee aweele of har- abl By Original Yield of
Plot N from _ |tolongest) ference Pp fro vestable ee peste, 8) stripped
OE Neh Aug. 30,| leaf on | on Apr. Se as suckers San aS as €C- | cane per
1910, to | Apr. 20, | 20, 1911. | {oto ¢2°| to orie- | PSE ES ve. | hectare.
AEE ta 1911. Apr. 20, inals.
: AQT
Meter. | Meters. | Meter. Kilos.
ia) Nees eS ey 0. 0495 2.6810 0. 0878 0. 900 88 54, 996 62, 496 240.8
Ve Base oes See . 0566 2.9621 - 0828 . 849 111 69, 370 62, 496 332.6
WA SAS jee 93 - 0385 2. 2284 - 0848 . 932 71 44, 452 62, 496 287.4
WiBac tetas . 0576 2. 8008 . 0960 - 948 93 58, 121 62, 496 (2)
WilisAr eee . 0416 2.3054 . 0810 - 875 55 45, 467 82, 668 280.4
SAD 3s ee . 0592 2. 9262 - 0816 - 939 106 87, 628 82, 668 350.5
The data for unfertilized plots V-A, VI—-A,
and VII-A are in-
cluded in Table VI for comparison with the corresponding fer-
tilized plots V-B, VI-B, and VII-B.
VIII, A, 3 Tempongko: Sugar-cane Experiments 163
In every case the fertilized plots showed a higher rate of
growth in length and a marked tendency toward heavier stalks
with more abundant leaf production. The per cent of harvest-
able suckers was also increased by fertilization. All of these
factors combined to increase the yield of stripped cane. Plot
VI-B that received the most fertilizer thus showed a yield of
cane 79 per cent greater than the corresponding check plot
VI-A. The gain in all cases was proportionate to the amount
of fertilizer used.
The rate of growth shown by sugar cane in the Philippines is
rapid during ten months following planting, reaching a maxi-
mum during the third and fourth months. The weekly rates of
growth of the various plots are shown in Table VII.
TABLE VII.—Average weekly growth in length of cane in experimental plots.
Pade s See]
zl Plot | Plot | Plot | Plot | Plot | Plot | Plot | Plot | Plot
From: To— |Plotl.| “Wy | a. | Iv. | vV-A.| V-B. | VI-A.|VI-B. |\VII-A.| VIL-B.
Meter.| Meter.| Meter.| Meter.| Meter.| Meter.| Meter.| Meter.| Meter.| Meter.
Aug. 30} Sept. 6 0.1123 |0.1075 |0.1151 (0.0883 |0.0764 |0. 1108 |0. 1024 |0.1225 |0. 0690 /0. 1004
Sept. 6) Sept. 18 | .1551 | .1251 | .1851 | .0950 | .1683 | .1283 | .1051 | .1938 | .1263 | .1780
Sept. 13 | Sept. 20 | .1061 | .1231 | .1153 | .1865 | .1848 | .1807 | .1870 , .1468 | .1106 | .0991
Sept. 20 | Sept. 27 | .0783 | .0693 | .0862 | .0690 | .1266 | .0859 | .0901 | .1386 | .1190 | .1287
Sept. 27/ Oct. 4] .0478 | .0434 | .0926 | .0820 | .0950 | .0831 | .1064 | .1185 | .0874 | .0892
Oct. 4] Oct. 11] .1296 | .0735 | .1124 | .0889 | .1017 | .1440 | .1400 | .1349 | .1151 | . 1089
Oct. 11] Oct. 18] .0676 | .0651 | .0658 | .0780 | .1111 | .1411 | .0682 | .1260 | .1403 | . 1029
Oct. 18] Oct. 25 | .0311 | .0882 | .0479 | .0566 | .0561 | .0940 | .0441 | .0788 | .0509 | .0914
Oct. 25] Nov. 1) .0835 | .0410 | .0489 | .0587 | .0595 | .0960 | .0422 | .0786 | .0680 | .0929
Nov. 1! Nov. 8 | .0413 | .0453 | .0564 | .0668 | .1050 | .1050 | .0544 | .0824 | .0673 | . 1093
Nov. 8] Nov. 15] .0451 | .0488 | .0428 | .0478 | .0743 | .0852 | .0441 | .0693 | .0441 | .0762
Nov. 15} Nov. 22 | .0529 | .0577 | .0407 | .0394 | .0732 | .0783 | .0414 | .0578 | .0383 | .0721
Nov. 22] Nov. 29 .0544 | .0562 | .0395 | .0417 | .0703 | .0633 | .0378 | .0497 | .0382 | .0627
Noy. 29} Dec. 6 | .0682 | .0587 | .0409 | .0500 | .0704 | .0690 | .0352 | .0520 | .0313 | .0618
Dee. 6! Dec. 18 .0382 | .0364 | .0310 | .0440 | .0587 | .0577 | .0277 | .0427 | .0380 | .0565
Dec. 13 | Dec. 20 | .0267 | .0324 | .0297 | .0405 | .0557 | .0613 | .0248 | .0412 | .0315 | . 0608
Dec. 20] Dec. 27 | .0297 | .0280 | .0273 | .0484 | .0518 | .0608 | .0232 | .0381 | .0280 | .0569
Dec. 27| Jan. 3 | .0258 | .0325 | .0299 | .0418 | .0522 | .0539 | .0256 | .0871 | .0254 | .0581
Jan. 3] Jan. 10] .0244 | .0312 | .0287 | .0462 | .0506 | .0443 | .0223 | .0371 | .0285 | .0482
Jan. 10| Jan. 17 | .0201 | .0290 | .0352 | .0352 | .0094 | .0378 | .0098 | .0373 | .0161 | .0480
Jan. 17| Jan. 24] .0197 | .0254 | .0294 | .0348 | .0092 | .0302 | .0082 | .0358 | .0142 | .0372
Jan. 24) Jan. 31) .0171 | .0215 | .0276 | .0320 | .0063 | .0262 | .0086 | .0297 | .0108 | . 0359
Jan. 31] Feb. 7/| .0106 | .0179 | .0248 | .0469 | .0033
Feb. 7] Feb. 14} .0168 | .0213 ; .0285 | .0248 | .0141
Feb. 14| Feb. 21 .0191 | .0178 | .0209 | .0219 | .0138
Feb. 27| Feb. 28 | .0175 | .0165 | .0169 | .0188 | .0094
Feb. 28] Mar. 7 | .0163 | .0131 | .0155 | .0170 | .0093
Mar. 7| Mar. 14 | .0137 | .0086 | .0106 | .0222 | .0112
Weekly average to
Apr 20S eeanens - 0082 | .0038 | .0056 | .0068 | .0031
The fertilizer should evidently be applied before the period of
maximum growth to be most effective.
164 The Philippine Journal of Science 1918
SUMMARY
The cane grew well in spite of late planting and long soaking
of the seed. The per cent of harvestable suckers varied from
0, where the cane was thickest, to 81 in the plot where the plants
were farthest apart. These low figures are doubtless due to
late planting, as neighboring estates where cane is grown with
even less space between the tops often produce from 200 to 300
per cent of suckers.
The sugar content of original plants has been shown? to ex-
ceed that of the suckers, and a correct balance between originals
and suckers will give, therefore, a maximum sugar output per
hectare.
The use of fertilizer was very beneficial on the soils used in
these experiments, and increased the yield of stripped cane to a
marked extent. Many fields are in a similar exhausted state so
far aS sugar cane is concerned, and would doubtless give corre-
sponding returns for capital spent in suitable fertilizer.
The results obtained in the preceding experiments clearly show
the necessity of artificially replacing the food elements which
long-continued planting has removed from many sugar hacien-
das, and indicate the increased output that may be expected from
such treatment.
* Stubbs, William C., Sugar Cane. Issued by the State Bureau of Agri-
culture and Immigration. [Louisiana. No date] (1897 ?), 1, 105.
THE TWO PHTHALOXIMES: A STUDY OF THEIR ABSORPTION
SPECTRA AND CONSTITUTION
By D. S. Pratt and H. D. GIBBs*
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
Two plates and 6 text figures
Phthaloxime was first described by Lassar-Cohn,? who made
it by the action of phthalyl chloride on hydroxylamine. The
same compound was later made by Lach,? who employed phthalic
anhydride and hydroxylamine. Orndorff and Pratt * have shown
that the course of this reaction depends upon the temperature.
A colorless phthaloxime is formed at 60°, and a lemon yellow
isomer results when the same reaction takes place at 100°.
These two isomers are very closely related, as shown by their
physical characteristics and chemical properties. The principal
difference between them is their color. Two structures are
theoretically possible for phthaloxime, depending upon whether
the hydroxylamine residue is in the symmetrical (1), or unsym-
metrical (2), position in respect to the benzene ring.
yn iT ae
NOH wi »o
ogi lest
. No a NOH
The symmetrical formula (1) has been generally assigned to
colorless oximes of this type regardless of the color of their salts.
Both the white and the yellow phthaloxime give alkali salts of
a brilliant red and of almost identical color in both cases. It
has not been found possible, as yet, to prove beyond question
which of the above formulas should be applied to phthaloxime,
although a careful study of its formation and reactions points
* Associate professor of chemistry, University of the Philippines.
7 Ann. d. Chem. (Liebig) (1880), 205, 295.
* Ber. d. deutschen chem. Ges. (1898), 16, 1781.
“Am. Chem. Journ. (1912), 47, 89.
165
166 The Philippine Journal of Science 1918
strongly to the unsymmetrical structure. The fact that phthal-
oxime may be made from phthalyl chloride and hydroxylamine
does not distinguish between the two structures, as the reaction
is not a mere elimination of hydrogen chloride with the formation
of the oxime, but takes place in two steps, giving phthalhydrox-
amic acid as an intermediate product. Ott® has recently shown
that the ordinary phthalyl chloride may be symmetrical, a fact
indicated by its absorption spectrum according to Scheiber.*®
It is evident that an unsymmetrical oxime may result from a
symmetrical chloride in the following manner:
Jol
—co cl Eon
| 4NH,OH > | \NHOH
Nea WW,
Phthalyl chloride.
NHOH
Cl yr
—c€ OH /\—c=0
| co HOH T2EO = | | 4 ont ae!
Nd N\A awe
No
Phthalhydroxamic acid.
NHOH
= —C=NOH
| 0H es 30> £0
Ce oy
‘NO ‘NO
Phthaloxime.
The reactions are entirely analogous to these between phthalyl
chloride and ammonia.” Phthalhydroxamic acid cannot be iso-
lated from solution as it loses water to form the oxime, but its
presence may be shown by the characteristic color given with
ferric chloride, and its alkali salts may be obtained as colorless
crystals. The reaction between phthalic anhydride and hydroxy]-
amine follows a similar course. The anhydride combines
with the free hydroxylamine giving a clear solution of hydrox-
amic acid. Since both the anhydride and the oxime are very
slightly soluble in water, it is evident that the first phase of the
reaction may be completed before dehydration with the result-
* Ann. d. Chem. (Liebig) (1912), 392, 245.
© Ibid. (1912), 389, 121.
* Scheiber, Ber. d. deutschen chem. Ges. (1912), 45, 2252..
——————— lL rr eee le
eS a ee
Te ee ee ee
VIIL A, 3 Pratt and Gibbs: Two Phthaloximes 167
ing formation of oxime takes place. Further heating of the solu-
tion causes an abundant crystallization of phthaloxime.
When phenylhydrazine acts similarly with phthalic anhydride,
the product of the first phase may be isolated. Anilidophthal-
amic acid is formed in this case,’ and has a structure analogous to
phthalhydroxamic acid.
0
2
a eel |
__C_NH‘NHC.H;
Nr So
Anilidophthalamie acid.
Phthaloxime may also be made by the action of hydroxylamine
on phthalimide in alkaline solution. Here again the formation
of an intermediate product precludes any conclusions being
drawn regarding the position of the =NOH group, although
phthalimide possesses a symmetrical structure. The reaction is
represented by the following equation :
0
(Sco ( \—c#0H
UU oD NH NELOH +120 ss Be ale LANE
NG INS
Ammonia is liberated and phthalhydroxamic acid formed. This
may be converted into either the white or yellow phthaloxime
according to the temperature at which the solution is heated after
being acidified.
The existence of two isomeric phthaloximes may be explained
by means of the unsymmetrical formula in a manner similar to
that employed with the benzaldoximes, and indicated graphically
by the formulas Ila and IIb where the syn type shows the hy-
droxyl in closer proximity to the unsaturated carbonyl group.
C=O Cc=0
\ VS
CoH O CeH O
i 1
N—OH HO—N
IIa Syn. IIb Anti.
* Hotte, Journ. f. prakt. Chem. (1887), II, 35, 268.
168 The Philippine Journal of Science 1913
A study of the absorption spectra of these and related com-
pounds was undertaken for the purpose of obtaining an insight
into their molecular arrangement and behavior and evidence
regarding the production of color in their salts.
If the isomerism between the white and yellow phthaloximes
is correctly indicated by the above formulas, Ila and IIb, it is
evident that their absorption spectra must be very closely related.
Macbeth, Stewart, and Wright ° have studied the action of light
on unsaturated centers in a molecule, and state that no great
change takes place in the general absorptive power of a molecule
when such a center is shifted in space with respect to a saturated
radical. The carbonyl group in phthaloxime represents the point
of maximum unsaturation, while the hydroxyl can hardly be
looked upon as the center of much residual affinity. Any relative
change in space between carbonyl and hydroxyl should produce a
slight modification in the absorption spectrum, but the type would
remain the same. Hartley *° has shown that the stereoisomeric
benzaldoximes have the same absorption spectra which show a
broad band in the benzene region.
Hantzsch +t has examined several isomeric oximes and states
that the absorption spectra of a and y benzyl oximes, the two
para nitrobenzaldoximes, and of the chlortoluquinonoximes show
great similarity in each case between the two isomers. The syn
series absorbs somewhat more strongly than the anti, as might
be expected from the greater proximity and consequent mutual
influence of the two radicals. Wilson and Heilbron ” have re-
cently prepared two semicarbazones of mesityl oxide, and find
corresponding differences due to nitrogen stereoisomerism.
Since these characteristics are manifested in the case under
discussion, it thus appears that the yellow phthaloxime should be
designated as syn-phthaloxime and the white isomer as anti-
phthaloxime as represented by formulas Ila and IIb.
Prior workers have pointed out that absorption bands are not
to be attributed to any definite molecular structure, but rather
to the existence of dynamic compounds which are not necessarily
capable of isolation. The presence of an absorption band is due
to intramolecular change from one modification to another, and
is expressed by an actual change of linking, or is due to the po-
° Journ. Chem. Soc. London (1912), 101, 599.
*Tbid. (1900), 77, 509.
“ Ber. d. deutschen chem. Ges. (1910), 43, 1651.
* Journ. Chem. Soc. London (1913), 103, 377.
VII, A, 3 Pratt and Gibbs: Two Phthaloximes 169
tential possibility of such a change. The oscillation or free
period in connection with the reversible transformation of one
tautomeric form into another is synchronous with the oscillation
of the light waves absorbed. This transformation must be
understood to include changes that cannot be graphically repre-
sented by fixed structural formulas. These peculiar cases are
best indicated according to the partial valency theory developed
by Thiele.t? This assumes that all the affinity of two atoms con-
nected by a double bond is not used in holding the atoms together,
but that there is a slight excess present in each atom. Thiele
designates this excess affinity by dotted lines. Application of
this idea to phthaloxime gives a formula that may be expressed
thus:
The two sets of partial valencies may be assumed more com-
pletely to neutralize each other during one phase of the benzene
vibration when the atoms are in closer proximity to each other
than during the succeeding phase when they are more widely
separated. This varying adjustment of forces in connection
with the disturbing influence of the hydroxyl group may be
thought of as causing the ultra-violet absorption band of phthal-
oxime. The equilibrium is essentially the same in phthalic acid,
the esters of phthalic acid, and very similar in phthalimide. All
of these compounds may be expressed by analogous formulas.
Moreover, they all give absorption spectra showing similar ultra-
violet absorption bands. This must be considered as evidence
of corresponding structure. The influence of the benzene ring
is essential in these cases.
The application of the partial valency theory to explain the
activity of carbonyl groups removes the indefiniteness inherent
in the method employed by Stewart and Baly ** to represent this
condition. These authors suggest that nascent carbonyl groups
be indicated by printing the oxygen in heavy-faced type, thus
| ” and that this condition is essentially dynamic in nature and
cannot be successfully represented by structural formulas which
*% Ann. d. Chem. (Liebig) (1899), 306, 87.
* Journ. Chem. Soc. London (1906), 89, 497.
170 The Philippine Journal of Science 1918
are static in their meaning. The term isorropesis was proposed
to designate the interrelation between groups of this type. The
activity of a carbonyl radical is not inherent in the group itself,
but is produced by the action of neighboring atoms that render
the group nascent. The causes underlying this action are more
easily understood by means of the partial valency theory. The
amount of affinity in excess of that utilized in holding the doubly
bound atoms together will depend upon the presence of free
affinity exerted by neighboring atoms. In the absence of such
forces, the energy of the two atoms will be mutually neutralized
and in equilibrium.
When phthaloxime is converted into its salts, a marked altera-
tion in molecular vibration is manifested to the eye by the change
from a colorless compound to a colored one. The new vibration
may be due either to a different equilibrium of the same molecule
induced by the presence of a positive metal atom, or to an actual
alteration in molecular structure.
COLOR DUE TO CHANGE IN EQUILIBRIUM BETWEEN PARTIAL
VALENCIES
If the production of color in the formation of salts of phthal-
oxime is due to a change in the vibration of the molecule un-
accompanied by atomic tautomerism, it must be dependent upon
a new equilibrium between the partial valencies of the unsatu-
rated groups. The change of equilibrium is not to be attributed
to the increased weight of the molecule and consequent reduc-
tion in the period of vibration. The replacement of the acidic
hydrogen by groups with high molecular weight, as in the case
of the benzoate, causes a change in the activity of the molecule
shown by a reduction in the persistence of the characteristic
absorption band in the spectrum. However, the type of
spectrum remains the same. Therefore, the activity of the
hydrogen is not greatly different from that of various organic
radicals, and the compound retains its true oxime condition in
every case. It is to be noted that an aqueous solution of oxime
shows a slightly more pronounced yellow tint than a correspond-
ing alcohol solution and that the color in both cases is decreased
by a trace of mineral acid. The ethers and esters of the oxime
do not behave in an analogous manner, but always give solutions
of equal color intensity that are unchanged by traces of acid.
The acidic hydrogen, therefore, influences the equilibrium to a
* Baly and Schaefer, ibid. (1908), 93, 1814.
ee SS ~--- °° |
ee ee) en
VIII, A, 8 Pratt and Gibbs: Two Phthaloximes 171
slight extent depending upon the solvent, although the activity
is not sufficient to cause any indication of a color band in the
absorption spectrum. The stronger general absorption of the
oxime as compared with the benzoate shows a tendency toward
the production of a band, as might be expected.
The replacement of hydrogen by a metal atom introduces a
strong positive sphere of influence that must have a greater dis-
turbing effect on the negative latent valencies. The more posi-
tive the metal or group introduced, the greater will be the
resulting change produced. The following table of optical
properties of phthaloxime and various derivatives shows that the
character of light transmitted by the crystals may be arranged in
a graded scale corresponding with the increasing basicity of the
substituting atom or radical.
TABLE I."—Optical properties of phthaloxime and derivatives.
| Character of light rays transmitted Degree of pleo-
Compound. through crystals. ‘chroism.
LEGS 2 J ee Sie) Ea AES Te nee oe a pa in ee ed Absent.
Ethyl ether of yellow oxime__-_-__ White and faint greenish yellow___________ Faint.
peeeienyur Grate 26 Wehitcand yellows === a Do.
Acid sodium salt of white oxime_| Pale yellow and orange ____________________ Marked.
Ammonium salt of white oxime_| Straw yellow and reddish orange __________ Strong.
Sodium salt of white oxime ----_- Pale purple and deeper purple_____________ Rather marked.
8 Determinations made by Professor Gill, mineralogical department, Cornell University;
see Orndorfi and Pratt, loc. cit.
The potassium salt forms very small crystals that are difficult
to examine, but in bulk the color appears darker than the corre-
sponding sodium salt. The differences existing among the above
salts in crystalline condition are very distinct, but cannot be ac-
curately shown spectroscopically. Alcohol solutions of the am-
monium, lithium, barium, sodium, and potassium salts were
photographed. All of these solutions in hundredth molar con-
centration showed a well-marked color absorption band increas-
ing in width and persistence in the order named. This was
partly due to the different dissociation constants of the various
alkalies, but this factor could not be eliminated in as much as the
addition of an excess great enough to compensate for the disso-
ciation always resulted in the formation of hydroxamic acid and
destruction of the oxime.
A very weak base such as pyridine dissolves phthaloxime with
slight change of color, and the solution gives an absorption spec-
trum showing no band in the visible region. This indicates that
gy oe The Philippine Journal of Science 1918
if a salt is formed it must have the true oxime structure. The
addition of increasing amounts of water to the pyridine solution
causes a progressive deepening of color and gradual production of
a color band until the characteristic red of the alkali salts is
obtained. This effect is explained by the increased basicity of
the pyridine hydrate formed upon the addition of water. The
salt is unstable, and could not be isolated from solution without
the entire loss of pyridine.
The silver salt of phthaloxime is insoluble in the ordinary
solvents, and its true absorption spectrum could not be obtained.
It dissolves readily in pyridine with a purplish red color, prob-
ably due to the formation of an addition product containing the
strongly positive silver dipyridine. A similar product was iso-
lated in the case of ammonia where one molecule of crystalline
silver salt was combined with one molecule of ammonia. These
addition products are deeply colored as might be expected from
the strength of the double base. That the absorption band of
their spectra heads at a different place than that characteristic
of the alkali oxime salts is probably due to the presence of addi-
tional latent valencies in the unsaturated nitrogen atom of the
pyridine-silver or ammonia-silver groups.
It is evident that the introduction of various positive atoms
or radicals into the phthaloxime molecule may cause different
changes in its optical activity. It may be assumed that the pre-
vious condition of equilibrium existing between the unsaturated
—CO and =NOH groups is completely changed, and that the
latent valencies of these groups no longer mutually neutralize
each other, but that a negative portion swings to the positive
metal. The equilibrium will be slightly different in various salts
depending upon the electropositiveness of the substituting atom
or group, but will always be of the same type unless further
complicated by the introduction of other unsaturated atoms.
The result of the new equilibrium between the positive group or
atom and the negative partial valency of an unsaturated atom is
shown by the disappearance to a greater or less extent of the
absorption spectrum characteristic of the original type and the
production of a new band in the spectrum.
The position of the new band and consequent color, in the broad
sense, of the salt given by any compound undergoing changes of
this general type will depend upon the resulting configuration
of the molecule. The presence of the benzene ring or its equiv-
alent in the molecule is probably essential whenever the absorp-
tion band of the salt falls in the characteristic quinone position.
VIII, A, 3 Pratt and Gibbs: Two Phthaloximes 173
The molecular equilibrium of phthaloxime salts may be rep-
resented by the formula:
=0.,
AIR 0:
CoH, O M
Ne Ze 4th
—=NO
This indicates merely the partial valency equilibrium between
negative carbonyl] and positive metal, and shows a ring forma-
tion resembling the quinoid configuration. It is to be noted that
neither phthalic acid nor phthalimide can give analogous salts,
although the compounds themselves present a condition similar
to that of the oxime. The addition of alkali to solutions of these
substances causes no radical change in the position of their ab-
sorption bands, but causes a marked increase in the width of the
original band of the latter, indicating a difference in degree of
the existing equilibrium rather than a change in character.
The application of the partial valency theory to colored salts
has been utilized by Werner ** in the case of the yellow benzil-
oxime. He gives these compounds the following structure:
Seo rs Pirie re ;
x
No=™.°
but makes no mention of the equilibrium that must exist between
the unsaturated groups before the entrance of the metal atom.
Hantzsch has also used similar conceptions in much of his later
work, and has applied partial valency structures to many com-
pounds in which it is otherwise very difficult to explain the ab-
sorption spectra.
Lassar-Cohn calls attention to the resemblance between phthal-
oxime and the nitrolic acids, and Hantzsch and Kanasirski **
have studied the absorption spectrum of the latter. They find
that ethyl nitrolic acid,
NO2
HsC—C
NOH,
* Ber. d. deutschen chem. Ges. (1908), 41, 1062.
* Ibid. (1909), 42, 889.
1194803
174 The Philippine Journal of Science 1918
shows only general absorption, while its red potassium salt gives
a broad absorption band heading at = 3050.
In this case there is no possibility for quinoid formation in a
ring in connection with conjugated linking between unsaturated
groups, and the colored salts do not give absorption spectra
showing a band in the quinone region. There is, however, a
marked difference between the spectra of the salts and free
acid. Hantzsch represents the equilibrium of the former by the
formula:
NO»
H3C—C M
NO
This explains the change in optical properties that takes place
when the acid is converted into its salts, and corresponds to our
oxime structure.
Certain diketones represented by the type of indandions are
colorless or very faintly yellow, but dissolve in alkaline solutions
giving highly colored salts. In this case the salt formation has
been shown to take place with a tautomeric change from the
keto to the enol form as represented by the formulas:
C=O Cc=0
Ye He
CoH CHR 5H yer
C0 \c“@oH(M)
Keto indandion. Enol indandion.
The alkali salt exists in the conjugated form according to
Hantzsch 78 who represents this condition as
= .
vee de
CH, der M
Ny Rulldeyh
Conjugated enol salt of indandion.
This class of compounds is evidently more nearly related to
the phthaloximes than are the nitrolic acids. There are several
important points of difference, however, that serve to throw light
* Ann. d. Chem. (Liebig) (1912), 392, 286. _
ee ee
VIII, A, 8 Pratt and Gibbs: Two Phthaloximes 175
upon the structure of the oximes. The absorption spectra of
the indandions have been carefully studied by Hantzsch, and
found to vary in a marked degree with change of solvent. Phenyl
indandion was shown to give only general absorption in ether
solution, but selective absorption in methyl alcohol with 1 well-
developed band and 2 step-offs. In the presence of alkali these
develop into 3 well-marked absorption bands. The equilibrium
of the enol-keto tautomerism in ether solution differs from that
in methy! alcohol, and causes a corresponding difference in the
absorption spectra.’®
The application of Hantzsch’s work to our problem gives ad-
ditional evidence concerning the structure of phthaloxime. If
the oxime were correctly represented by the symmetrical for-
mula, it might be expected to resemble the indandions both chem-
ically and spectroscopically, and undergo enol-keto tautomerism
The absorption spectra would show this equilibrium, and the ap-
proximate amount of the enol form in solution could be deter-
mined by titration with bromine.”° Molecular rearrangement
of this type would result in the following equilibrium:
o=0 C—OH(M)
CsHy NOH = GH, NO
c=0 NGO
Solutions of phthaloxime do not react with aqueous bromine,
however, and no chemical or optical indications of enol-keto
tautomerism could be observed. Moreover, the absorption spec-
tra of the oximes in various neutral solvents are practically iden-
tical, do not show evidences of an enol-keto band, and are of an
entirely different type from those given by the indandions. The
other alternative for salt formation with a symmetrical oxime
would be direct replacement of hydrogen by a metal atom, giving
salts analogous in many respects to the salts of phthalimide.
Since neither of the above conditions is characteristic of phthal-
oxime, it seems very probable from spectroscopic evidence alone
that only the unsymmetrical structure will explain the facts.
Oximido-oxazolone is colorless or faintly yellow, and also
forms highly colored salts with colorless metals. Hantzsch *
* Hantzsch, loc. cit.
* Meyer, Ann. d. Chem. (Liebig) (1911), 380, 212.
21 Ber. d. deutschen Chem. Ges. (1909), 42, 1007; (1910), 43, 68.
176 The Philippine Journal of Science 1918
represents the chromophoric development in this case by the
formulas:
j
C C
Nf \C=NOH Sper m
| | a ela
Eee O (O== 0)
Oximido-oxazolone. Oximido-oxazolone salts.
(Colorless.) (Colored.)
He has found that this oxime shows only general absorption in
its spectrum, while solutions of its salts are strongly selective
with a well-marked band in the color region. It is evident that
conditions in compounds of this type are similar to those in
phthaloxime as far as the production of color upon salt forma-
tion is concerned. There is no possibility for quinoid configura-
tion of a ring in the oximido-oxazolones, yet the change in their
absorption spectra upon the addition of alkali closely resembles
that shown by phthaloxime. It does not seem essential, there-
fore, to assume an actual quinoid structure in the latter case, but
merely that the two rings act similarly toward the conjugated
partial valencies in both classes of compounds, and that the gen-
eral effect of a positive metal atom in the molecule is analogous.
COLOR DUE TO MOLECULAR REARRANGEMENT
There are several factors which render it improbable that the
salts of phthaloxime possess a different molecular structure from
that of the oxime. The red silver salt reacts easily and at low
temperatures with alkyl iodides giving ethers that undoubtedly
possess the true oxime structure. These ethers are colorless in
the case of the colorless isomer, and faintly yellow when derived
from the yellow oxime. They are broken down by solutions of
the caustic alkalies into substituted hydroxylamines, and give
absorption spectra closely resembling the parent oximes. No
ethers have thus far been made that show the color characteristic
of the salts, and if formed as the first phase of the reaction be-
tween silver salt and alkyl iodide they must be very unstable.
Since the two phthaloximes have been shown to retain their
identity when converted into salts,”* any formula representing a
different arrangement of the molecule to explain color must in-
clude the doubly bound nitrogen upon which the isomerism
* Orndorff and Pratt, loc. cit.
VILL A, 3 Pratt and Gibbs: Two Phthaloximes 177
depends. Two possible formulas representing the oxime salts ©
may be expressed as:
OM
4 ZOOM
Phe CFE 10
’ 6f14
mee or an SUmpe
i eee €—, N90;
the second of which would explain color formation as depending
upon the quinoid condition of the benzene ring and might be con-
sidered as in equilibrium with the first. The theory of partial
valency may also be applied to the second formula giving a con-
jugated linking in the side chain that may be represented by
the formula:
0€ M
The salts would then belong to the enol-nitroso type.
No method is available to decide definitely between these two
explanations of the very marked change that takes place when
phthaloxime is converted into its highly colored salts. The par-
tial valency theory explaining color as dependent upon a changed
condition of equilibrium brought about by a positive metal atom
without actual molecular rearrangement has much to recommend
it, and seems to be in better accord with our present ideas of
chromophoric chemistry.
ABSORPTION SPECTRA OF THE PHTHALOXIMES, THEIR METHYL
ETHERS, ACETATES, AND BENZOATES
The complete curves of the absorption spectra of the two
phthaloximes are shown in fig. 1. Solutions in absolute alcohol
were employed when not otherwise stated, and the spectra
photographed with a Hilger spectrograph 2? using a nickel arc
as the source of light.
The curves are plotted with logarithms of thickness of layer
in millimeters of ten thousandth molar concentration as ordi-
nates, and oscillation frequencies of the limits of transmission
as abscissa.
* The purchase of this instrument was made possible through the gen-
erosity of Mr. Enrique Zobel, Mr. Antonio Roxas, Mr. Manuel Earnshaw,
Dr. Ariston Bautista y Lim, the San Miguel Brewery, and the Germinal
Tobacco Factory.
178 The Philippine Journal of Science 1913
Oscillation frequencies.
22 24 26 —28, 3000) 32 > 34 36" 38 4000 ae Aa 46
100,000
>
o
4.6
4.4
4.0 10,000
3.8
w
=
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Relative thickness of layer in millimeters of 1/10,000 molar solution.
roa ale pe
EEE
SACRE
eee eee
Fig. 1. Full curve=white phthaloxime.
Dot curve=yellow phthaloxime.
Dash curve=benzoate of white phthaloxime.
100
Description of fig. 1.—The region of greatest difference be-
tween the two curves is found in the total absorption at high
concentrations. The upper limit of these curves from log. 5.3
to 5.7 represents higher concentrations than can be conveniently
VIII, A, 3 Pratt and Gibbs: Two Phthaloximes 179
handled with alcohol alone as a solvent. A mixture of equal
parts of alcohol and acetone proved satisfactory for this region.
The yellow isomer shows greater total absorption in the visible
spectrum. With decreasing concentration the curves approach
until they are practically identical, but separate again as they
reach the absorption band at * 3400 where the white isomer.
shows slightly greater persistence. The benzene bands, numbers
1, 2, 4, and 6, are clearly defined in neutral or acid solution al-
though not separately plotted in fig. 1.
The absorption curve of the benzoate of white phthaloxime is
also shown in fig. 1. The spectra of the methyl ethers and ace-
tates were also studied, but are not plotted as the curves fall be-
tween the oximes and the benzoates. All of these curves are very
similar. The absorption bands extend to about the same dilution
for each compound, but the intervening transmitted portion is
very different in each case. The transmission band at = 3676
decreases from about 2.5 in the oximes and methyl ethers to
2.4 in the acetates and 2.15 in the benzoates. The transmission
bands bounding the other benzene absorption bands show about
the same decrease; that is, the transmission band heading at
+ = 3870 persists to about log. 2.82 in the oximes, 2.25 in the
acetates, and 2.20 in the benzoates.
THE METHYL ETHERS OF THE TWO PHTHALOXIMES
The methyl ethers of the two oximes were made by treating the
respective silver salts suspended in ether with methyl iodide.
The reaction proceeds rapidly at room temperature with the
separation of silver iodide. The ethers were extracted from the
residue and recrystallized from alcohol in the form of long
needles, that of the white oxime being colorless while the cor-
responding derivative of the yellow oxime is faintly yellow. Both
ethers melt at 133° uncorrected.
THE BENZOATES OF THE TWO PHTHALOXIMES
The two benzoates were similarly made from the silver salts
and benzoyl chloride. They crystallize from alcohol in columns,
one colorless and the other faintly yellow. Both melt at 171°.5
uncorrected. The benzoates may conveniently be prepared also
from benzoyl chloride and an alkali salt of the oxime dissolved in
water.
180 The Philippine Journal of Science 1918
THE ALKALI SALTS OF THE TWO PHTHALOXIMES
The profound changes that ‘take place in phthaloxime on
the addition of alkali are manifested in the absorption spectra
by the appearance of a broad absorption band extending from
about + = 1800 to 2860, and heading at + =2300. The ab-
sorption band of the oximes heading at = 38400 decreases
regularly with increasing concentrations of alkali, and practically
disappears when the amount of alkali is sufficiently great to
effect the complete transformation into the red salt. These dif-
ferences with various concentrations of alkali are shown in fig. 2.
Oscillation frequencies.
2000 22 24 26 28 300032 34 36 38 400042 44 A6
10,000
Ww
a
w
2
wy
A
nN
~
~m
le oss tol yi al
> SEE Lees .
pi fi [ot otal LAN aoe
Ba tal ale Foy
Relative thickness of layer in millimeteys of 1/10,000 molar solution.
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
—_
Fig. 2. Full ourves = white phthaloxime with 1/16, 1/8, 1/4, 1/2, and 1 equivalent of sodium
ethoxide.
Dot curves=yellow phthaloxime with corresponding alkali.
Description of fig. 2.—In order to avoid confusion arising from
the large number of lines, the curves with one-sixteenth, one-
eighth, and one-quarter molecular equivalents of alkali are not
VIII, A, 3 Pratt and Gibbs: Two Phthaloximes 181
drawn throughout the entire regions measured. It is sufficient
to state that they lie between the curve of the oxime itself and that
formed with one-half equivalent of alkali.
These curves are plotted from photographs made through ab-
solute alcohol solutions wherever possible. Since the desired
concentration could not always be obtained with this solvent,
90 per cent alcohol was used when 1 equivalent and one-half
equivalent of alkali were employed in the 1/100 molar solu-
tions, and 99 per cent alcohol for the 1/1000 molar solutions.
Ninety-five per cent alcohol solutions were used for the other
1/100 molar concentrations. These small amounts of water have
no appreciable effect upon the curves.
The difference between the yellow and the white modification
of the oxime is here manifested in the color absorption band.
This has a greater persistence in the yellow than in the white,
and shows that the salts of the former are somewhat more deeply
colored than the corresponding salts of the latter.
Oscillation jen o6i
2000 22 24 26 3000 32
Beer l ts
ee
_ Se
10,000
/10,000 molar solution.
=
roa)
ce
b
Nee
Os
1,000
©
Rea ZEN &
Soe Zane
i ae
Fig. 3. Salts of white phthaloxime in 90 per cent alcohol.
Full curve=potassium salt.
Dash curve=sodium salt.
Dot curve=barium salt.
Dash and dot curve=ammonium salt.
=
ro)
Relative thickness of layer in millimeters of 1/10,000 molar solution.
Logarithms of relative thickness in millimeters of 1
w
oS
182 The Philippine Journal of Science 1918
THE ABSORPTION SPECTRA OF PHTHALOXIME SALTS IN 90 PER CENT
ALCOHOL
Weighed quantities of the pure salts were dissolved in the
requisite volume of water and absolute alcohol added at once
to make a 90 per cent alcohol solvent. In this manner exactly
1 equivalent of alkali to 1 of oxime was easily obtained. Photo-
graphs were made on Cramer’s spectrum plates to cover as much
of the color absorption band as possible, and the curves in fig. 3
plotted from these.
Description of fig. 3.—The curves show that the ammonium,
barium, sodium, and potassium salts give absorption bands head-
ing at : = 2300 in each case, but appearing at increasing dilu-
tions. The original ultra-violet oxime band heading at 7 = 3400
was most pronounced in the ammonium salt and least in the po-
tassium. The barium and sodium salts give intermediate curves.
The residual oxime band gives an indication of the relative dis-
sociation of the different salts, and corresponds in persistence
inversely with the strength of the base. The silver salt of
phthaloxime in crystalline form shows a deeper red than the
corresponding potassium salt, but could not be included in the
series because of its insolubility.
THE ABSORPTION SPECTRA OF PHTHALOXIME AND ITS SALTS IN
PYRIDINE
Pyridine is the only suitable solvent for the silver salt, and
gives a deep purplish red solution containing an addition product
of salt and base.
Description of fig. 4—The absorption band appears at greater
dilution, and heads ats = 2140. Itis of the same general type
as the corresponding band given by the alkali salts, but shows
by its position farther toward the red that a slightly different
molecular equilibrium is represented in the compound. The
curve given by oxime in pyridine shows general absorption ex-
tending into the visible spectrum, but retaining the oxime type.
It is probable that no true salt is formed since a weighed amount
of oxime did not gain in weight when dry pyridine vapor was
passed over it. The dash curve represents oxime dissolved in a
mixture containing equal volumes of water and pyridine. The
color of this solution is deep red, and the absorption spectrum
clearly shows the presence of a true salt.
1
;
‘
> eel ee ee ee ee
?
VIIL, A, 3 Pratt and Gibbs: Two Phthaloximes 183
THE ABSORPTION SPECTRA OF PHTHALOXIME SALTS IN AQUEOUS
PYRIDINE
The absorption spectra of the ammonium, sodium, potassium,
and silver salts of the white oxime in pyridine solution contain-
ing 14 per cent water are plotted in fig.5. The addition of water
is necessary to dissolve the alkali salts, as their solubility in pyri-
dine is slight.
Oscillation frequencies.
6 2000 .22 24 26 28 3000 32
16 |
aa oh
Beer | \ |
oe
3.8
ad
f=»)
N
>
IN
Ls}
os
°
10,000
<3
aK
3.2
3.0
Relative thickness of layer in millimeters of 1/10,000 molar solution.
ne
©
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fig. 4. Full curve=white phthaloxime in pyridine.
Dash curve=white phthaloxime in 50 per cent pyridine and 50 per cent water.
Dot curve=Silver salt of white phthaloxime in pyridine.
184 The Philippine Journal of Science 1913
oye See
16 18 2000 22 24 3000 32 34
is)
LS)
ine)
a
US)
a
ins)
tS
iS
nN
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Relative thickness of layer in millimeters of 1/10,000 molar solution.
Fig. 5. Salts of white phthaloxime in pyridine containing 14 per cent water.
Full curve=silver salt.
Dash curve=potassium salt.
Dot curve=sodium salt.
Dash and dot curve=ammonium salt.
Description of fig. 5.—These curves bring out the difference
in persistence and width of the color band and the corresponding
residues of the ultra-violet oxime band. Since there is very little
difference in the persistence of the latter in each case, it is reason-
able to assume that the hydrolysis of the salts does not vary
greatly in this solvent. The width of the color band and the
dilution at which it appears are very different, especially with the
weak ammonia base. These curyes bring out the effect of dif-
ferent substituents and the relation between color and positive
affinity better than any other series we have obtained. The ad-
dition product of silver salt and pyridine has been largely de-
stroyed, and the absorption curve now heads at approximately
the same point as that of the normal salts.
A solution of silver salt in alcoholic ammonia was prepared and
photographed. The curve of its absorption spectrum falls be-
tween that of silver salt in pyridine and silver salt in pyridine con-
taining 14 per cent water. This solution is unstable, and rapidly
loses its red color with the formation of metallic silver. The
addition product may be obtained by passing dry ammonia over
VIIL A, 8 Pratt and Gibbs: Two Phthaloximes 185
a weighed amount of silver salt in a porcelain boat. Decompo-
sition occurs with gradual loss of weight in a few hours. The
results of one experiment are as follows:
Substance Gain Gain
(gram). (gram). (per cent).
0.2133 0.0153 6.81
.0145 6.80
.0123 5.76
-0118 5.58
Calculated for
CsH.0;NAg’“NHs3 6.30
The boat and contents were then heated at 100° with a loss
of weight corresponding approximately to the ammonia pre-
viously absorbed. The color remained a brownish gray, indi-
cating no recovery of the original silver salt.
THE ACID SALTS OF PHTHALOXIME
When an alcoholic solution of phthaloxime is treated with
alcoholic potassium acetate, an orange-colored crystalline salt
is precipitated.2* A study of the absorption spectrum of this
double salt clearly showed that in solution it was identical with
the original oxime in the presence of one-half an equivalent of
potassium ethoxide. Sodium acetate forms a similar double salt
which is more difficult to crystallize and isolate. The underly-
ing reasons for this fact are to be found in the relative solubili-
ties of the normal sodium and potassium salts of phthaloxime.
We have found that 100 cubic centimeters of absolute alcohol
at 30° will dissolve 0.0590 gram of the potassium salt and only
0.0076 gram of the corresponding sodium salt.
Since the absorption spectra of the double salts were found to
be identical with those of the oximes plus one-half an equivalent
of corresponding alkali, we concluded that these salts could be
crystallized from alcoholic solutions with equal ease by the addi-
tion of the proper amount of the hydroxide or ethoxide of the
metal. This was found to be the case, and the fact that sodium
or potassium acetate dissociates in solution, giving a small
excess of hydroxyl ions over hydrogen ions, explains why these
double salts were originally obtained by the addition of alkali
acetates, while the formation with alkali hydroxides was over-
looked. The double salts may also be prepared by mixing equal
molecular equivalents of alcohol solutions of oxime and the nor-
mal alkali salt and concentrating to crystallization.
* Orndorff and Pratt, loc. cit.
186 The Philippine Journal of Science 1913
COLORLESS ALKALI SALTS OF PHTHALOXIME
The effect of temperature upon molecular equilibrium is little
understood, but there is undoubtedly a decreased activity at low
temperatures. Alcohol solutions of phthaloxime show less
yellow color when cooled in a mixture of solid carbon dioxide
and ether. This may be due to a decreased activity of hydrogen
toward the partial valencies of the unsaturated groups, or may
be caused by a change in the equilibrium of molecular rearrange-
ment. When a cold alcohol solution of sodium ethoxide was
added to the above oxime solution, crystals of sodium salt were
precipitated in an almost colorless form. These showed no
increase of color as long as they were kept cold in the freezing
mixture, but rapidly turned red after filtering from the mother
liquor, due in all probability both to the rise in temperature and
the condensation of water. The colorless crystals may be taken
as the true oxime type of salt, regardless of which theory be
applied to explain the colored compounds.
THE ABSORPTION SPECTRA OF PHTHALHYDROXAMIC ACID
Alkaline solutions of phthaloxime salts suffer rapid transforma-
tion into salts of phthalhydroxamic acid ?* with loss of identity
between the white and the yellow isomer.?* It appears that the
difference between the two forms depends upon the integrity
of the double bond between carbon and nitrogen, and that this
is destroyed when the hydroxamic acid forms. Moreover, the
free hydroxamic acid when heated in solution gives phthaloxime,
the white isomer forming at 60° and the yellow at 100°. The
formation of hydroxamic acid may be due to the increased activ-
ity of molecular vibration when hydrogen is replaced by a metal
atom or to the tendency of the rearranged molecule to take up the
elements of water. However, phthaloxime suspended in distilled
water gradually forms hydroxamic acid upon standing even in
the presence of mineral acid and without passing through a
colored stage, so it is not essential to assume a different molecu-
lar condition as necessary for the transformation. Alkali
appears merely to accelerate the rate of reaction, without in-
fluencing the final product. This is further evidence that the
oxime and its salts possess identical molecular structure.
For purposes of photographing the absorption spectrum of the
hydroxamic acid, alcohol solutions of oxime were treated with
an excess of alkali and allowed to stand until colorless.
* Lassar-Cohn, loc. cit.
*° Orndorff and Pratt, loc. cit.
VIII, A, 3 Pratt and Gibbs: Two Phthaloximes 187
Oscillation frequencies.
22 ZOE RAG ose See Same soe © SO) A000) 42) 144
iol a) oe ol a
oo eS ee
aS eee
10,000
w
Lo>)
Sse
5
w
nn
w
o
nm
@
n
iN
se eae
PEPE
BEEP
nN
Le)
100
N
ro)
@
Relative thickness of layer in millimeters of 1/10,000 molar solution.
a
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
‘ Nn e ‘ sy
a
Fig. 6. Full curve=phthalhydroxamic acid.
Dash curve=phthalylphenylhydrazine.
Dot curve=anilidophthalamic acid.
Description of fig. 6—The absorption spectrum of phthal-
hydroxamic acid shows a small band in the ultra-violet heading
at + — 3560 and indications of benzene bands. This is evi-
dence that the condition present in oxime, phthalic acid, phthal-
imide, etc., is still present, although the persistence of the
characteristic band is greatly decreased in the case of the
hydroxamic acid. The spectroscopic behavior of phthalhydrox-
amic acid, therefore, corresponds with the formula generally
assigned to this compound.
188 The Philippine Journal of Science 1918
ACTION OF PHENYLHYDRAZINE ON PHTHALOXIME
When an alcohol solution of either the white or yellow phthal-
oxime is gently warmed with phenylhydrazine, the following
reaction takes place:
oa ; 20H
CoH, De +H2N-NH-CGceH; — CcoHs O
\c=NnoH Nc@
NH-NH-CcHs ~
Phthaloxime. Anilidophthalamic acid. ~*
The anilidophthalamic acid thus formed was recrystallized
from alcohol until colorless, and found to be identical with the
compound described by Hotte 2’ who obtained it from phthalic
anhydride and phenylhydrazine.
0.1698 gram gave 17.2 cubic centimeters nitrogen over water at 31°.5;
barometer, 763 millimeters.
Calculated for onnd
Gabe Ee (per cent).
Nitrogen 10.93 10.96
0.1974 gram dissolved in absolute alcohol required 7.70 cubic centimeters
of N/10 sodium hydroxide for neutralization. Theory, 7.71 cubic centi-
meters.
The absorption spectrum of anilidophthalamic acid is plotted
in fig. 6, and indicates by the band heading at + = 8700 that
the structure is analogous to phthalhydroxamic acid and correctly
represented by the above formula.
PHTHALYLPHENYLHYDRAZINE
If the alcohol solution of phthaloxime and phenylhydrazine be
heated on the water bath for an hour, the reaction proceeds fur-
ther with the splitting off of one molecule of water. A neutral
yellow compound is formed identical with Hotte’s phthalylphenyl-
hydrazine. The same product results when anilidopthalamic
acid is heated, the reaction going to completion rapidly at 100°.
This compound crystallizes from alcohol in long yellow prisms,
and melts at 182° uncorrected.
(1) 0.1854 gram gave 20.0 cubic centimeters nitrogen over water at 29°;
barometer, 762.5 millimeters.
(2) 0.1740 gram gave 18.8 cubic centimeters nitrogen over water at 30°;
barometer, 763.7 millimeters.
(3) 0.2280 gram gave 0.5761 gram CO, and 0.0821 gram H.0O.
* Journ. f. prakt. Chem. (1887), II, 35, 268.
VIII, A, 3 Pratt and Gibbs: Two Phthaloximes 189
Calculated for Round
Cus Hio 02 N2 (per cent).
Carbon 70.58 70.44
Hydrogen 4.20 4.09
Nitrogen se 11.76 11.82
11.77
The absorption spectrum of phthalylphenylhydrazine is also
plotted in fig. 6. It shows a well-developed ultra-violet band
heading at * 3600 and a step-off extending from += 2400
to 3060. The characteristics of this spectrum throw grave doubt
upon the symmetrical structure,
CcH, »N NH-G.Hs
\c=o
given by Hotte. We have found his method of preparation
analogous in every way to the formation of phthaloxime from
phthalic anhydride and hydroxylamine. The replacement of the
oxime group of phthaloxime by the phenylhydrazine residue
corresponds to similar reactions studied by Just,?* and undoubt-
edly results in a similar structure. Moreover, a careful study
of the absorption spectrum in comparison with those of various
phenylhydrazines and osazones described by Baly and Tuck *°
and by Baly, Tuck, and Marsden *° leads us to believe that this
compound may not be a hydrazone. We hope to continue this
investigation, and in a later article to present conclusive evidence
concerning the structure of this interesting compound and its
derivatives.
* Ber. d. deutschen chem. Ges. (1886), 19, 1205.
* Journ. Chem. Soc. London (1906), 89, 982.
° Ibid. (1907), 91, 1572.
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ILLUSTRATIONS
PLATE I
Yellow phthaloxime. 1/1000 molar solution. Thickness of layer, 32 to 2
millimeters.
PLATE II
Fig. 1. Potassium salt of white phthaloxime in 90 per cent alcohol. 1/100
Fig. 1.
molar solution. Thickness of layer, 1, 2, 4, 6, 8, 10, 12, 14, 16,
18, 20, 22, 30, 50, 75, and 100 millimeters.
. Silver salt of white phthaloxime in pyridine. 1/100 molar solution.
Thickness of layer, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18,
20, and 22 millimeters.
TEXT FIGURES
Full curve=white phthaloxime.
Dot curve=yellow phthaloxime.
Dash curve=benzoate of white phthaloxime.
. Full curves=white phthaloxime with +4, 4, 3, 4, and 1 equivalent
of sodium ethoxide.
Dot curves=yellow phthaloxime with corresponding alkali.
. Salts of white phthaloxime in 90 per cent alcohol.
Full curve=potassium salt.
Dash curve=sodium salt.
Dot curve=barium salt.
Dash and dot curve=ammonium salt.
. Full curve=white phthaloxime in pyridine.
Dash curve=white phthaloxime in 50 per cent pyridine and 50
per cent water.
Dot curve=silver salt of white phthaloxime in pyridine.
. Salts of white phthaloxime in pyridine containing 14 per cent water.
Full curve=silver salt.
Dash curve=potassium salt.
Dot curve=sodium salt.
Dash and dot curve= ammonium salt.
. Full curve=phthalhydroxamic acid.
Dash curve=phthalylphenylhydrazine.
Dot curve=anilidophthalamic acid.
191
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PRATT AND GIBBS: TWO PHTHALOXIMES. ] [PuHiL. Journ. Scti., VIII, A, No. 3.
28 23 35 37 Go 33 40 45 60 29: <F
siisaetlcaitndtichantivalitir lint nieluiniitetetbalal bled no if AE
.
‘MMU
HU 11
11 AAO a hi
MUM LL USM TY li
T
Fig. 1. Potassium salt of white phthaloxime in 90 per cent alcohol. 1/100 molar solution.
Thickness of layer, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 30, 50, 75, and 100
millimeters.
28 23 20 31 34 35 «36 «37 «3 39 40 j
vtivalinitonluntuahustadatrhut elite tidied i wh tft
|
al
eM! UA
NUM |
ee
aw’ aT
#
&
&
z
&E
@
=
Ei
aw
_
Fig. 2. Silver salt of white phthaloxime in pyridine. 1/100 molar solution. Thickness of
layer, 1, 2, 3, 4, 5, 6, 7, 8 9, 10, 12, 14, 16, 18, 20, and 22 millimeters.
PLATE Il.
THE OPTICAL EFFICIENCY OF TINTED GLASSES IN RELIEVING
EYE STRAIN
By D. S. Pratt
(From the Laboratory of Organic Chemistry, Bureau of Science,
Mamila, P. I.)
One plate
In the Tropics, and during certain seasons of the year in tem-
perate regions, the harmful effects of excessive bright sunlight
on the eyes have been more or less mitigated by employing tinted
glass. At the present time a large variety of colors and tints
are supplied in blanks from which plane surfaces or lenses of
any formula may be ground. The color or tint used has gen-
erally been a question of personal preference and skillful adver-
tising, rather than the result of any data regarding the quality
and quantity of light transmitted by the glass.
It is well known that ultra-violet light exerts an extremely
harmful influence upon the retina of the eye due to its marked
actinic property, and that prolonged exposure to light rich in
these short wave lengths will cause blindness. Colorless glass is
sufficient to cut off the greater part of the ultra-violet spectrum
and give protection in special cases. j
The various portions of the visible spectrum differ markedly in
their physiological effect. The longer waves at the red end
are more or less converted into heat radiations within the eye
and act as an irritant, while those of shorter length comprising
the indigo and violet possess greater actinic property and resemble
the ultra-violet. The intermediate portion of the spectrum is,
therefore, most restful, and ideal protection would be afforded
by a glass capable of transmitting sufficient light throughout
this portion while at the same time reducing the intensity of
the red and eliminating the ultra-violet.
The different types of optical glass investigated were samples
of various tints, carefully polished with approximately parallel
plane surfaces. Light from a nickel-iron arc was employed,
and a Hilger spectrograph with special Cramer plates used in
*These samples were prepared and furnished by Messrs. Clark & Co.,
Manila, P. I.
193
194
photographing the various spectra.
The Philippine Journal of Science
1913
Table I shows the limits
of the transmitted portion with the various glasses.
TABLE I.—Spectra transmitted by various tinted glasses.
Type of glass.
Roéntgen
Clear crown optical
ave lengths.
3,035 to 6,990
2,970 to 6,950
Shade No. 1, blue 3,020 to 6,950
Shade No. 3, blue 3,030 to 6,950
Shade No. 5, blue 3,040 to 6,950
Shade No. 2, amber 2,980 to 6,840
Shade No. 3, amber 3,520 to 6,840
Shade No. 4, amber 3,845 to 6,840
Shade No. 6, amber 4,630 to 6,840
Shade No. 1, London smoke 3,220 to 6,940
Shade No. 3, London smoke 3,275 to 6,940
Shade No. 4, London smoke 3,320 to 6,940
Shade No. 5, London smoke 3,360 to 6,940
Shade No. 6, London smoke 3,460 to 6,940
Shade No. 1, amethyst 2,980 to 6,940
Shade No. 3, amethyst 3,005 to 6,940
Range of transmitted spectra.
Great accuracy cannot be attained by this means in measur-
ing the limits of transmission at the red end of the spectrum.
In the case of colorless glass the limit is dependent upon the sen-
sitiveness of the plate toward the longer wave lengths. The
tinted glasses show decreased intensity of the spectrum in this
portion rather than well-marked selective absorption. The fig-
ures in the above table defining the red end of the transmitted
spectra are included for relative comparisons rather than as
definite limits.
The following table gives the wave lengths corresponding to
the middle of the range covered by each of the seven primary
colors, and is included for reference.
TABLE II.—Wave lengths of the primary colors.
Color. ee
Red fet) Sa 7, 000
Orange... 2 2s 5, 972
WVellow ters -Seeere ee 5, 808
Green of) 22 een 5,271
Blu@-.2 abe - 5 see 4, 732
Indigaren. =< 5= s+ 4,383
Violet 2 sate soeeeee 4, 059
The Rontgen and clear crown optical glasses transmit the
entire visible spectrum unchanged, and only afford protection
=—- —— >
VII, A, 3 Pratt: Tinted Glasses 195
from light of wave lengths below 3,000. The three shades of
blue show practically the same limits, but in addition cause a
reduction in the intensity of the red. This effect is so slight that
these tints possess little to recommend their use. The four sam-
ples of amber differ greatly in the light transmitted. The light
shade designated as No. 2 removes less ultra-violet than the blue,
while the darker tint represented by No. 6 cuts off all the blue
and indigo. This gives excellent protection from the short wave
lengths, but fails to moderate the remainder of the visible spec-
trum to any great extent, and results in sharp contrasts that are
not restful. Amber No. 4 is to be recommended when sharp
definition is desired with the greatest protection possible under
the conditions. In the great majority of instances this is not the
case, and a glass combining the good features of the amber with
a reduction of intensity throughout the visible spectrum is more
to be desired.
The glass designated as shade No. 1, London smoke, shows a
general reduction in all regions of the visible spectrum with the
red eliminated to a slightly greater extent than the green and
blue. The amount of ultra-violet cut off is not greatly in
excess of that caused by clear glass, nor is the limit shifted to
much extent by the darker tints, although the effect on the visible
spectrum is progressively emphasized. The shade known as
No. 6, London smoke, affords the most complete protection, but
would hardly transmit sufficient light under ordinary circum-
stances. No. 4, London smoke, is probably the most satisfactory
of all the glasses examined. It does not distort the color balance
to which the eye is accustomed, as does the amber, but causes
more the effect of natural shade and is consequently very restful.
The larger proportion of short wave lengths transmitted by the
smoke tints is of less importance than the general and correctly
proportioned reduction in the visible spectrum.
The two shades of amethyst resemble the blue in their limits
of transmission, and give selective absorption of so slight a char-
acter that they cannot be considered as supplying satisfactory
protection.
It is hoped that this brief description of the optical behavior
of various tinted glasses available for eye protection may render
some assistance in choosing the most efficient color and shade
for the purpose desired.
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ILLUSTRATION
Spectra of nickel-iron are transmitted by various glasses.
‘Réntgen. 9. No. 6, amber.
lear crown optical. 10. No. 1, London smoke.
o. 1, blue. 11. No. 8, London smoke. Bey
. 8, blue. 12. No. 4, London smoke. a
. 5, blue. a 13. No. 5, London smoke. i
Drie mber. 14. No. 6, London smoke.
No. 3, amber. 15. No. 1, amethyst.
No. 4, amber. : - 16. No. 8, amethyst.
197
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PRATT, D. S. The Optical Eficieney of
_Heving Eye Strain. ae
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THE PHILIPPINE
JOURNAL OF SCIENCE
A. CHEMICAL AND GEOLOGICAL SCIENCES
AND THE INDUSTRIES
VoL. VIII AUGUST, 1913 No. 4
THE RELATION OF SEISMIC DISTURBANCES IN THE PHILIP-
PINES TO THE GEOLOGIC STRUCTURE
By MIcuEL SADERRA MaAs6* and WARREN D. SMITH
(From the Weather Bureau, and the Division of Mines, Bureau of Science,
Manila, P. I.)
Three maps
In the light of studies of the last ten years, stimulated by the
tremendous cataclysms of Messina and San Francisco, entirely
new principles have been introduced into the study of seismic
disturbances of the crust of the earth. The old centrum theory
of Mallet is generally discredited.
Beyond a doubt, many seismic disturbances are due to causes
other than vulcanism. Many of the worst disasters we have
experienced have nothing to do with volcanoes, and that volca-
noes are nearby is only a coincidence, or may be explained by the
fact that the place where great disturbances in the earth’s crust
occur is naturally a zone of weakness and where molten material
would be expected to seek an outlet. At the time of the Messina
earthquakes, Mount Etna, which can be seen from Messina, was
comparatively quiet. The great disturbance at Messina, as is.
generally known, was due to an adjustment along the line of a
+ Assistant Director of the Weather Bureau.
118865 199
200 The Philippine Journal of Science 1918
great fault in the earth’s crust, which is marked by the Straits of
Messina.
The work of the Italian Geologic Survey has demonstrated
that these disturbances are propagated along very definite lines.
So thoroughly did the Italian geologists do their work that by
superimposing upon a geologic and topographic map of the Prov-
ince of Calabria another map showing the location of cities and
all the works of man, with all historical data regarding earth-
quakes, one can see at once that: (1) Certain points are more
subject to earthquakes than others; (2) points removed from
these lines have suffered less or not at all; (3) at intersections
of these lines the greatest disasters occurred. These lines, which
follow more or less definite systems, proved to be the projections
of various earth lineaments such as fault lines, joint lines, forma-
tion contact lines, and axes of mountain ranges.
The great California earthquake of April, 1906, is a striking
example of this. This earthquake was due to a dislocation along
the well-known San Andreas rift, and, although the waves from
this disturbance were propagated, to varying distances, on both
sides, the greatest disturbance occurred along the line of this
fault.
When one can indicate a point on a map and say definitely
that here the crust of the earth is unstable, seismic geology is
shown to be of very great practical interest to humanity in gen-
eral and to engineers in particular, and especially is it pertinent
in geologically young parts of the world like the Philippine
Islands where mountain building is in progress and where the
evidences of recent vertical movement of various portions of
the island mass actually can be measured.
Concrete examples of what these disturbances mean are to be
had in the earthquakes of Messina and of San Francisco and
in the eruption of Taal Volcano.
The people of Messina had been warned repeatedly, but com-
mercial interests were so great that they took no heed of their
danger, and consequently millions of dollars worth of property
as well as thousands of lives were lost at the time of that disaster.
The same is true of San Francisco. The reported property loss
at the time of that catastrophe amounted to 490,000,000 dollars.
The disturbances in the region of Taal were primarily due to
the voleano, but Taal Voleano is located along a line of crustal
weakness, and at that time a very appreciable displacement
occurred along one or more lines passing through Taal Volcano.
vu, a, 4 Saderra Masé and Smith: Seismic Disturbances 201
One of these lines ran from the volcano to the coast through the
town of Lemery, and the other from Taal Volcano to the barrio
of Sinisian, making with the sea a triangular strip several square
kilometers in area. This whole block dropped a meter or more,
so that the sea washed inland for a distance of a kilometer over
the main highway along this coast. The road between Lemery
and Sinisian had to be reconstructed. The damage to buildings
in the town of Lemery was considerable. Fortunately no very
large structures were located along these lines, but had there
been any the property loss would have been much more con-
spicuous. We may not see in our lifetime a recurrence of dis-
asters either at Messina or San Francisco, but the time will
surely come when there will be further displacement along these
great earth rifts. It is true that there never will be as great
disasters in the Philippines, due to the fact that most of the
Filipinos live in basket-like houses which are the very safest at
the time of an earthquake, but large engineering works have been
constructed, others are being planned, and large public buildings
are continually being built; hence it is of vital importance thor-
oughly to investigate this question in the light of all the data we
now possess.
The scope of the present paper is: (1) To outline the physio-
graphy and geomorphology of the Philippines; (2) to discuss
the kinds and distribution of the rock formations and the major
structural features of the Islands; (3) in the light of these, to
show the origin of each of the important seismic disturbances of
the past; and (4) to draw some practical conclusions.
We are of the opinion that most of the seismic disturbances in
the Philippines should be attributed not to volcanoes but to
displacements along the major structure lines of the Philippine
Islands. In view of the catastrophe of Taal Volcano and of
eruptions at other points like Camiguin and Mayon, the layman
is apt to have his perspective altered, and he is naturally prone
to attribute certain phenomena to causes which are not causes but
are results of factors not yet ascertained. It should be borne
in mind that volcanoes are merely incidents in the growth of the
Archipelago. Both volcanoes and earthquakes may be traced
to the existence of lines of weakness and crustal displacements.
Many earthquakes are due entirely to volcanic phenomena, but
we believe we can prove that the major earthquakes and the
majority of earthquakes in the Philippine Archipelago are not
due to vulcanism.
902 The Philippine Journal of Science 1913
Until the year 1863 nothing was written on Philippine earth-
quakes.? Even at the present time there exist but few papers
based on modern seismologic principles, and all of these have
been written during the last ten years.
The Manila Observatory from its foundation as a private
institution in 1865 has directed its attention to earthquakes, but
for many years its work was confined to segregating and publish-
ing exact monthly observations without making a complete study
of the subject. Its collection of monthly curves in which are
contained the hourly observations of the Bertelli microseismo-
graph is exceedingly valuable on account of the long period of
time covered.
The earthquake of June, 1863, which practically destroyed
the city of Manila and many of the neighboring towns and
caused the death of more than 400 persons, led to the nomination
of a commission to investigate the architectural character of the
buildings and the nature of the soil of Manila in so far as these
might be a source of danger in the future. As at that time the
only engineers in the Philippines were those who were members
of the corps of military engineers, the commission was formed -
from among these, but their work appeared to be limited to the
establishment of several more or less successful principles and
practical rules to which the plans of the new buildings to be
erected in Manila were to conform.
Ten years later the commander of military engineers, D.
Mariano Cortes y Aguillo, wrote a memoir on the same subject.’
Notwithstanding the undoubted merit of this work as a practical
guide for architects, little account was taken of it by the author-
ities, and it was not published until after the earthquakes of
1880. The author discusses the different seismic theories with-
out adopting any of them regarding Philippine earthquakes.
He concluded, after the examination of the damaged buildings
and other existing data, that the most violent seismic movements
in Manila are in an approximate north and south direction.
After the earthquakes of 1880, a commission composed of
engineers of public works was appointed to study with care
the ruins caused by these earthquakes, to point out the defects in
the structure of the buildings that had been damaged, and to
? The more or less accurate accounts of earthquakes which may be found
scattered in the histories of the Philippines are not here considered.
* Los terremotos—Sus efectos en las edificaciones y medios practicos para
evitarlos en lo posible. Manila (1881).
vul, 4,4 Saderra Mas6 and Smith: Seismic Disturbances 203
formulate rules which would be more practical than the ones
previously drawn up for the rebuilding and repairing of the city.
This second commission, therefore, was not directly concerned
with the study of the causes of the earthquakes of 1880, nor
with the determining the extent and probable epicenter of the
same. José Centeno, engineer of mines, was entrusted with this
task. His memoir‘ is one of the best that has been published
from a descriptive point of view. He personally covered the
whole territory in which these earthquakes had been most
violent, and hence. was able to determine, with the precision
- possible in such cases, the meizoseismic areas of the three de-
_ structive earthquakes that took place from July 14 to 21, 1880.
It is to be regretted that in this investigation, which reflects
much credit upon him, he did not direct his observations to the
discovery of rifts and faults which would have indicated the
nature of the dislocation, which took place in the Eastern Cordi-
llera, and which were the causes of these earthquakes. He could
not prescind from the ideas then prevalent of the relation of
earthquakes to volcanoes, and, if he does not actually attribute
the July earthquakes to the influence of Taal Volcano, at least he
makes mention of several small eruptions which were supposed
to have occurred in the same year, as though he wished to in-
dicate in what direction investigations were to be made if there
should be an inquiry as to the origin of those earthquakes.
A short time before this, Centeno had been sent on a commis-
sion to the Peninsula of Surigao where several very severe earth-
quakes had taken place in 1879 and which had left indelible
impressions of their violence in the shape of numerous fissures
and subsidences. In his report, he assigns Mainit Lake as the
epicenter of the earthquakes. Like many other writers he sup-
posed this lake to be an extinct voleano. He could easily have
assigned another origin, because the great number of fissures
and subsidences along the ridge of mountains and especially in
Point Bilat—which is its extreme northwest extension—made it
rather clear that their character was tectonic. It may be that
some spasmodic movement had occurred which had closer relation
to the slower geologic movements in this part of the island,
and it was these the author took cognizance of, since he quotes
as proof that the depth of the port of Surigao had changed during
the earthquakes of 1879.
*Temblores de tierra ocurridos en Julio de 1880 en la Isla de Luzon.
Madrid (1885).
204 The Philippine Journal of Science 1913
Six months had scarcely elapsed since the Manila earthquakes
when a large series of seismic movements began in Nueva Vizcaya
which lasted from January until November, 1881. Enrique
Abella y Casariego, engineer of mines, was commissioned to visit
the affected province, to investigate as to what likelihood there
was of any greater seismic cataclysm happening in the future,
and if there were to see if it would be possible to make the inhab-
itants emigrate to other provinces not so affected. Abella’s
work ° is a very able and complete study of the local and super-
ficial character of the earthquakes and of their probable duration,
and his predictions with regard to their continuance were per-
fectly realized, for as he prognosticated the earthquakes ceased
shortly afterward, and up to the present no other of any great
importance has occurred. In his discussion of the origin of these
earthquakes, this author shows that he, too, was influenced by
the current volcanic theories and hence searched for possible
connections between the Province of Nueva Vizcaya and Mayon
Volcano which a short time before had shown signs of greater
activity.
The Pangasinan earthquake of 1892 gave Abella the oppor-
tunity of writing another interesting memoir.’ In this work he
does not limit his studies to the earthquakes, but adds many valu-
able notes on the geology of Pangasinan, La Union, and Benguet
Provinces, thus coming more into line with modern seismolo-
gists. Notwithstanding this, when he draws his final conclu-
sions, he places most weight on the existence of volcanic rocks
and other volcanic signs and remains, both ancient and modern,
as if it were impossible to discover the origin of these earthquakes
without recurring to volcanic action either directly or indirectly.
Several other very interesting and useful geologic monographs
are due to the indefatigable labors of Abella.’
In 1895 Saderra Mas6® published a book on earthquakes in
which he did not pretend to give a complete seismologic study,
*Terremotos de Nueva Vizcaya en 1881. Madrid (1884).
‘Abella y Casariego, E. Terremotos experimentados en la Isla de
Luzon ... en Pangasinan, Union y Benguet. Manila (1898).
* Apuntes fisicos y geolégicos de Nueva Vizcaya. Madrid (1884). Ra-
pida descripcién fisica, geol6gica y minera en bosquejo de la Isla de Panay.
Manila (1890). El Mayén 6 Volcan de Albay. Madrid (1885). Ema-
naciones voleAnicas subordinadas al Malinao. Madrid (1885). El Monte
Maquiling y sus actuales emanaciones volcdnicas. Madrid (1885). La
Isla Biliran y sus azufrales. Madrid (1885).
* La Seismologia en Filipinas. Manila Observatory (1895).
vu, A,4 Saderra Mas6 and Smith: Seismic Disturbances 205
but merely a codrdinated collection of data which might serve as a
basis for the future study of the earthquakes of the Philippine
Archipelago. Many of these data were in the archives of the
Manila Observatory and had not been published previously,
while others were to be found scattered in histories, periodicals,
and other publications.
The only important conclusion he draws is that the seismic
center dangerous for Manila does not lie in the existing volcanoes
south and southeast of the city, but in the eastern range of
mountains and especially in the part east-northeast and northeast
of Manila. :
The same writer*® has given accounts of the more important
earthquakes that have taken place in the different parts of the
Archipelago. During the first period he endeavored as a rule
to trace a relation between earthquakes and volcanoes. In the
second period—that is, 1900 to 1912—he inclined to the more
modern ideas in certain of his papers,*° although he exaggerates
the importance of volcanic manifestations when he speaks of the
different epicenters of regions of greater seismic activity.
Since 1907 this investigator has written several short papers
on the seismicity of the different regions of the Archipelago as
a preparation to a more complete-work like the present. In
these articles he has attempted to indicate by the alignment of the
different epicenters the possible existence of seismotectonic lines,
in conformity with the recent principles of seismology.
In 1899, Koto** published a valuable study in which he
discusses the different tectonic lines and volcanic belts of the
Philippines and their connection with Celebes, Borneo, and the
Moluccas. It is a thorough and complete study of great value,
* Monthly Bulletins of the Manila Observatory, 1890 to 1897, and from
1900 to 1912.
* Report on the seismic and volcanic centers of the Philippine Archi-
pelago. Manila (1904); Volcanoes and seismic centers of the Philippine
Archipelago. Washington (1904), as part of the census of the Philippine
Islands.
* The earthquakes of Ambos Camarines, Bull. P. I. Weather Bur. (1907),
172; The earthquakes of the Batanes Islands and southern Formosa, ibid.
(1909), 97; The seismic centers of northern Luzon, ibid. (1909), 131;
Submarine seismic centers near the coasts of northern Luzon, ibid. (1909),
167; Seismic centers near western Mindanao and Jolo, ibid. (1909), 203;
Seismotectonic lines in southern Luzon, ibid. (1911), 409.
“On the geological structure of the Malayan Archipelago, Journ. Coll.
Sci., Imp. Univ. Tokyo (1893), 5, pt. II, 2.
206 The Philippine Journal of Science 1913
and must be taken into account when drawing the tectonic lines
of the Philippines.
As a general study of the geology and vulcanism of the Phil-
ippines, Becker’s report 7° is the most complete work that has
appeared. In it is to be found an excellent résumé and criticism
of all the writings on the subject that had been published up to
that date. A shorter but more recent work is the article by
Smith."*
The names of several Austrian, German, and French geologists
and explorers to whom we owe the first geological data on the
Philippines should also be mentioned. The principal ones are:
von Richthofen, Carl Semper, Oebbecke, K. Martin, Jagor, Roth,
R. von Drasche, and J. Montano. Likewise, attention is called
to the works of the eminent French seismologist, Montessus de
Ballore, who published many articles on Philippine earthquakes
during the years 1895 to 1901. In one of his books? he gives
a summary of these articles on the earthquakes of the Philip-
pines. This author must be considered as the first to apply to
this Archipelago the principles of modern seismology by refer-
ring its earthquakes, not so much to imaginary volcanic agencies,
as previous authors had done, but to the principal and geological
accidents; in other words, to tectonic lines. Hence, the chapter
referred to above must in justice be reckoned the first and most
important contribution to the study of Philippine seismology.
SUMMARY OF THE PHYSIOGRAPHY OF THE PHILIPPINE ISLANDS
To present a clear idea of the underlying causes of seismic
disturbances in the Philippine Islands, it is necessary to make
some general statements. The Philippine Islands form a link
in the chain of outliers of the old Australasian continent.
According to the “horst” theory of the formation of continents
and ocean basins, the Philippine Islands lie at the very edge
of the Asiatic horst. In June, 1912, the German survey ship
Planet sounded to a depth of 9,780 meters about 60 kilometers
off the northeast coast of Mindanao.**® Soundings to the west-
* Report on the geology of the Philippine Islands, 21st Annual Rep. U. S.
Geol. Surv. Washington (1901).
“The essential features of the geology of the Philippine Islands, This
Journal, Sec. A (1910), 5, 307.
* Les tremblements de terre. Paris (1906).
* Zeitschr. Ges. Erdk. Berlin (1912), No. 6, 471; No. 8, 629-631; carte
des sondages du “Planet” a l’Est des Philippines, 4 1: 15,000,000, Abt. 31.
vu, 4,4 Saderra Masé and Smith: Seismic Disturbances 207
ward of the Philippines have not yet located anything like such
tremendous depths. We may then conceive of the Philippine
Islands as being at the edge of the continental platform or on
the brink of a tremendous “Graben” (Plate I). This platform
was subsequently raised above sea level and complexly folded at
the time of what is known as the “Miocene revolution” which
extended from New Hebrides through the Philippines north-
ward to Japan; westward across Burma, India, Persia, and
Egypt; northward to the Vienna basin; and westward even to
the Pyrenees. Following this crumpling of the crust, a gradual
tilting of the Philippine block toward the east seems to be going
on at the present time. This is evident from the raised coral
reefs on the western coast of northern Luzon, the western coast
of Palawan, and from the raised deltas and beaches on the
western coast of Zamboanga Peninsula with the existence of
drowned river basins which we know of as certain on the
eastern coast of Luzon, and at other points in the Archipelago
about which we can conjecture although we have no definite
information.
Von Richthofen,* ten years ago, noticed a peculiarity of the
Philippine Archipelago in connection with the Japanese, Riu Kiu,
Kurile, and Aleutian chains of islands; namely, a series of arcs
with their convex sides turned toward the Pacific. One of
these arcs is well marked in the Philippines by the tectonic line
passing through southeastern Luzon, Samar, and the Eastern
Cordillera of Mindanao. Northern Luzon does not conform very
well to this arc, but we may imagine that there has been a fault
and offset at the narrow portion of Luzon at the northern end
of Tayabas Peninsula.
Besides this dominant curved line, and those parallel to it
in the eastern part of the Archipelago, there are in the Philip-
pines several other distinct tectonic lines as shown in Plate II.
One of these is the Palawan line, another is the Sulu Archipelago
line, others are the parallel lines through Panay, Negros, and
Cebu—all trending northeast and southwest. Masbate seems
to be the “keystone” in the Philippine structure. The eastern
prong of this island conforms closely with the outermost arc
of the Archipelago, while the western prong conforms with one
of the northeast-southwest lines passing through eastern Panay.
* Geomorphologische Studien aus Ostasien, Sitzungsber. d. k. pr. Akad.
d. Wiss. z. Berlin (1902), 40, 944-975.
208 The Philippine Journal of Science 1913
Taking up the physiography of the Islands in detail, there is
in the northern part, on Luzon, to the eastward, first a cluster
of volcanoes containing Bulusan, Mayon, Isarog, and Iriga; then
the narrow Albay Plain; west of this a belt of Tertiary sediments;
and farther west a trough occupied by Ragay Gulf. The anti-
clinal, marked by Tayabas Peninsula, consisting of folded Ter-
tiary sediments, lies west of this; then the volcanic group
consisting of Banahao, Cristobal, and Arayat; west of these, the
central plain of Luzon, partly a tuff plain and partly made up
of alluvium; and farthest to the west a line of extinct volcanoes
marked by the Zambales Cordillera. In northern Luzon a zonal
arrangement exists, but is not so marked. Recent volcanoes are
few, Caua in Isabela Province being the only one we know of in
that section. |
In the Visayan Islands there is this same general zonal arrange-
ment of formations, but the evidence of vulcanism is not so
marked as in Luzon. The islands are marked by anticlines and
the narrow straits by synclines.
This is likewise true of Mindanao. Along the eastern coast
there are recent and Tertiary sediments flanking a core of
igneous rocks on the immediate west, and dipping eastward
toward the “fossa,” or trough, just east of Mindanao; then the
great Agusan trough; west of this an interrupted volcanic chain
marked by such prominent points as Matutan and Apo; the
great alluvial fiat occupied by the Rio Grande de Mindanao;
the regular zone of voleanic peaks marked by Malindang and the
old craters south of Lake Lanao and those in the unexplored
region south of the Rio Grande; farther west a belt of folded
Tertiary sediments; then the synclinal marked by Sibuguey
Bay; and last, the anticlinal marked by Zamboanga Peninsula.
Cross folding, probably with faulting, has broken up the
Philippine block in such a way as to produce numberless islands
in line with the main tectonic lines running through the larger
islands.
Types of mountains.—Of the various kinds of mountains such
as folded, block, and volcanic mountains, the two dominant
types in the Philippines are the first and the third. We suspect
the existence of mountains of the block type in some places
where we have not sufficient data to prove it. It might seem at
first sight that the majority of the mountains of the Philippines
are volcanic, but these are merely superimposed upon the folded
mountains or are located along other lines of weakness. While
a”) a
ae. ee >
vul, 4,4 Saderra Mas6 and Smith: Seismic Disturbances 209
there are a few active volcanoes in the Philippines, most of the
volcanoes are extinct, or dormant, as shown by the many worn-
down voleanic stocks, preserving in varying degrees their former
outlines.1§
The principal folded mountains are the Central Cordillera of
Luzon, the Eastern Cordillera which has its southern contin-
uation in Tayabas Province, and the cordilleras of Cebu,
Leyte (?), eastern Mindanao, and various other parts of the
Islands.
Block mountains are rare in the Philippine Islands, but at
Bambang on the main line of the Manila and Dagupan railway
in Luzon there are some hills which are due to the Tertiary
sediments being tilted up like blocks. From the railroad the
tilted beds are seen presenting a bold escarpment to the east,
undoubtedly due to a fault, but dipping gently to the southwest.
On Panay Island the secondary ranges—those flanking
the Central Cordillera—are tilted blocks of Tertiary sediments.
The strike of these secondary ranges conforms exactly to the
strike of the sediments. Their eastern slopes correspond in-
variably to the dip of the formations. On the upstream side
the slopes are precipitous where the upturned edges of the
sandstone and the shale beds can be seen. Displacements along
the bedding planes of these formations are frequent and have
undoubtedly given rise to many local quakes.
Kinds of rocks.—Before discussing the tectonic features of the
Islands it will be necessary to consider the distribution of the
various classes of rocks. We have the following kinds to con-
sider: (a) Deep-seated igneous, (0) extrusives, (c) intrusives,
(d) Tertiary and older sediments, (e) metamorphic rocks, (f)
wecent alluvial and pyroclastic deposits.
(a) The deep-seated igneous rocks are diorite, gabbros, pyrox-
enite, peridotite, and syenite. These rocks have all been fully
described by Iddings.*® Their distribution is the principal thing
- of importance in this discussion. The deep-seated rocks are
* These various voleanoes have been taken up in other articles in more
or less detail. The centers of volcanic activity at the present time are
Taal Voleano in Batangas Province; Mount Mayon in Albay Province,
Luzon; Mount Canlaon in Negros; and Camiguin Island just north of
Misamis, Mindanao. All of these volcanoes have been in eruption within
the last ten years, and to them can be attributed many of the minor
seismic disturbances to which the Archipelago has been subjected.
*This Journal, Sec. A (1910), 5, 155.
210 The Philippine Journal of Science 1913
naturally not very widely distributed on the surface and usually
are found only in the cafions of the central ranges. They are
particularly abundant in northern Luzon, throughout the Central
Cordillera; in Palawan Island; the Western Cordillera of Panay;
the Central Cordillera of Cebu and Leyte; the Eastern Cor-
dillera of Mindanao; on Masbate Island; in fact, wherever the
streams have been able to cut through the overlying, more recent
formations.
(b) In all parts of the Islands there is a large amount of
extrusive material which forms a mantle over the deeper lying
formations. Naturally these are found around the volcanic
areas, and these extrusives are very pronounced in the Zambales
Range of southwestern Luzon and in various parts of the Cen-
tral Cordillera lying above the old igneous and the Tertiary
sediments. In the Central Cordillera of Luzon there exist great
patches of andesite, marking probably early Tertiary volcanoes.
In the Zambales Mountains there is a development of andesite,
marking probably a still later period of volcanic activity. On
Mount Arayat, which rises isolated out of the central plain of
Luzon, basalt occurs, and around Taal Volcano and on the Bi-
nangonan Peninsula there is a considerable amount of basalt.
Extrusives are particularly well developed in the southeastern
volcanic cluster of southeastern Luzon, comprising the well-
known peaks of Bulusan, Mayon, Isarog, etc. They are found
overlying much of Masbate, particularly in the central portion;
also in western Panay, a portion of Cebu, most of northern
Negros, central Leyte, and notably in Mindanao, there being a
broad belt of extrusives running north and south through the
Apo and Matutan Ranges. Also, there is a great patch of
basaltic material around Lake Lanao and a great volcanic mass,
of which Mount Malindang is the center. There is also great
development of these extrusives covering almost the entire
Islands of Basilan and Jolo and the lesser islands of the Sulu
Archipelago.
As yet, we know of extrusives in Palawan only in the northern
part. The principal mountainous mass of Mindoro, Mount
Halcon, is largely andesitic.
There is one general conclusion which can be drawn from the
distribution of the extrusives in the Philippine Islands; namely,
that the entire recent volcanic activity consists, as far as we
know, of basaltic materials, and the older stocks are without an
exception andesitic.
vil, a, 4 Saderra Maso and Smith: Seismic Disturbances 911
(c) Small and large intrusions of diorite, granite, and basalt
are innumerable throughout the Islands. In the Central Cordi-,
llera of Luzon the intrusions seem to be generally diorite. They
cut both the Tertiary sediments and the overlying extrusives.
In the Province of Ambos Camarines in southeastern Luzon
granitic intrusions cutting the diorite and possibly the sediments
can be seen. In the Sulu Archipelago we have found a number
of small basaltic intrusions cutting some of the recent sediments.
Owing to the absence of an accurate base map of the Philippine
Islands and the fact that our work has been largely of a recon-
naissance nature, these intrusions have not been mapped in
detail or with sufficient accuracy for us to state whether or not
they follow any general system of jointing or earth lineaments.
(d) Flanking all the cordilleras on both slopes there is a
greater or less development of sandstones, shales, and limestones
which have been bowed upward in the general Miocene uplift
.referred to above, with some minor crumpling at various points.
The folding in the northern part of Luzon has apparently been
a gradual and gentle uplift of the strata. In Tayabas Peninsula
the flexures are sharper. In the Zamboanga Peninsula the
strata have been so intensely compressed that schists are the
result. These schists have been considered by some to be older
than the Tertiary, but there seems to be no good reason for not
referring them, in part at least, to the Tertiary. The central
portion of Mindanao consists of gently folded sediments. The
major axis of folding in the Philippines is in general north and
south ; along the outside arc of the Islands, northwest and south-
east; on the inside, northeast and southwest; but in central Min-
danao in the Cotabato Valley the axis of folding is more nearly
east and west.
(e) Metamorphic rocks occur more or less pronounced in
various parts of the Islands. In the Province of Ilocos Norte
there is a considerable development of schist, and in Ambos
Camarines there is schist and gneiss along the border of the
granite intrusion referred to above. Schists have been found at
one locality in the Central Cordillera of Cebu; at various points
in Palawan; on the Zamboanga Peninsula alluded to above; in
the Province of Bukidnon, Mindanao; on the Surigao Peninsula
and just east of the Gulf of Davao; at one point on the Tayabas
Peninsula; and on the Caramoan Peninsula, southeastern Luzon.
These schists appear to be for the most part metamorphosed
sediments.
212 The Philippine Journal of Science 1913
(f) Recent alluvium from the mountains deposited upon coral
shelves results in a greater or less development of coastal plains
‘around all of the islands. The coastal plains are for the most
part negligible, but some of the intermontane plains are very im-
portant. The northern three-quarters of the central plain of
Luzon is largely alluvium. The Albay Plain is largely alluvium
as is the case in the great valleys of the Cagayan, Agusan, and
Cotabato Rivers. Also, the central plain of Panay shows a
very considerable accumulation of detrital material.
Around Manila we have, in addition, a great area of pyro-
clastic material which is cut through by the Pasig River. This
is known from well logs and river sections to be at least 100
meters thick.
TYPES OF SEISMIC DISTURBANCES
Modern seismology, in rejecting every agent and force ex-
terior to our planet as causes of earthquakes, reduces the classes
of shocks to the following three types: volcanic, tectonic, and
rockfall.
Many examples of these three types are to be found in the
seismological records of the Philippine Weather Bureau, and a
few of the more characteristic will be briefly mentioned.
To the volcanic type belong all those earthquakes that are
intimately connected with volcanic eruptions caused by explosions
or sudden outbursts of steam. These volcanic earthquakes,
contrary to popular belief and to the ideas generally held for
many centuries by scientists, are in reality of but slight im-
portance and occur only in certain restricted districts.
The recent eruption of Taal Volcano, January 27 to February
8, 1911, offered a very typical series of these earthquakes. On
the night of January 27, severe earthquakes occurred on Luzon
and in adjacent regions, while at the same time or very shortly
afterward it was noticed that the principal crater of the volcano
increased in volcanic activity. This activity as well as the
frequency and intensity of the shocks went on increasing during
the 28th and 29th, until at approximately 2.26 on the morning |
of the 30th there took place the greatest and most destructive
eruption recorded in the history of the voleano. After this
paroxysm of eruptive activity the volcano returned to its normal
state in a short time, although the earthquakes continued to be
very frequent during the three following days, January 31 and
February 1 and 2, thus indicating that there was still an ac-
cumulation of energy in the interior of the volcano. During
eh a
;
vul, a,4 Saderra Mas6 and Smith: Seismic Disturbances 213
the eruptive period—January 27 to February 7—995 shocks
were recorded in the Manila Observatory, all of them between
I and V of the Rossi-Forel scale. Some of the principal shocks
were perceptible at a radius of from 120 to 200 kilometers.
The meizoseismic area of the earthquakes was a prolonged
zone which took in not only the volcano itself, but also the
south-southwestern part of Laguna de Bay and the bordering
territory as far as the sea, some 20 kilometers away (Plate II).
The decrease of perceptible intensity of the seismic action out-
side the epicentral area was, according to many comparisons
made on the spot, 1 degree of the Rossi-Forel scale for every 15
kilometers. The same result was also deduced from the fact
that the maximum intensities of several of the earthquakes as felt
in Manila, a distance of 63 kilometers, were from IV to V of the
scale, while in the epicenter, judging from the effects in the
ground and on buildings, they were from VIII to IX. These
same earthquakes, which had an intensity VIII to IX in the
epicenter and IV to V at a distance of 63 kilometers, were also
registered at Taihoku (Formosa) some 1,000 kilometers away,
but not in any more distant observatory.
The reports of previous eruptions of Taal also make mention of
numerous volcanic earthquakes, which no doubt possessed the
same characteristics as those that occurred recently. A curious
fact is noted in these reports; namely, that while in the recent
eruption the meizoseismic area extended 20 kilometers to the
south-southwest, in the previous eruptions it extended to the
north-northeast for about 30 kilometers as far as Laguna de Bay.
From this it is easy to recognize the direction of the rift on which
the volcano originated.
In 1871 a series of volcanic earthquakes occurred on the
voleanic Island of Camiguin, north of Mindanao. These earth-
quakes culminated in the opening of a small crater whose
activity lasted four or five years. They were first felt in
February, and went on increasing in intensity and frequency
until the morning of April 30, when the volcano exploded and
the earthquakes suddenly ceased. The greater number of these
_ shocks were perceptible on the island only, although many were
also heavily felt on the neighboring coasts of northern Min-
danao and southern Bohol, while only four or five, whose in-
tensity in the epicenter was between VII and X, were noticed at
a distance of 250 kilometers.
The following table gives some idea of the number and in-
tensity of the shocks preceding the eruption of Camiguin.
214
The Philippine Journal of Science
1913
TABLE I.—Number and intensity of shocks preceding the eruption of Camiguin.
[Reported from Camiguin.]
| Date Earthquakes. Remarks.
| ARGh: 16 c ence area Two slight earthquakes ____________-____..-
} bY fees ene ee Frequent shocks during day and night_-_-___
| 19) oe eee 0 (Tee RS LS ye See SE One of intensity VIII.
19! 205s eu GOSS sb oe Ae Ee eee One of intensity VII.
| 20252 Eo eo Ea do. 2632 So ee LE EE
QU oer ee Oe Es ee ee ee = One of intensity IX.
! ee a ee ele ee do, Fee ee eae ee eee eee One of intensity VIII.
| 23 tO Sees eae Gosh et % = aah Pe See Eee eee Ree
je Mar. towse 9252. sees. |e es (Oo) FS eee eee seen ee ee
7 Ora ee ee net (sh ee OOias =o ete Fase ee ee One of intensity VI.
bitows =e eee Less frequent; not more than 10 per day ___
baa pti oF ae Se Go) 222 S42. See ee Ee Sede ee Two of intensity VI.
bs Eee eee Sere
10\21- See ee Do.
| 11 to 13
ito ITs fee Less frequent; 4 or 5 per day _______________
18 todO 2 nes More frequent and violent than during pre-
ceding days.
20:0 31-2 =e ee Less frequent; not exceeding 6 per day ___-
APY -ol-t0\29 2a | Frequent during the entire month; number
never less than 6 to 10 per day.
Cas Rea oe. | At 7a. m., with a terrific detonation and
|
|
i
|
emitting a cloud of vapor, rocks, and
ashes, a volcano burst on the north-
northeastern end of the island, only a
few meters from the shore. After this
- explosion, semifluid lava continued to
rise quietly for about three years, build-
ing up a cone approximately 400 meters
high. The ashes of the first explosion
were carried to distances of 200 kilo-
meters. Within a radius of 2 to3 kilo-
meters from the new crater, the destruc-
tion was complete. The earthquakes
ceased almost completely a few days
after the eruption. There was no loss of
life as the people of Catarman, the town
nearest to the volcano and the only one
destroyed by it, had deserted their homes
long before, some having left for other
islands as early as the end of February.
—_
The tectonic type of earthquakes is caused by the sudden
relief of strains, due to contractions and foldings in the crust
of the earth; when these pass the limit of equilibrium and the
modulus of elasticity of the crust, they give rise to rents and
fractures and other sudden movements of more or less severity
depending on the degree of the accumulated strain.
This type
vul, A,4 Saderra Mas6 and Smith: Seismic Disturbances 215
comprehends the greater number of earthquakes felt in all parts
of the world and in particular all those of greater intensity
and extent. To it belong practically all the great Philippine
earthquakes enumerated by Saderra Maso ”° and especially those
which occur in eastern Mindanao, in the Valley of the Agusan,
and on the Pacific coast, regions which appear to be closely
related to the great submarine trough, ‘the Philippine deep”
of 9,780 meters, already referred to. Further on we shall
discuss some of the tectonic earthquakes of greater importance.
The rockfall type embraces the earthquakes of small extent,
which, having their focus or seat of origin at a slight depth,
are brought about by the fall of rock in caves and underground
passages, by landslides, and in certain cases by the settling of
superficial rock masses displaced by tectonic seismic motions. It
appears that this is the predominant type of shocks felt in several
nonvolcanic regions of the Philippines, but earthquakes of this
type are very often extremely difficult to recognize on account
of the distance between the seismic stations and the large extent
of the uninhabited mountainous and forest districts in which
they occur, so that it is impossible to fix the limits of the area
where many of the earthquakes are perceptible. We consider
as typical instances of this class of earthquakes those of 1881
in Nueva Vizcaya. From January to October of that year there
was a continuous series of earthquakes, the maximum of intensity
and frequency occurring in September. To get an idea of this
seismic period, the well-known catalogue of the missionary
Xavert should be consulted. This catalogue takes in sixty-three
days between January and October, and contains the record of
196 earthquakes with the times at which they occurred. Phrases
such as “almost continuous,” “many more,” “the whole day,”
“the whole night” appear twenty-five times in the list, thus
indicating that the smaller earthquakes were not counted.
Abella, who examined the effects of these earthquakes in the
field, found that the meizoseismic area was of very small extent
and that its center coincided with the town of Bambang. The
great majority of the shocks were only perceptible within an
area of 60 kilometers, so that only 5 of intensity VII to IX
exerted any influence beyond the province. Much of the data
supplied by Abella fully confirms his statement which is further
strengthened by an examination of the records of the hourly
* Catalogue of violent and destructive earthquakes in the Philippines,
1599-1909. Manila (1910).
118365——2
216 The Philippine Journal of Science 1918
observations of the Bertelli microseismoscope or tromometer
made in the Manila Observatory.
With the catalogue of Xavert before us, these observations
have been examined again, and we have not been able to find
any movement which could coincide with the Nueva Vizcaya
* earthquakes other than the ones corresponding to the larger
shocks mentioned above and three or four other doubtful ones.
The experience of seventeen years shows us that this tromometer,
still in use at the Observatory, indicates perfectly all earthquakes
of any great extent and of intensity III or greater whose
epicenter lies within a radius of 200 kilometers from Manila.
Abella deduced from these facts that the seat of origin of the
earthquakes must be very superficial and of small extent, and
hence the conclusion that there was little likelihood of any greater
ones happening in the future was fully verified. Such earth-
quakes could not in any way be classed as tectonic, and hence
the author attributed them to volcanic influences, suggesting
that the subterranean forces, which at that time had given
greater activity to Mayon Volcano, might possibly have extended
toward the northwest and affected the Province of Nueva
Vizcaya, some 400 kilometers from Mayon. After an examina-
tion of Abella’s report, it seems evident that the earthquakes
of Nueva Vizcaya belong to the rockfall type; and this opinion
‘is strengthened by a consideration of the topography of the
province. The whole province is an elevated mountainous region
of the nature of a plateau separated from the plains of Luzon
to the south by a line of steep cliffs, while on the west it is
bounded by a series of peaks whose precipitous western slopes
rise abruptly from the deep cafion of the Agno River.
Besides the earthquakes of Nueva Vizcaya, many of those
that take place in the Mountain Province, which comprises the
former districts of Benguet, Bontoc, and Lepanto, possibly are
of the same character. In many parts of this region, particularly
in the western side where coraliferous limestone predominates,
recent fractures and subsidences are to be met with at every
step. The same might be said of other parts of the Archipelago
having a similar geological structure.
DISTRIBUTION OF SEISMIC DISTURBANCES
In the Philippines as in all other seismic regions of the globe,
most earthquakes originate along determined lines which consti-
tute special features of the topography of the Archipelago.
If we add to the Catalogue of violent and destructive earth-
quakes in the Philippines 1599-1909, cited above, the earthquakes
vu, 4,4 Saderra Mas6 and Smith: Seismic Disturbances 217
which have occurred since that time, we have the distribution
of tectonic epicenters “1 as given on the map (Plate II).
The region which has suffered the most from violent earth-
quakes during the past fifty years is without doubt eastern
Mindanao and particularly the Agusan Valley. We have no
seismic data of this region from a period more remote than
1889, but this is doubtless owing to the undeveloped state of
that part of the Archipelago and to the consequent lack of
communication with the outside world. The great deep-sea
trough which exists along the east coast of this part of the
island indicates that many earthquakes must have occurred there
since it first began to form. The same may be said of the coasts
of Samar which also are exposed to the influence of the same
“deep,’”’ and hence that they also are as unstable as the eastern
coast of Mindanao. The principal epicenter of Samar is near
the northeast coast.
In the Island of Mindanao there exist also the following
seismic regions: The Gulf of Davao and the district of Cotabato
between Apo Volcano and Illana Bay; the coast along Illana Bay
and the district of Lanao; the extreme western part of the island
near Zamboanga. Basilan Island and the Sulu Archipelago
are also in a region of great seismicity, although the epicenters
seem to lie in the neighboring seas. The district of Dapitan in
the northwest is affected by a submarine epicenter situated
between Dapitan and southern Negros. All the central part of
northern Mindanao comprised within the district of Misamis
appears to be a region of much greater stability, but the neigh-
boring Island of Camiguin has suffered much at different times
from volcanic earthquakes.
The Visayan Islands, in addition to what has already been
mentioned of Samar, have two regions of great seismicity, Panay
and Leyte. An epicenter lies in the Iloilo Straits between Panay
and Negros, while within the Island of Panay at a distance of
about 30 kilometers from the southeast coast there is another
more important one where originate very violent earthquakes,
but apparently of the rockfall type. In Leyte there are two
voleanic epicenters, one in the southeast and the other in the
north and northeast, and there is probably a rockfall epicenter
to the west close to the Camotes Islands.
The Islands of Cebu and Bohol, and perhaps also Oriental
Negros, may be considered as stable. However, Oriental Negros
“The word “epicenter” is used in the broad sense, as the region where
important earthquakes originate.
218 The Philippine Journal of Science 1918
was very probably in the past the scene of many volcanic
earthquakes, although the data we possess are very deficient.
Volcanic formations more recent than the Pliocene do not occur
in Cebu. :
The principal seismic regions of southeastern Luzon and
adjacent region are those of Camarines, Albay, and Masbate
with three principal and well-defined epicenters—the first along
the central depression of Ambos Camarines, the second to the
north of San Bernardino Strait, and the third in the Island of
Masbate or near its northern and southern coasts. Between
Sorsogon Bay and the Gulf of Albay there is also an epicenter
of small extent.
The southern part of Luzon constitutes the second seismic
region of greater importance in the Archipelago. Four epi-
centers may be distinguished in it; namely, one in the east near
the coast which appears to stretch from the north of the Bay
of Lamon to the south in the sea between Mindoro and Marin-
duque; a second between Mindoro and Luzon; a third in the
China Sea along the coasts of Cavite and Zambales; and the
fourth, which may be called the Manila epicenter, is situated
in the Eastern Cordillera and its spurs, between Laguna de Bay
and the Gulf of Baler. The volcanic epicenters of Taal and
other volcanoes are not reckoned.
Northern Luzon from parallel 16° northward contains 4
extensive seismic regions: That of Pangasinan whose long axis
appears to cross the island approximately from east to west from
Casiguran Bay to Lingayen Gulf, following the edge of the
great central plain of the island. The Nueva Vizcaya epicenter
may be considered as belonging to this central seismic region.
The second region includes the various epicenters of Ilocos
Sur and Norte, some of them in the sea close to the coast,
others probably at the extreme east of the plain or coastal
belt which borders these provinces. The third region, which
is an important one, is situated along the central mountain chain
of the Mountain Province, and extends as far as the Babuyanes
Islands. Within the confines of the extensive Cagayan Valley
there are very important tectonic lines, but they have not, since
1645, given rise to any very great earthquake. However, there
are frequent earthquakes of slight extent and intensity, those
occurring in the north being probably of volcanic origin, while
those in the south are due to epicenters whose influence seems
to decrease.
In the extreme northern part of the Archipelago and outside
the limits of Luzon there are at least two epicenters close to the
vu, A, 4 Saderra Mas6 and Smith: Seismic Disturbances 219
meridian 122° east—one stretching from the volcanic Island of
Camiguin to the northeast coast of Luzon and the other not far
from the Batanes Islands.
In Luzon, therefore, no province is free from the effects of
earthquakes, for although it is true that in some, such as Tar-
lac, La Union, Isabela, Cavite, and Pampanga, no epicenter seems
to exist, still they are affected by the movements which originate
in other provinces.
Seismotectonic lines.—The map, Plate II, gives the location
of the principal seismic areas (red ellipses) of the Islands
(the stars indicating the principal epicenters in these areas)
and the general direction of certain principal mountain chains.
Each figure includes one or more epicenters, and shows the gen-
eral shape and extent of the meizoseismic areas corresponding to
the greatest earthquakes which have occurred within the re-
gion limited by the same. The figures 3, 5, 7, 8, 9, 10, and 20
bear a heavy line to indicate that the earthquakes originating
near the same place have been too many to be specified. ‘Twenty-
five different areas are recorded, and 5 of these (12, 13, 15,
17, and 18) are undoubtedly due in large part to rockfall and
voleanic activity, the other 20, in our opinion, being due to
tectonic causes. This is probably quite contrary to the general
belief regarding the earthquakes in the Philippines. The tec-
tonic areas are 1 to 11, 14, 16, and 19 to 26. The areas of
greatest seismicity are 2, 3, 4, and 21, where at the present time
there is no known volcanic activity and where probably there
has been none since the end of the Tertiary period.
FoJlowing the methods of other students of seismology, we
have connected the various epicenters shown on the map by lines
and have also added a few more of the latter where no epicenters
are indicated. There is a remarkable coincidence between these
lines and the principal lineaments in the Philippines. The va-
rious lines are denoted A—A, B—B, etc., on Plate II so that
they can be easily referred to.
Line A—A, which is drawn through many epicenters, passes through
the nerthwest corner of the Province of Ilocos Norte, follows approximately
the coast west of the city of Vigan, and then cuts across the northwest
portion of Pangasinan Peninsula. It is impossible definitely to state
whether this line marks a fault line which lies along the coast, or is due
to a contact between the recent sediments and the older rocks which here
lie close to the coast, but we are of the opinion from geological studies
in the Province of Ilocos Norte that the latter is true.
There is a very small development of coastal plain in this region and
also rocks of doubtful age which may possibly belong to the Jurassic against
which these very recent sediments abut. There is also a considerable
230 The Philippine Journal of Science 1918
development of raised beaches and raised coral reefs along this coast,
making it plain that elevation has taken place along this line in recent
times. Whether this elevation has been accompanied by differential move-
ment, we are unable to say.
There are no evidences of recent volcanic activity in any part of the
region, but granites, schists, and some very old andesite are present.
Line B—B connects epicenters of northern and southern Luzon, cuts
through Dalupiri, the westernmost of the Babuyanes Islands, then very
closely follows the Central Cordillera southward through the Agno Valley,
thence to the eastward of the Zambales Range, and on through the Island
of Mindoro, where it cuts the latter west of the great volcanic stock of
which Mount Halcon is the principal peak. There is no information with
regard to the rocks on Dalupiri. However, the rocks of the Central
Cordillera in Luzon have a core of plutonic rock, chiefly diorite, flanked
by Tertiary sediments which have been arched upward, and in various
points along the crest of this arch extrusive rocks can be found in
abundance. No volcanic activity now manifests itself in that region, but
it is a region of hot and of salt springs. It is a line along which there
was considerable extrusion of igneous rocks in the past, but there is no
evidence of this now; therefore, seismic disturbances which take place along
this line at the present time are due to displacement along a line of weak-
ness rather than to any volcanic activity. Jt is significant that all of these
points where either past or present volcanic activity is manifested are
found to lie along more or less definite, and in many cases, straight lines.
Line C—C is the next prominent line which runs at right angles to
the B line, and lies either on, or very close to, 4 epicenters. At the upper
end of the central plain of Luzon the mountains rise rather abruptly,
and present a front which has a general east and west direction. It is
possible that this line represents a fault line where the central plain
represents the downthrow side. That area has not been studied in detail,
but it appears as if there is a definite break along that line. In a more
arid region one would expect to find definite escarpments facing southward,
but in a region of high rainfall like the Philippine Islands these escarpments
naturally would very soon be obliterated so that their existence can only
be inferred.”
D—D is a very prominent line which runs along the Archipelago close
to the 122d meridian. It connects the epicenters of the Batanes Islands,
Cagayan Valley, Casiguran Bay, east of southern Luzon and Mindoro,
and west of Mindanao. The northernmost part of the line, outside of
Luzon. follows very closely the Batanes and Babuyanes volcanic chain,
studied by Ferguson * and represented by the cones Yami, Mabudis, Inem,
Iraya, Balintang Rocks, Babuyan Claro, Camiguin, and Didicas. Within
Luzon it passes not far west of Caua Volcano, southward along the
structural Cagayan Valley, following the trend of the Eastern Cordillera
until this turns toward the southwest, or rather when it seems to be
interrupted by the gap forming Casiguran and Baler Bays. From the
latter bay it follows the eastern coast of Luzon and passes to the Mindoro
Sea through the voleanic region of Tayabas Province. Farther on toward
the south it passes fairly close to Tablas Island which is oriented in this
= Herrmann, Raf., This Journal, Sec. A (1911), 6, 331.
* Manuscript report.
vu, 4,4 Saderra Mas6 and Smith: Seismic Disturbances 971
direction, thence to the west coast of Panay, ending finally between Basilan
and Jolo. The general topographic features suggest that this is a very
characteristic tectonic or structural line, although definite geological recon-
naissances are wanting to confirm such a hypothesis.
Line E—£E passes through many epicenters. It lies just west of the
epicenter near Bayombong, Nueva Vizcaya, passes through some epi-
centers near the east coast of Luzon and Lamon Bay and at the south-
east corner of Leyte, and connects with the epicenters located around the
northern point of Surigao Peninsula. This line is seen to conform to the
Central Cordillera of Leyte, to the coast range of Masbate, and the syn-
cline marked by Ragay Gulf; but we are not certain that it conforms
to any particular lineament in Luzon, as it passes through country about
which there is little gevlogical information. There are closely folded
sediments whose strike is northwest-southeast in the eastern portion of
Masbate, and Adams™ has visited Leyte and mapped the cordillera showing
its axis to be approximately along this line.
Line H—H, which has been called “The Taal Volcano line,”” starts
from the northwestern part of Mindoro and in a nearly northeast direction
crosses Taal Volcano, the western portion of Laguna de Bay, extending
into the Eastern Cordillera, east of Manila, and thence runs toward Baler
and Casiguran Bays. The southern portion of this important line from
Mindoro Strait to Laguna de Bay has been accurately identified; * while
the probability of its continuation across the Eastern Cordillera toward
the Pacific has been demonstrated by Saderra Maso. This line passes
through the epicenter of Manila, located in the Eastern Cordillera, east
and east-northeast of this city.
Line F—F is located along the epicenters west of the Zambales coast
and another located a short distance north of Mindoro. It intersects
several of the lines, already mentioned, near Cape Santiago, southern
Luzon. It does not follow any well-marked rift, but follows approximately
the trend of the Bataan coast of Luzon.
Line G—G begins north of Mindoro, passes along the western coast of
Cavite, follows the western border of the Central Plain, across Pangasinan
Province, and thence along the axis of the coastal ranges of La Union
Province. A displacement along this line would account for the earth-
quakes described in charts VI, X, XIII, XV, XVI, XIX, and XXIII” with
their epicenters apparently around or in the northern part of Manila Bay.
It is a contact line between andesite with the alluvium of the central plains
and between Tertiary sedimentaries and igneous rocks in Union Province.
Line J—I cuts through the Dapitan epicenter and three others which lie
close to it. It also follows approximately the long axis of the Island of
Cebu and of the Zamboanga Peninsula, but it is drawn west of the axis
of the Zamboanga Peninsula as it is believed that some earthquakes have
originated from displacements along the west coast of this peninsula.
Line J—J does not nass through any very important epicenter, but
cuts through San Bernardino Channel and follows the east coast of
“This Journal, Sec. A (1909), 4, 339.
* Saderra Maso, Miguel, Bull. P. I. Weather Bur. (1911), 409.
* Pratt, Wallace E., The eruption of Taal Volcano, This Journal, Sec. A
(1911), 6, 63.
“La Seismologia en Filipinas. Manila Observatory (1895).
299 The Philippine Journal of Science 1913
Panay, passing through the center of the Island of Guimaras. We have
drawn a line along these points for the reason that there is a contact on
the Island of Guimaras between recent sediments to the westward and
the igneous rocks found toward the east. It is our belief that the earth-
quakes which have been experienced on the eastern coast of the Island
of Panay are due to displacements along this contact. The continuation
of this line also might explain the trend of this coast of Panay.
Line L—L passes through an epicenter at the southern point of the
Island of Samar and another near the end of the southeastern prong of
Leyte, through the Island of Camiguin on which is located a dormant
volcano, and then follows the trend of Misamis Bay, in Mindanao, and
finally passes close to an epicenter situated in the middle of the sea between
Cotabato and Zamboanga. Formations at the lower end of Samar and
Leyte are but little known, but there is the volcano on the Island of Cami-
guin mentioned above, and where the line crosses Mindanao there is more
or less basalt. Misamis Bay probably marks some sort of a rift in the
formations.
Line M—M passes through many epicenters in the Island of Mindanao.
It intersects the L line at a point east of Dumanquilas Bay, passes through
an epicenter west of Pollok, then follows very closely the trend of the
Cotabato River to the point where the river turns northward, and thence
through an epicenter east of Mount Apo. From here it passes close to an
epicenter located in the sea east of the southeastern point of Mindanao.
Note the agreement between this line and the lower course of the Cotabato
River which is probably more than a coincidence.
Line N—WN connects important epicenters in Camarines, Nueva Vizcaya,
Samar, Leyte, and the northeast coast of Mindanao. It passes through
the narrow Strait of San Juanico, separating Samar from Leyte, and along
the Camarines Valley northwestward it strikes the eastern coast of Luzon,
south of Casiguran Bay. In the Albay Valley it follows the contact line
of the northern volcanic cluster along which the most violent earthquakes
of the Camarines seem to originate, probably due to differential move-
ments between the sedimentaries and the volcanic area, or possibly in the
sedimentaries alone. Farther in the interior of Luzon this line would pass
very close to the Nueva Vizcaya epicenter, but this epicenter is considered
as rockfall.
Line N’—N’ is a secondary one which would pass through the Sorsogon
and northern Samar epicenters. This line nearly coincides with the contact
between the sedimentaries and extrusives, west of Sorsogon; eastward it
follows the alluvial and littoral deposits of the lowland extending from
Sorsogon to Gubat. In San Bernardino Strait and in the northern part
of Samar it nearly conforms to an indentation of the “Philippine trough,”
along which are located some epicenters affecting Catanduanes, Albay, and
northern Samar.
Line O—O begins close to the epicenter at the southern point of Samar,
continues southward to the Island of Dinagat, through the epicenter at
the northern point of Surigao Peninsula, then approximately conforms to the
Matutan Range, through the epicenter near Mount Apo, and finally passes
through the Island of Sarangani. We do not know the composition of
the rocks of the central part of the Island of Dinagat, but on Surigao
Peninsula crystalline schists flanked by Tertiary and recent sediments have
ee. ee ee eee ee ee ee
ME ses —"
eS —————————————— =.
vu, A, 4 Saderra Masé and Smith: Seismic Disturbances 223
been noted. In the neighborhood of Lake Mainit the rocks are volcanic,
although a short distance east of this body of water is a belt of metamor-
phics. In the Matutan Range the rocks are largely extrusives of more
or less recent date.
Line P—P passes through three epicenters and along very important
structural lines in the Archipelago. Beginning at the north, it passes
between the Islands of Catanduanes and Luzon, through Batan Island,
‘south through an epicenter near Biliran Island, and thence through an
epicenter located near the southern end of Leyte. From here it extends
through one in Butuan Bay, thence traversing very closely the structural
line of the Agusan Valley in Mindanao, and finally emerges from Mindanao
near the town of Mati. Very little is known’ about the geology of the
parts of the Archipelago traversed by this line. In the Island of Batan
the rocks are largely sedimentary; however, their strikes do not coincide
with this line at all.
The Agusan Valley in Mindanao is very clearly a structural
valley. What the condition of the rocks is, with depth, we do
not know, as the alluvial filling in the Agusan trough conceals
everything. This line is one of the most important in the
Archipelago, and has been described in previous articles.** In
the first of these Saderra Maso says:
“We call this line the ‘Line of the Agusan -River Valley’ because the
portion of it which lies within the said valley has been the seat of the
greatest number of violent earthquakes which occurred during the last fifty
years.” The first seismic district of importance of this line comprises the
large Gulf of Davao, which is 120 kilometers long and 50 to 70 kilometers
wide. The average depth of this basin is 800 meters, increasing, however,
toward southeast in such manner as to exceed 1,650 meters west of Cape
San Agustin. * * * To the west of the gulf rise the gigantic Apo
Volcano, the Matutun and several other cones of less importance, which
constitute the northern boundary of the volcanic zone extending, as it
seems, from Mount Apo as far as the Celebes, * * *,
“The extensive valley of the Agusan River runs from south-southeast to
north-northwest, almost parallel to the east coast of Mindanao, * * *,
The entire bottom of the Agusan Valley consists of marine sediments con-
taining an abundance of recent shells: only at the mouths of the water
courses, which descend from the mountains bounding it east and west,
is found gravel containing well-worn pebbles of andesite and other igneous
rocks. Every geologist who has visited this part of eastern Mindanao
received the same impression, to wit, that its emersion from the sea is of
quite recent date, and its elevation is still increasing. Some of them
assigned the post-Pliocene period as the epoch of the formation of the
sediments found in the Agusan Valley, * * *. This valley and the Davao
Gulf appear to be portions of one and the same synclinal.”
Line Q—Q begins near Placer on the northeast coast of Surigao
Peninsula, and passes through an epicenter in Butuan Bay and the
* Saderra Maso, Miguel, Bull. P. I. Weather Bur. (1910), 283; (1911),
225.
* Italics are ours.—Authors.
DPA The Philippine Journal of Science 1918
northern course of the Rio Grande Valley. This line seems to be necessary
to explain the anomalous course of this river. Line O and line M seem to
explain this satisfactorily.
Numerous other lines might be suggested, but we have included
all for which we have any geological basis and a few others as
suggestions.
DISCUSSION OF IMPORTANT EARTHQUAKES
In discussing the various important earthquakes, little will
be said about those previous to 1870, save the greatest which
occurred in 1645, but we shall consider the entire series
represented by the charts published in La Seismologia en Fili-
pinas, and discuss most of them separately.
Earthquake of 1645, Luzon (3-9).°° This earthquake com-
pares favorably in magnitude with the greatest mentioned in the
history of the world; its meizoseismic or epicentral area was
not less than 490 kilometers from north to south; that is, from
the southern coast of Batangas and Tayabas to the northern
part of Cagayan. On the western coast it seems to have been
of less intensity, at least the chronicles of the time are silent
about its effects in these parts, while they deal very much
with the destruction caused in Manila and neighboring provinces
of the south, east, and north, and the tremendous effects produced
as far north as Lalloc. in the Cagayan Valley, and in the east-
ern part of the Central Cordillera; that is, in the Mountain
Province. That such an earthquake was due to tectonic move-
ments, there cannot be the slightest doubt; furthermore, it is
very certain that its origin was along a north and south line
and that this line was within the Island of Luzon and not
beyond its eastern periphery; it may be reasonably supposed
that it was along the seismotectonic line D—D. The question
arises whether the dislocations which then occurred along that
line or fault were of such proportions as to be responsible for
the many singular topographi¢ features now existing along it
in the Provinces of Nueva Ecija, Nueva Vizcaya, and Isabela.
Moreover, as the origin of that earthquake seems to have been
very close to the city of Manila, our opinion is that some
dislocations occurred at the same time along the fracture
represented by the line H—H. Similar occurrences of lines
crossing each other are frequent in severe earthquakes. For
example, the earthquake which occurred in 1870, having its epi-
center in the northwestern portion of Luzon, apparently was
* Figures refer to Plate II and indicate the location.
Ee ——
ae ee ee oe
vur, A,4 Saderra Mas6 and Smith: Seismic Disturbances 225
of tectonic origin, and might be explained as due to a displace-
ment along the line A—A.
The great number of earthquakes which occurred in 1871
were of volcanic origin, having as their epicenter the Island of
Camiguin. The destructive area includes Camiguin, Bohol, and
that part of Mindanao known as Misamis; also, the southwest
corner of Leyte.
Earthquakes of July 11 (3) and of November 5, 1871 (17),
are both clearly of tectonic origin. The destructive area in the
case of the first comprises the Central Cordillera of Luzon; and
that of the second is located along line H—E or, perhaps, line
P—P.
Earthquake of December 29, 1872 (7). The destructive area
comprises roughly that portion of Luzon adjacent to line F—F,
but it is possible that these disturbances originated from the
Taal Volcano fracture. No eruption of Taal Volcano is recorded
for this year.
Earthquakes of August 25 (22, 23) and October 16, 1874
(8, 9). In the former, the destructive area comprises the
Zamboanga Peninsula, and is clearly tectonic, probably due to
dislocations along the line J—J; in the latter, the destructive
area comprises the region east of Manila Bay, more or less
elongated north and south, and possibly has some connection with
the line D—D. Taal Volcano was probably not the cause of this
disturbance.
Earthquakes of May 1 (7, 8) and of July 5, 1877 (10, 11).
The former was felt over most of southwestern Luzon, probably
emanated from Taal Volcano, and probably was due to move-
ments propagated along the line G—G which follows the western
limit of the central plain of Luzon. The latter may have been
of volcanic origin, as the whole southeastern volcanic region is
comprised in the destructive area, or it may have had its origin
in some movement along the line marking the Philippine “deep”
(X—X).
Earthquakes of August 13, 1878 (7, 8), and of July 1, 1879
(17). The former seems to have had its epicentral area located
near Manila Bay, resulting from disturbances along the line
G—G mentioned in the last paragraph. The latter had its
destructive area in northeastern Mindanao and Surigao Penin-
sula, and was possibly due to the Agusan line, but more likely to
displacements along the line H—E.
Earthquakes of July 14 and 25, 1880 (5, 6, 8, 9). The
destructive area shown on this chart indicates that the disturb-
ances originated somewhere in the Eastern Cordillera of Luzon.
2°26 The Philippine Journal of Science 1913
Two originated along line H—H,; and the third, in the eastern
part of Laguna Province, along line D—D.
The earthquakes of July 25, 1880 (5, 8, 9), show that the des-
tructive area conforms pretty closely to that shown in chart VII.
These should both be classed as tectonic.
Earthquakes of May 15 (4, 5, 6, 8) and of July 11, 1881
(15). In the case of the former, the destructive area is confined
to the Eastern Cordillera in north-central Luzon, and is clearly
of tectonic origin. That of the latter had its center on the
Island of Guimaras, just south of Panay. This is clearly of
tectonic origin, and it was probably due to displacements along
the contact between the Tertiary sediments of the western half
of the island and the igneous rocks of the eastern half.
The earthquake of July 16 in Ilocos Norte Province, Luzon
(2), was undoubtedly due to disturbances along the line A—A.
Earthquakes of September 10, 1881 (5). The area of destruc-
tion during these earthquakes was very local, being in the south-
ern part of Nueva Vizcaya, and may be attributed to purely
local causes, possibly rockfall.
The earthquake of September 30, 1881 (4, 5), again centers
in Nueva Vizcaya, and was probably of the same origin as the
previous one.
Earthquake of April 30, 1882 (7, 8). The destructive area
was very local and was centered just north of Manila Bay, but
more to the westward near the contact between the material
of the valley floor and the volcanic rocks of the Zambales
Mountains, hence there seems to be some reason for conjecturing
that it is due to tectonic causes. On September 12, a very
similar earthquake occurred in the same region.
Earthquakes of July 25 (7, 8) and 28 (2), 1882. During the
former, the epicentral area is situated between Taal Volcano
and the China Sea, and hence may be of volcanic origin. That
of July 28 is located along the Cordillera of Luzon in the
northern part, and hence may be called tectonic.
The earthquake of September 11, 1882 (7), has its focus
somewhere near Taal Volcano.
Two earthquakes on September 17 (10) and 21 (2, 3), 1882.
In the case of the former, the destructive area is centered about
the southeastern volcanic cluster in Luzon. The latter has its
epicenter in north-central Luzon, but the longitudinal axis of
the destructive area runs slightly north of east. We do not
know of any prominent structural line in that region running
in that direction. The course of the Abra River, where it makes
a sharp right-angled bend to the west in the latitude of Vigan,
"ee ee
vu, 4,4 Saderra Mas6 and Smith: Seismic Disturbances ea
is suggestive of some prominent earth lineament. On Sep-
tember 6, 1862, October 9, 1901, and May 25, 1907, very similar
earthquakes occurred in the same region, having their main line
of propagation in nearly the same direction.
On October 10, 1882, there was an earthquake, the destructive
area of which centers about San Miguel Bay in southeastern
Luzon (10). Very little is known about the formation on the
Caramuan Peninsula, so that we are unable to give any theory
for the disturbances here.
Two earthquakes of February 10 (3, 4) and of July 14, 1883
(10). The former originated in the Province of Nueva Vizcaya,
and probably was due to causes already mentioned. In the
latter, the earthquake clearly originated from volcanic disturb-
ances, as the destructive area comprises the southeastern
voleanic region of Luzon.
Earthquake of July 27, 1883 (7, 8), is clearly volcanic, or
at least related to the fracture passing through Taal which is
included in the destructive area.
Earthquakes of January 10 (10) and March 22, 1884 (5).
Both of these were very likely of tectonic origin; one had its
epicenter in the northwestern portion of Pangasinan Province
where there is no sign of recent vulcanism. This probably is
due to displacements along line G—G. The second one had its
epicenter near the southeastern volcanic region, but on the west
side of the peninsula, where there is a slight uplift of Tertiary
sediments, which may indicate this to be due to tectonic causes.
Lately, in 1907, there occurred two destructive earthquakes in
the same region, probably due to the same causes.
Earthquake of April 20, 1884 (7). This was not destructive,
but, according to the distribution of the effects of the earthquake,
it probably was of tectonic origin and can be attributed to
displacements along line G—G.
Earthquake of October 29, 1884, had two destructive areas
(6, 8, 9) more or less separated, the epicenter of one being just
north of Laguna de Bay and the other just north of the south-
eastern volcanic cluster (10). As there is no sign of a volcano
at present north of Laguna de Bay, it is probable that the line
H—H runs through this region.
Earthquakes of December 17 and 24, 1884 (5, 13), are clearly
of tectonic origin. In the former, the displacement undoubtedly
took place along the line C—C; and that of the latter was
probably due to movement along the line which runs northwest
and southeast, through the straits between Leyte and Samar,
which is indicated by the line N—N.
298 The Philippine Journal of Science 1913
Only one earthquake (2, 3) is shown on this chart, and that
seems clearly to have originated along line A—A.
Earthquakes of July 23 and 24, 1885 (5, 6). The first seems
to have its epicenters northwest of Dapitan Peninsula. In 1897
another destructive earthquake occurred under the sea in the
same region due to the same origin. It is very likely that this
is of intertectonic origin, due to line J—J. There is no record
of any volcanic demonstration emanating from the Dapitan
Peninsula. It seems very clear from the great lineal extent of
the destructive area of this earthquake north and south that
the line J—J is responsible; hence this would be called tectonic.
The earthquake of the 24th of the same month seems to be
similar to that of December 17, 1884.
Earthquake of November 16, 1885 (7, 8). This is clearly of
voleanic origin as it seems to have been most generally felt in
the southwest volcanic region of Luzon.
Earthquake of November 19, 1885 (5), is similar to that of
July 24, 1885, and is also tectonic.
Earthquakes of April 10 (15) and August 2, 1886 (7). The
first one is undoubtedly tectonic and is connected with line J—J.
The second may be in part volcanic, but, on account of its
extension to the northwest, we believe that it can be referred
to the tectonic line G—G.
Earthquakes of February 1 (3) and 2, 1887 (14). The former
seems to have been localized in north-central Luzon and may
or may not be tectonic. It is possible that this disturbance was
due to rockfall. The latter earthquake seems to have affected
the whole Island of Panay, and was probably due to rockfall,
because a recent examination of this island has shown that
landslides of considerable magnitude are of frequent occurrence
on this island. In these two regions violent earthquakes of like
character and probably of the same origin occurred in 1902
and 1904. :
Earthquake of March 24, 1887 (10), was unquestionably of
volcanic origin due to disturbances in the southeastern volcanic
cluster of Luzon. The two earthquakes here shown of June
19 (6, 8) and October 1, 1887 (10, 11, 12), respectively, were
only light ones. The second one emanated from the same
voleanic region as the earthquake just mentioned, but that of
June 19 was undoubtedly of tectonic origin in the Eastern
Cordillera.
Earthquakes of June 27 (20, 21), May 3 (2, 3), and August
19 (4), 1888. The first is undoubtedly tectonic as we know of
no voleanoes anywhere in that portion of Mindanao, but we
vu, a, 4 Saderra Mas6é and Smith: Seismic Disturbances 999
also do not know enough about the geology of that portion to
say with any certainty that there is a tectonic line running
at an angle to the main Agusan line. The reader is referred
to an article by Saderra Masé * on this subject. On Plate VIII
of that paper the author has indicated the several epicentric
areas near the “Philippine deep.” Most of these areas are
elliptical, with their long axes extending north and south or
northwest and southeast, but one of these has its long axis
extending slightly north of east and south of west. The second
seems to have had its center in the Cordillera of northern Luzon.
The third is a clear case of movement along line D—D, or the
Cagayan line.
Earthquakes of January 1 (17), February 5 (22, 23, 25), May
26 (7, 8), and of October 6, 1889 (17, 20, 21). The first is
clearly due to movements along line H—E; and the second, to
movements along line M—M. The third without question is due
to the lines or fractures H—H and F—F. The fourth affected
the whole Agusan Valley region, and the eastern coast can be
attributed to the “Agusan line,” or rather to the Pacific
structural “deep.”
In addition to the above list of earthquakes in the article
La Seismologia en Filipinas, we desire to add the following
important earthquakes.
Earthquake of 1892, Pangasinan, Benguet, and La Union
Provinces (5). The nature of this earthquake seems to be
tectonic beyond doubt, since it occurred in a region where no
recent volcanic formations are to be found. The northern part
of its epicentral area comprises the uplands of Baguio, where
the tremendous upheavals which occurred in recent geologic
periods are clearly evident. Almost in the center of the epi-
central area rises Santo Tomas, an andesitic block mountain
due in part to faulting, while in the southern part lies the
alluvium of the Pangasinan plains. It seems highly probable >
that the cause of this earthquake can be found in some important
dislocation which occurred near the Santo Tomas mountain
mass. This epicenter belongs to line C—C.
Earthquake of 1893, Agusan Valley, Mindanao (20), is un-
questionably the greatest which has occurred in this region
during the last three centuries. The permanent sinking of part
of the floor of the valley and the faulting on the divide between
the headwaters of the Agusan Valley and the Gulf of Davao
suggest a folding movement of the Eastern Cordillera as a
* Bull. P. I. Weather Bur. (1910), 279.
230 The Philippine Journal of Science 1918
whole or a slip toward the east in connection with the changes
which possibly occurred in the deep trough running along the
east coast. Therefore, this earthquake must be classified as
most typically tectonic, as it occurred along a most definite
structural line.
Earthquakes of 1897. The fearful happenings of this year
bring to the mind the somewhat fabulous occurrences of 1641,
when earthquakes in Luzon occurred at the same time as erup-
tions in Mindanao, Jolo, and Sanguir. During this year destruc-
tive tectonic earthquakes were felt in northern Luzon (2),
northern Samar (11), Masbate (12), and eastern and western
Mindanao (19, 22, 23, 24), while as a climax Mayon Volcano
had one of its worst eruptions. The most typical and important
of these earthquakes was the one occurring in western Min-
danao. Its origin or epicentral area seems to have been under
the sea, west of Zamboanga Peninsula, where two very important
iines, J—Z and D—D, intersect. It must be considered as one
of the most memorable of Philippine earthquakes on account
of the most extraordinary seismic wave ever noticed in the
Archipelago. Furthermore, it seems to have been connected
with the rising of some temporary islands near the northwest
and northeast coast of Borneo. ©
Earthquake of 1902, Illana Bay, Mindanao (23), shook heavily
the districts of Cotabato and Lanao; its epicentral area coim-
prised part of the bay, where the telegraphic cables were broken
and buried under mud; the eastern coast and plain of Cotabato;
and the northern coast with the uplands of Lanao district as
far as the lake. In this last region there had been great volcanic
activity during the Tertiary period, as is shown by the basalt
flows which cover it and by some old volcanic cones rising toward
the south and east; but, during the historic period, only one
doubtful eruption is reported. Consequently, considering the
’ wide extension of this earthquake and its effects upon land and
the bottom of the sea, it should be classified as tectonic and
connected with line M—WM.
Earthquake of November 8, 1912, Sorsogon. The meizo-
seismic area of this earthquake where it was felt with intensity
VIII-IX, causing considerable damage, was rather small, being
only some 35 kilometers long by 10 kilometers broad. It took
place in the town of Sorsogon, the mountains to the north and
northwest, part of the coast toward the west, and the lowlands
extending toward the south-southwest as far as Gubat. Its
center nearly coincides with the contact between the volcanic
vul, a, 4 Saderra Masé and Smith: Seismic Disturbances 931
and the alluvial formations. Plate III shows the isoseismals
of this earthquake and the geology of the region.**
The Sorsogon epicenter lies on the secondary seismotectonic
line N’—WN’ which future events may prove to be, as it has been
stated elsewhere,** the continuation or a branch of the Camarines
line N—N.
It has been suggested by Mr. Wallace E. Pratt that this earth-
quake was due to differential movement between the igneous
and the sedimentary block to the eastward and northward as
shown on the map. This seems to be highly probable.
PRACTICAL CONSIDERATIONS
1. The fact of the instability of the earth’s crust has been
proved time and again both by tremendous catastrophes and by
laboratory experiments. It has been demonstrated that many
of these devastating earth movements take place along definite
lines of weakness in the crust. The location and extent of
these lines can usually be fairly accurately determined by a
geological examination.
2. The points of intersection of such lines are dangerous as
can be shown by an examination of the Province of Calabria
in Italy.*4
8. Volcanoes are only incidental phenomena, and are results
rather than causes. They are usually found to be lined up along
some rift line.
4, Points of danger in the Archipelago are:
a. Along the Taal rift line from the town of Lemery to Los Bajos
on Laguna de Bay, and possibly farther to the northeast.
b. All “made” land and recent alluvium. The California Earthquake
Commission (1908) reported that the intensity of the shocks and
the destruction were greatest and the amplitude of the waves
longest in the “made” ground.”
c. The Agusan Valley, Mindanao.
d. The Straits of San Juanico.
e. The district northeast of Manila near the east coast and northwest
of the Island of Polillo. Three prominent lines intersect in two
places close together in this region.
f. That part of Batangas Peninsula which ends in Cape Santiago.
* Adams, G. I., and Pratt, W. E., This Journal, Sec. A (1911), 6, 449.
* Bull. P. I. Weather Bur. (1912), 447.
“ Hobbs, W. H., Some principles of seismic geology, Beitrégen zur
Geophysik (1907), 8, 224,
* Report of California Earthquake Commission. Washington (1910).
118365——3
232 The Philippine Journal of Science 1918
5. Types of structures best suited to Philippine conditions:
a. Bamboo houses. All the parts of a bamboo house are tied together
with rattan. These houses are strong, elastic, and light, and
behave like immense baskets.
b. “Strong material,” locally used to distinguished wooden, well-nailed
houses from bamboo structures. Floor joists well anchored.
c. Sand-lime brick tied to steel frame should be cheaper than concrete,
and in case of warping walls can be removed easily and new
steel put in.
d. Reénforced concrete, perfectly safe if properly made, but expensive
and apt to receive permanent warping and fissuring™ from the
twisting motion of some earthquakes.
Ordinary brick walls with roof of unanchored tiles make one
of the worst possible types of construction as demonstrated at
Messina.
6. The necessity of geological examinations of all dam, pipe line,
and bridge sites should be emphasized. Tremendous damage
was done to these kinds of engineering structures in the San
Francisco earthquake. It is well known that the breaking of
the water mains by the earthquakes left the city at the mercy
of the fires which shorily broke out.
7. The Harbors of Cebu, Iloilo, and Zamboanga, owing to
their approximating the shape of a funnel or double funnel, are
more or less in danger from tidal waves.
8. Manila Harbor, owing to the comparatively small entrance
and rapidly widening basin, should be entirely safe in this
respect.
SUMMARY AND CONCLUSIONS
There is a close relationship between seismic disturbances and
geologic structure.
The majority of earthquakes are of tectonic origin, in the
Philippines, at least.
Volcanoes are secondary phenomena.
The area of greatest seismicity in the Archipelago is in the
Agusan Valley, Mindanao.
There is a close relationship between the orographic and other
geomorphic lines and the lines connecting the principal epicenters
in the Archipelago.
Seismic disturbances. can be studied and disasters can, to a
large extent, be avoided.
*In the severe Sorsogon earthquake, November, 1912, a new school-
house of reénforced concrete and concrete blocks was considerably damaged
in both portions; the reénforced concrete portico sustained more or less
fissuring.
ee
ILLUSTRATIONS
Sketch map of the Philippine deep.
Harthquake map of the Philippine Islands.
telation of the Sorsogon earthquake to the geology of that region.
fae? 233
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| pimestone with Sphzroidina dehis- |_-----------.--------------------------- fees
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raminiferal limestone and tuffs | Manchar siwaliks (vertebrate fossils)| Pontian.
vith andesitic sills.
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foraminiferal tuffs.
eal) (Gralie $4 oe Se ae ea saa nes Aquitanian.
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neutli, Ostrea multicostata.
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aed oe a eee ee ed PPR 8 7 TENT eke SE Soe Oe ee ee Suessonian.
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Inouye, and Smith.
TABLE III.—Tentative correlation of the Far Eastern Tertiary."
Series. Philippines. Borneo. Java. Formosa. Japan. New Hebrides. India. Europe
Pliocenes sas ase = Raised coral reef limestone_-#_--------------- Dimestone=- === =2=== == 2-22 === == Raised coral reef limestone ______ | Marine beds with Mytilus, Conchocele_| Limestone with Sphwroidina dehis- |____..____-..----______________________ eae
WY Saale CS cens. Plaisancian.
Pre-Pliocene ------------ Limestone and marl beds. Fossil elephants’
teeth reported from two localities in Lu-
zon and one in Mindanao: Foraminifer- & 3 [Beds containing fossil plants and | Foraminiferal limestone and tuffs | Manchar siwaliks (vertebrate fossils)| Pontian.
al marls of Karrer probably belong here LETS GENE DN Soo cree oc oe ses Re Sie cea oa sias Sroo acon soe cecoec those containing numerous speci- with andesitic sills.
also. lI mens of Carcharodon megaladon.
Miocene: Wpnerilimestone withismall tepidocyclines: (eee H with small Lepidocy- Timestones with small Lepidocy- | 7 imestones with Lepidocyclines | Limestones with Lepidocyclines, Li- | Limestones with Lithothamnium, |........--..-.------------------------- Burdigalian.
Upper--------------- clines and Lithothamnium. clines. and Lithothamnium. thothamnium. Foraminiferal tuffs.
Limestones with Cycloclypeus. Volcanic tuff and sands, with
Cycloclypeus. Limestones with
Lepidocyclines and Cyclocly-
. d shal ith Vi Uu S ee d hal 1 Sand hales: ] ith Gaj --------------2-------------------- Aquitanian.
IMiddle==—"=s2 3-222 Sandstones and shales wit CUP CROC LOS Cem ern re ene reer es OE es ANOS CONES ease oe ae ee Soe ee Sandstone, shale, coal seams _-____ Bnd stones ae esricon seams as Rete RE eae ee Pres aa Arenaceous) groupsmVrcdrua eer
Coal seams. Viearya callosa in the overlying neuili, Ostrea multicostata.
beds.
MOWw er. sete sot Se Middle limestone, with large Lepidocyclines -| Group G_____.-_---_-------------- Htagehbrecheux 22-3525 ee oS ee ee ee | a te a ee ee | nes ee ee ea aE ee ee Cee Argillaceous group_--__-----_-----__-
Oligocene_--------------- Lower limestone with Nuwmmulites. Coal | Group Dand C with Nummulites. | Limestones with Nuwmmulites___|________________---__-__-----___--__|-----_--------_-_----------------=----==|----=--- === ------ == == Nari formation with Orbitoides pa- ie
seams. pyracea. SriAn.
Group B with Operculina ________ ‘li ith 1 Toft. ith oy (on Kirth ith Nj it aay Bartonian.
TMS ee Some coal seams. Exact position doubtful__ Fi : Quantzosemare nlite siwaib ke Coa) iy | eee eee eee eee uffs wi ummulites NOTES C0 | Oe irthar wi ummulites an alll taitetane
Group A with Orthophragmina sears: GD), Bona
omphalus.
(Win cent arin ee eer tre Sm ren eens eS LE See US a Ree AS ee eee ee eee Sandstone; shales} coaliseamsyascerses pase eee een re ere Ranikot)= 2230 oe oo sceoeeso se een eee Suessonian.
COE Sere Uae a iawe bec Segui We Awe 5 Sead seo tt ee iy et ee Se RAE oe hg eo ees mee cM pares re eee SU ee Ee | eet) ev Yoh ee ae Thanetian.
a en re a mee ee a Ee ok ee ome we i a ee ear ee | ee 8 eS (Oe ee i ee | Montian.
118365 Ain : - rep .
8 The authorities drawn upon for this table are: Becker, Koto, Verbeek, Martin, Douvillé, Chapman, Oldham, De Lapparent, Fukutome, Inouye, and Smith.
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CONTRIBUTIONS TO THE STRATIGRAPHY AND FOSSIL INVER-
TEBRATE FAUNA OF THE PHILIPPINE ISLANDS
By WARREN D. SMITH
(From the Division of Mines, Bureau of Science, Manila, P. I.)
Twenty plates
CONTENTS
INTRODUCTION. I. STRATIGRAPHY—Contd.
J. STRATIGRAPHY. Fossil Localities.
Philippine Stratigraphy and Correlation over the Far East:
General Statement. Japan, Formosa, Borneo,
The igneous rocks. Java, New Hebrides, etc.
The metamorphic rocks. Conclusions.
The Sedimentary Series. II. PALEONTOLOGY.
The Tertiary. List of Species.
The Pre-Tertiary. Description of Species.
Comparison with Java.
INTRODUCTION
This paper is intended to serve as an introductory contri-
bution to the large subjects of the paleontology and stratigraphy
of the Philippine Islands. Much more material than is given now
awaits time for the necessary studies. I have been gathering
this material during eight years of exploration in the Philippine
Islands when most of my time has been spent in economic work;
hence, I cannot claim to have done more than open the subject.
The generally~ poor state of petrifaction as found in those
specimens which have been obtained, the limited library facilities
in Manila in this particular subject, and the fact that consecutive
time has not been available for study will account for some
of the more or less fragmentary discussions. Twelve new
species and 2 new varieties are described. It might have been
expected that a larger number of new species would have been
described, but where there has been the least doubt I have
referred the form to a species already described. I have in-
cluded generic descriptions translated from Zittel,t and I have
omitted specific descriptions of old species. I have done this for
the following reasons: For the general student in paleontology
*Handbuch der Paleontologie. Munich (1876-1880), 2 and 4.
235
236 The Philippine Journal of Science 1913
the generic description is often sufficient, and as this monograph
may possibly be the basis of future paleontologic work in the
University of the Philippines I have followed this procedure
for the convenience of students. If more detailed information
regarding the species is desired, the student can go to the
original descriptions, using the references furnished in the text.
Where good plates are available, descriptions are rarely needed.
The first part of this paper gives a general summary of the
lithology and distribution of Philippine rocks with more detailed
discussion of the Philippine sedimentary series, making com-
parisons with Java, particularly, and with other neighboring
islands. There exists a very close similarity between the
stratigraphy of the Philippines and Java, and nearly every
species can be duplicated in collections from Java now deposited
in the Geologisches Reichs-museum in Leiden. The same might
be true of Borneo and Celebes, but geological investigations have
not proceeded far enough in those islands to be of as much
assistance as those that have been carried on in Java.
I have made the determinations of the species in this paper
‘under considerable difficulties, for when the work was started
there were practically no books on paleontology in Manila, and
even at the present time we have only a few of the important
works. The existing Spanish collections of fossils and living
shells in Manila were almost useless, and there was only one
fossil from the Philippines, Vicarya callosa, which had been
figured, and that in a short preliminary brochure by K. Martin
of Leiden.
In 1908 I took a portion of the Bureau of Science collection
to Leiden and compared the specimens with Martin’s Javan types
and the Semper collection of Philippine fossils as yet undescribed.
From Leiden I proceeded to London where I worked over con-
siderable material and studied the literature in the British Mu-
seum of Natural History.
Before undertaking this work I offered several groups of
fossils to different specialists in the United States to be worked
up, but met with no success, these men invariably giving the
excuse that they had more than they could do at home. I met
with better success abroad, and Professor Douvillé of Paris has
identified the greater part of our foraminiferal material, and
his results have been published.?
Rather than delay the rest of the work longer, I have proceeded
with my own limited resources with the hope that the results
? This Journal, Sec. D (1911), 6, 53.
rr
VII, A, 4 Smith: Fossil Invertebrate Fauna 937
will have some value. My aim has been to put on record,
even though it has to be revised later, what we have in the
Philippines in this department of science.
I wish to make special acknowledgment of assistance rendered
to Dr. K. Martin, professor of geology and head of the Geo-
logisches Reichs-museum in Leiden; to R. Bullen-Newton, Esq.,
paleontologist, British Museum; to Prof. H. Douvillé, pro-
fessor of paleontology in l’Ecdle de Mines, Paris; to Dr. William
H. Dall, curator of conchology, United States National Museum,
Washington.
PART I. STRATIGRAPHY
PHILIPPINE STRATIGRAPHY AND GENERAL STATEMENT
The same general groups of rocks exist in the Philippines as
are found in other parts of the world. There are deep-seated
igneous rocks, intrusives, and volcanic flows; there are metamor-
phic rocks and sediments, both consolidated and unconsolidated.
Although the Philippine Islands may appear to the layman to
be almost entirely volcanic, there is a wide distribution of the
sedimentary series. In the latter the fossils are found, and
consequently we can pass rapidly over the discussion of the
igneous and volcanic rocks.®
Andesites.
Hornblende andesite.
Pyroxene andesite.
Hornblende-pyroxene andesite.
Olivine-bearing pyroxene ande-
site.
Hornblende-biotite andesite.
Basalts.
Dacites.
Leucite tephrites.
Granite.
Syenite.
Quartz diorite.
Plutonic and intrusive...............-2..:----/ seas
Gabbro.
Peroxenite.
Peridotite.
HE SEETI SEV Core ey nee eee Ee
* Teneous rocks of the Philippines will be found described in the following:
Becker, G. F., Geology of the Philippine Islands, 21st Ann. Rept. U. S.
Geol. Surv. (1901), pt. 8, 493; Smith, W. D., The essential features of the
_ geology of the Philippines, This Journal, Sec. A (1910), 5, 307; Iddings,
J. P., The petrography of some igneous rocks of the Philippines, This Jowr-
nal, Sec. A (1910), 5, 155.
938 The Philippine Journal of Science 1913
Andesites and diorites are the predominant rocks in the Phil-
ippines. This will give an idea of the composition of the sedi-
‘ments, which, of course, have been derived: largely from the
erosion of these rocks.
THE SEDIMENTARY SERIES
The Philippine sedimentary formations consist of limestone,
sandstone, shales, conglomerates, volcanic tuffs, and cherts.
This group includes the usual general classes to be found in
any part of the world. The following list shows the order of
their abundance: (1) shales and clays; (2) limestones; (3) sand-
stones and conglomerates; (4) tuff (waterlaid and subaérial) ;
(5) cherts.
Besides these there are numerous subaérial deposits, piedmont
deposits, etc.
Shales and clays.t—The shales predominate in the coal meas-
ures, varying in composition and texture from almost clay to
sandstone and usually are gray, but in places they may be buff
and yellow. They make up many hundred meters of thickness
of strata in the Philippines. Their greatest development is in
the Visayan Islands, where the most extensive coal fields also
occur (Plate I).
The clays vary in composition from very impure varieties
high in iron content to those which are practically pure kaolin.
However, the latter are limited.
The clays of the coal measures usually contain too much free
silica and not enough combined silica to be suitable for cement
manufacture.
Besides the shales of the coal measures there are thin beds
of shale intercalated in the great tuff series near Manila. I
have found a few plant remains in these shales, and these
indicate that this formation is comparatively recent. Surpris-
ingly few plant impressions have been found in the coal measures.
Certain shale horizons show a great abundance of Foramini-
fera and other microscopic forms. On these I have done little
work. Karrer® has described 27 new species of these minute
organisms from the shales near Iba, Zambales, Luzon. These
comprise species in the following families: Uredille, Milliolide,
*No attempt is made here to describe these formations in detail as the
numerous geologic papers already published by this Bureau furnish these
data.
*Karrer, Felix. Die Foraminiferen der Tertiaren Thone von Luzon, ap-
pendix to Fragmente zu einer Geologie der Insel Luzon, von Drasche, R.
Wien (1878).
VIII, A, 4 Smith: Fossil Invertebrate Fauna 239
Lagendez, Nodosaride, Glandulinide, Frondicularide, Pleurosto-
mellidz, Cristellaridzee, Polymorphinide, Textularide, Globigeri-
nidx, Rotidz, and Polystomellide. It can be seen from this then
that minute forms like these are abundant. Similar shales in
Cebu and on Batan Island are likewise rich in Foraminifera.
Limestones.—These are for the most part coralline or foram-
iniferal. They are very pure chemically, the magnesia content
being generally less than 2 per cent. On Guimaras Island a
slightly higher percentage has been noted in some samples.
They vary in color from cream-white through buff to black.
They have an extensive development, and vary in age from
Oligocene to Recent.
The recently elevated limestones which are very widely dis-
tributed in the Philippines are for the most part simply raised
coral reefs being largely composed of triturated and recemented
coral fragments, although in places the reef has been little
disturbed. Great masses of astreas, helioporas, meandrinas,
turbinarias, etc., intact in the center of a mass of indurated
limestone, are very common. These reefs occur at various eleva-
tions from sea level to more than 2,000 meters. The raised
reefs have very much in common with those in many parts of
the Pacific Ocean and China Sea region.* The best development
of these raised reefs is along much of the Cebu coast, the coast of
Ilocos Norte, in the limestone just west and north of Baguio in
central Luzon, and near the north coast of Mindanao.
Becker long ago called attention to the mantle of coral lime-
stone which must have entirely covered Cebu Island at some
past time. It is possible for one to walk from the living reef
fringing the shore to the highest pinnacle of the island in the
Central Cordillera and, except for occasional short breaks where
some stream has cut down through the mantle, to keep always
on the limestone. This means that there is apparently no break
between the present and the Pliocene. But this is what one
would expect.
Other phases of the limestone are frequently encountered as
a recemented rubble formation, well shown in the lower narrows
of Danao River in Cebu.
°On this subject the following papers should be consulted: Newton, R.
B., and Holland R., On some fossils from the Islands of Formosa and Riu-
Kiu, Journ. Coll. Sci., Imp. Univ. Tokyo (1902), 17, art. 6; Chapman, F.,
On the tertiary limestones and foraminiferal tuffs of Molekulas, New
Hebrides, Proc. Linn. Soc. N. S. W. (1907), 32, pt. 4; Becker, G. F., 21st
Ann. Rep. U. S. Geol. Surv., Washington (1901), pt. 3.
240 The Philippine Journal of Science 1913
The soft marly limestone of Cebu is best developed at Naga,
Cebu, where good raw cement materials occur. Much the same
formation is found over extensive areas of Pangasinan Province.
According to the Foraminifera these limestones and marls
contain, Douvillé’? has recognized three principal horizons, as
shown in Table I.
TABLE I.—The Philippine Tertiary.
(After Douvillé.)
Philippines. Borneo,
e Upper limestone with small Lep. c.f. verbeeki miogypsina. H Burdigalien.
Lepidocyclines.
b Sandstone and shale. Clycoclypeus communis, Or- G
bitolites alveolinella, Mio- F Aquitanien. } Miocene.
gypsina.
a@ Middle limestone with large Lep. insulae-natalis, formosa, E
Lepidocyclines. richthofeni.
Lower limestone with Num- Nummulites niasi Verb.,
mulites, coal measures. Amphistegina c.f. niasi, Le- D Stampien. Upper Oligocene.
pidocyclina.
In an article on coal-mining operations on Batan Island in the
early days of the American occupation, Reinholt® writes as
follows:
The sedimentary series belong unquestionably to the Tertiary Period.
Professor Mayer of Ziirich and Doctor Dall of our Smithsonian Institution,
agree, from the examination of fossils collected and personally submitted
by me, that the upper limestone should be referred to the Oligocene epoch.”
This does not agree exactly with Douvillé’s findings which were
based on the Foraminifera. I have collected Ampullinopsis on
Batan Island, but from the lower limestone.
Sandstones and conglomerates.—In the coal measures there
are several small seams which may be called grit. Sometimes
the quartz fragments in this grit are over 2 centimeters in
diameter. In addition there is at least one thick stratum of a
very impure, grayish sandstone overlying the uppermost coal
seams in most parts of the Islands, and this is particularly well
developed in Cebu. This formation more properly should be
called an arkose rather than a sandstone, because it contains more
feldspathic, hornblendic, etc. material. There is very little
pure quartz sandstone in the Archipelago.
The conglomerates are of two classes—basal and subaérial.
The greatest development of conglomerate in the Islands is
that bordering the igneous complex of north-central Luzon, as
‘This Journal, Sec. D (1911), 6, 77.
* Eng. Mag. (1906), 30, 510.
*“The presence of Ampullinopsis among the shells is indicative of this
age.”—Letter from Dr. Wm. H. Dall. [Footnote in the original.]
VIll, A, 4 Smith: Fossil Invertebrate Fauna P41
is seen in sections along the Bued and Agno Rivers. This is
basal. Other great deposits of conglomerate are encountered
farther north at an elevation of nearly 2,000 meters. In some
localities this formation is fairly rich in fossils, as in Trinidad
Gap, Benguet.
Probably the best geological sections in the Archipelago are
on Panay. These show great thicknesses of conglomerate and
sandstone. The conglomerates here are bedded and conformable
to the strata above and below.
Tuffs.—There is a great deposit of pyroclastic material, with
intercalated beds of sand and silt extending over a considerable
area of southwestern Luzon, particularly over Cavite and Ba-
tangas Provinces and the country adjacent to Manila. A great
deal of this material probably came from Taal Volcano, but
also from other vents, many of which in a former period existed
throughout this region. When first quarried, the material is
soft, but gradually hardens on exposure. It is buff.to gray in
color. It was extensively used in the Spanish régime, and is
still quarried to a less extent for building purposes. This stone
is known in the trade as “Guadalupe stone.” Fragments of
pumice, black hornblendes, fragments of feldspar, etc. give the
rock a very heterogeneous composition and coarse'texture. The
maximum thickness of the deposit is probably more than 100
meters. The best exposures are to be seen in several quarries
along the banks of the Pasig River. This deposit has yielded
a few fossils.
Adams,” who has studied this tuff more closely perhaps than
any one else, says of these fossils:
Occasionally a log of wood has been encountered in drilling, and plant
remains, fish teeth (fig. 3), and one mammalian tooth (fig. 4) have been
found in the beds. The presence of the plant remains has been recorded
by many observers. The greatest depth at which a log of wood has been
found is in the Alabang wells southeast of Manila where one was cut by
the drill at a depth of between 130 and 132 meters. The mammalian
tooth was obtained from the Pasig well at a depth somewhere between
81 and 85 meters. [Figs. 3 and 4 refer to Adams’s article.]
* This Journal, Sec. A (1910), 5, 78.
1913
Journal of Science
ippine
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242
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243
Fossil Invertebrate Fauna
Smith
Vill, A, 4
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1913
The Philippine Journal of Science
244
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VII, A, 4 Smith: Fossil Invertebrate Fauna 945
Cherts.—In Ilocos Norte, Pangasinan, Balabac, Panay, and
other localities there are outcrops of hard, red cherts or jaspers,
in some places as hard structureless bowlders, and in others as
fissile beds. When I first found these in Ilocos Norte, I compared
them with the cherts of California. On examination with a
microscope they were found to contain fragments of radiolarian
tests. These rocks have a wide distribution in this part of
the world, and have been provisionally assigned to the Jurassic
by Martin.??
Table II is a provisional table of Philippine stratigraphy
revised from similar ones which have appeared in my earlier
papers. This gives the vertical distribution, as near as we now
know it, of the various sedimentary formations and their rela-
tions to the different igneous rocks.
It is my opinion that while some of the coal measures belong
to the Eocene, most of the coal seams occur in the Miocene,
particularly the uppermost and the poorer seams such as the
East Batan.
Old “slates” and other rocks——Masses of indurated sediments
almost slaty in character are found in certain islands and are
pretty certainly older than the Tertiary.
Abella called attention to these in Misamis, Mindanao, and near
O’Donnell, Luzon.'*
In a report made in 1900, Becker '* wrote as follows:
* * * Tf such strata exist, it may be that they are so folded
up with the greatly disturbed Eocene that they have not hitherto been
differentiated. From the descriptions of Surigao and Misamis, it would
seem, too, that considerable areas of slate are there exposed and that
portions of these rocks are not highly metamorphosed. This region may
possibly yield fossils. In carrying on geological investigations in the
Philippine Islands, the indications afforded by the constitution of neighboring
islands should evidently be borne in mind, for if the similarities which might
be expected do not manifest themselves, the cause of difference demands
elucidation.
Ferguson *® describes from the Island of Masbate a series
of slate-like rocks on Kaal Creek. Some of these slate rocks are
reddish, containing psilomelane lenses; other portions are
darker and invariably lined with a minute network of quartz
and calcite veins.
“This Journal, Sec. A (1907), 2, 235-253.
* Reisen in den Molukken. Leiden (1908), pt. 3.
* Manantiales Minerales de Filipinas. Manila (18938), 144.
“Op. cit., 547.
“This Journal, Sec. A (1911), 6, 404, 405.
246 The Philippine Journal of Science 1913
He says:
Little can be said as to the absolute age of the Kaal formation. No
fossils have been found, but judging from its position, its extreme contor-
tion and considerable metamorphism, it is my belief that it may be classed
provisionally as pre-Tertiary, * * *.
My own comment at the time was:
Metamorphism is no longer considered an indication of age; Tertiary
rocks have been subjected to profound dynamic stresses and are met-
amorphosed. Without fossils the question can not be satisfactorily settled.
I am still of this opinion with regard to this particular form-
ation. ;
On the Island of Panay there is a series of much indurated
sediments which is quite distinct from the later sediments known
certainly to be Tertiary. These were encountered in the upper
reaches of the Ulian River almost in the heart of the cordillera.
Their position, lithology, strike, and dip all preclude the pos-
sibility of their belonging to the younger series. In fact, an
intervening basal conglomerate makes this practically a certainty.
This formation for the most part consists of very hard, fine-
grained material with fairly well-developed slaty cleavage.
In the same region, but not exactly associated with these beds,
are some red and green beds which have proved to be cherts and
serpentines. In these we found on microscopic examination of
thin sections some structures similar to those seen in the Ilocos
Norte cherts.
‘Mr. Dalburg, formerly of this Bureau, recently brought from
Bulacan Province, Luzon, rocks similar to those found in Panay.
Slide preparations of these rocks revealed excellent sections of
radiolarian tests of Cenosphera affinis Hinde and Dictyomitra
tenuis Hinde.
Similar forms have been described by Hinde*® in rocks col-
lected in central Borneo by Molengraaff. From his description
of these cherts and diabase tuffs I am more than ever inclined to
the opinion expressed in 19051" that these formations are
Mesozoic and that they are equivalent to those of the Moluccas,
Borneo, etc.
The crystalline schists—The crystalline schists are, in my
opinion, in part at least, of Tertiary age, and, as far as I can
tell from field evidence, they are in some places, at least,
metamorphosed Tertiary sandstones and shales. However, in
** Hinde, Appendix to Molengraaff’s Borneo. Amsterdam (1899).
" This Journal, Sec. A (1907), 2, 145.
VIll, A, 4 Smith: Fossil Invertebrate Fauna 247
northern Mindanao, in Surigao Peninsula particularly, there is a
metamorphic area consisting of argillo-arenaceous and micaceous
schists with quartz stringers. These may possibly be older than
the Tertiary, but there is no fossil evidence nor has any
satisfactory field evidence been brought forward to show that
they lie below the Tertiary series, although similar schists
are found in that position in Java. We may yet find the same
to be the case here.
Distribution—The general statement may be made that the
oldest rocks probably are those found in the deep cafions of
the cordilleras of Luzon. In many other parts of the Islands
where we might hope to find them we encounter everything
covered by a sheet of volcanic rocks, as is the case with much
of the western part of Mindanao, or else by a mantle of coral
limestone, as in Cebu. Flanking these older rocks, and dipping
away from them both to the east and west, are the Tertiary
sediments, limestone, sandstone, shale, and the intercalated coal
seams; above these are andesites and basaltic flows, while the
youngest consolidated formation of all is the tuff of the vicinity
of Manila. It is not easy in our present state of knowledge to
delimit all of these formations; indeed, many which appear to
be of different age are, in reality, contemporaneous. Another
noteworthy fact is particularly well exemplified in Cebu, namely,
that there is no apparent break in the limestone from the coral
reef on the shore to the capping of the cordillera in the center of
the island, at a height of 1,000 meters. It probably sank below sea
level and subsequently rose so gradually that the whole island was
covered with a mantle of coral. This mantle has since largely
been removed by erosion. The map (Plate I), showing the
general distribution of the various formations throughout the
Archipelago, was prepared in this Bureau from data from
various sources, but mainly from our own surveys.
COMPARISON WITH JAVA
Martin 7° in his paper concerning Tertiary fossils in the Philip-
pines which was translated by Becker as a complement to his
~ report on the geology of the Philippines, called attention to the
_ strong resemblance of the fauna of the Philippines to that of Java
based on his examination of the Semper collection now in the
Reichs-museum in Leiden. The Semper collection contains the
following fossils already determined:
* Samm. d. geol. Reichs-mus. in Leiden (1896), 5, 58-69.
1183654
248 The Philippine Journal of Science 1913
Martin’s list (1896).
Species. Age in other parts of this region.
Terebra jenkinsi K. Mart.
Terebra bandongensis K. Mart.
Conus sinensis Sow.
Conus insculptus Kien.
Conus palabuanensis K. Mart.
Conus loroisii Kien.
-Pleurotoma gendinganensis K. Mart.
Pleurotoma carinata Gray.
Pleurotoma coronifera K. Mart.
Pleurotoma neglecta K. Mart.
Turricula bataviana K. Mart.
Fusus verbeeki K. Mart.
Latirus madiunensis K. Mart.
Pyrula gigas K. Mart.
Tritonidea ventriosa K. Mart.
Nassa verbeeki K. Mart.
Murex verbeeki K. Mart.
Murex djarianensis K. Mart.
Murex brevispina Lam.
Murex pinnatus Wood.
Murex microphyllus Lam.
Murex capucinus Lam.
Murex grooti Jenk.
Ranella spinosa Lam.
Ranella elegans Beck.
Ranella raninoides K. Mart.
Ranella gyrina Linn.
Cypraea smithi K. Mart.
Strombus isabella Lam.
Rostellarea javana K. Mart.
Vicarya callosa Jenk.
Potamides jenkinsi K. Mart.
Turritella terebra Lam.
Natica mamilla Lam.
Arca granosa Linn.
Cardita decipiens K. Mart.
Venus squamosa Lam.
Clementia papyracea Gray.
Corbula scaphoides Hinds.
Callianassa dyki K. Mart.
E denotes Eocene; M, Miocene; P, Pliocene; J, later Tertiary in general;
Q, Quaternary; L, living species.
Only one of these, Vicarya callosa, has been figured.
L.
L.
PG
L.
2; M.
1.
L.
L.
BERUUUEOUTE ROS! SEES! BRS RUT RR UR U ERECT RE
ore Post
Martin calls particular attention to Vicarya callosa Jenk.
(Plate VI, figs. 4 to 7). It is indeed the most characteristic
fossil in the Philippine Tertiary invertebrate fauna, and is a
most important zone fossil. Wherever it has been found so far,
it occurs in the gray shale just above the coal seams. Investi-
VIII, A, 4 Smith: Fossil Invertebrate Fauna 949
gators of Philippine coal deposits will find this form most useful
for purposes of correlation.
The following stratigraphic column from Verbeek and Fen-
nema’® can be seen at a glance to duplicate the Philippine
sequence of formations in many items almost exactly.
Stratigraphy of Java.
(Beginning at the bottom.)
I. Argillaceous schists, quartzites with quartz veins, without petrifac-
tion (schists of the Carimuon diawa).............-----:-----s:-1--0ceee-=+ Age ?
II. Schists with serpentine, mica, chlorite, and argillaceous material,
quartzites, some calcareous beds and interposed sills of eruptive
rocks, diabase, gabbro, quartz porphy’ry.............---..----------- Cretaceous.
III. Gray quartzose argillites with beds of coals, breccias of diabase,
quartz, etc., conglomerates of quartz and granite, marls with alveo-
lines and limestone with nummulites......LLower Tertiary or Eocene.
IV. Eruptive rocks in the preceding stage, the oldest andesites, with
the characters of diorites and diabase......Lower Tertiary, Eocene.
Wer Merrane vet = Nano ula ris 258 ce ha ccs se acct cd esesce cee ckes Oligocene.
VI. Eruptive rocks at the base of the Miocene.
VII. The Lower stage of the Upper Tertiary, called the “Breccia Stage,”
composed of breccia of eruptive Tertiary rocks with grits, shales,
with some marl and beds of limestone.................... Lower Miocene.
VIII. Eruptive rocks of the preceding stage...................-------- Lower Miocene.
IX. The middle stage for the Upper Tertiary, called the “Marly Stage,”
containing much marl and marly sandstones, but less of sandstone
and shales; some calcareous beds. Middle Miocene with the upper-
most beds in part Pliocene.
X. Eruptive rocks of the preceding stage........ Middle and upper Miocene.
XI. The most recent stage of the Upper Tertiary called the “Calcareous
Stage;” much limestone and marly limestones alternating with
CECE eg |e ee Se eR eee em Upper Miocene and Pliocene.
XII. Recent volcanic rocks; volcanoes. Miocene, Pliocene, Quaternary,
and Recent.
XIII. Old post-Tertiary sediments with some fossil mammals....Quaternary.
XIV. Recent post-Tertiary sediments....................2...2---:e:::c-e:ceeeeeeeeeeeeeeee Recent.
If we examine each of these formations in turn, we can see
considerable similarity to the formations of the Philippines.
No. I can be duplicated almost exactly in various parts of
northern and southern Mindanao, at Placer in Misamis, and on
the Zamboanga Peninsula.
No. II can be duplicated on Palawan Island. However,
I am loath to believe that these rocks are Mesozoic without more
evidence.
No. III is exactly what we find on Batan and Cebu Islands.
No. IV we have in Benguet, Cebu, and in various other parts of
“Verbeek, R. D. M., and Fennema, R., Description Géologique de Java
et Madoura. Amsterdam (1896), 38.
250 . The Philippine Journal of Science 1918
the Philippines. The older andesite in Benguet can scarcely
be distinguished from diorite, and grades into it.
We have at Alpaco near Naga, Cebu, a marl which corresponds .
very closely to No. V in this table, and is most certainly
Oligocene.
In Cebu Island there are eruptive rocks at the base of
the Miocene, principally andesites, which correspond to No. VI.
There are volcanic breccias in the Philippines, some of which
correspond to No. VIJ. The volcanic breccia in northern and
central Luzon, particularly well developed around Baguio, is,
in part, of this formation.
The marly limestone of the Danao district, Cebu, is probably
equivalent to No. IX of this table.
Undoubtedly much of the eruptive rock of the Philippines
should be referred to the same stage as represented by No.
X in this table; that is, middle and upper Miocene. Diorite
intrusions have been found in Benguet cutting Miocene lime-
stone.
The upper Miocene and Pliocene “Calecareous Stage” shown
in No. XI can be exactly duplicated in the Philippines; it is
particularly well developed in Cebu where many of the fossils
illustrated in this paper were collected. This formation is
characterized by the foraminifer, Lepidocyclina, and by the
manne alga, Lithothamnium.
No. XII can be duplicated at many points in the Philippines.
No. XIII is represented in the Philippines by Pleistocene
deposits in the Agusan Valley, Mindanao, the great tuff deposits
around Manila, etc. A few fossil teeth of mammals have been
found in the latter formation.
No. XIV is represented in the Philippines.
FOSSIL LOCALITIES
The principal fossil localities (Plate II) in the Philippines ©
are as follows:
1. Liguan, Batan Island, Albay Province, Luzon. This locality contains
shale, sandstone, and limestone, but No. 1 refers to the hard,
bluish to buff limestone, occurring near the military mine.
2. Caracaran River, Batan Island; hard, bluish to buff limestone,
probably the same as No. 1.
8. Sitio of Manila, Batan Island; limestone. This formation contains
numerous specimens of Ampullinopsis, a form which is referred
by Dall to the Oligocene.
4. Calanaga Bay, Batan Island; marl and limestone alternating in
thin beds, dipping at various angles from 20° to 45° to the north.
They are grayish to yellow and contain numerous Foraminifera,
VII, A, 4 Smith: Fossil Invertebrate Fauna 951
21.
22.
23.
24.
41.
42,
43.
Moncao Bay, Batan Island; just north of this bed is a considerable
series of limestones and shales.
Bilbao, Batan Island; thin grayish shale overlying lignite seams.
Batan, Batan Island; gray shale overlying the East Batan coal
seam; contains Vicarya callosa, etc. and numerous species of
Corbula.
Gaba Bay, Batan Island; grayish marl something like No. 4.
Agundi, Batan Island; coast limestone.
Caracaran River, Batan Island; thin-bedded shales, alternating
with limestone beds. These probably belong to the Miocene and
overlie the principal coal beds.
Nagtagan Island near Batan; limestone which is the same formation
as that which occurs on the west end of Batan Island.
San Ramon Point, Batan Island; shale.
White to cream-colored upper limestone near Dapdap, Batan Island.
Loboo River, Batangas Province, where the trail crosses to the Loboo
Mountains. This is a dark grayish coarse indurated shale with
bowlders in it. It is very hard and difficult to pick. This prob-
ably belongs to the Miocene. In 1905 I visited this locality and
was of the opinion that this shale immediately overlay the basal
conglomerate from the bowlders which occurred in it. Subsequent
experience in the Philippines necessitates a modification of my
former conclusion. This formation may not be very near the
basal conglomerate. In fact, the whole lower Miocene and Hocene
may be deeply buried at this point. Therefore, the statement,
made at that time, that coal would probably not be found under-
lying this shale, ought to be omitted. -
From a cream-colored limestone overlying the above formation in
the same locality as No. 20.
Limestone at Point Ilihan on the Batangas coast; not visited by
me; probably Pliocene. Collected by C. M. Weber.
Point Buri, Batangas coast; limestone. Collected by C. M. Weber.
Tlaga Creek, Batangas; Miocene limestone like No. 21.
Baguio, Benguet, 1 kilometer west of the city hall. This is a
reddish sandstone, very friable, which is very rich in fossil clam
shells. The peculiar heterogeneous composition and reddish color
of this sandstone is due to the fact that it is made up of detritus
from volcanic rocks upon which it rests. It is more in the nature
of an arkose. This is probably Miocene.
Benguet Road, Mountain Province, Luzon, on the zigzag just below
McElroy’s old camp. This is a coal-black limestone containing
numerous bivalves. The black color is due probably to impurities
at the time of formation of this deposit.
Trinidad Water Gap at the southern entrance to Trinidad Valley.
There is a basal conglomerate which outcrops just below the
limestone on the trail just at the entrance to the gap. It is rich
in the same kinds of fossils as are found at locality 41.
Trinidad Water Gap, across the stream on the northeast side of the
river. This is a coral reef which contains numerous coral frag-
ments of species still living in the China Sea. It is now about
1,500 meters above sea level.
252
45.
46.
272.
273.
274.
275.
276.
277.
278.
279.
280.
281.
282.
283.
284.
285.
286.
287.
288.
289.
298.
356.
609.
778.
The Philippine Journal of Science 1913
Limestone ridge 2 kilometers west of the city hall and north of the
observatory, Baguio, Benguet. This bluish to white limestone is
very rich in poorly preserved fossils; the characteristic species
is Turbo borneénsis. It is probably upper Miocene or early
Pliocene. This is the uppermost limestone in the Benguet district.
Benguet Road, Mountain Province, Luzon; 2 kilometers above Twin
Peaks. This is a very hard, light- to brown-colored formation;
probably Miocene at this point.
On south slope of Mount Mangilao near Danao. This locality is
at the base of the upper limestone and at the summit of a lower
limestone horizon. There is a marl below this which is ap-
parently unfossiliferous. The fossils were picked up where they
had already weathered out of the formation; elevation about 200
meters above sea level.
This is a yellow marl found in Sibod Gulch, Naga, Cebu; probably
Miocene.
Talamban near Panopoy; upper limestone, white and irregular.
Opan on Mactan Island, Cebu; Recent raised coral limestone.
An upper coral bed on Mactan near Cebu.
Soft white chalky limestone cliffs on the Minanga River, Cebu,
Toledo Road near Camp One. This is probably Pliocene limestone.
Hard buff-colored limestone above the coal seams at Guilaguila,
Cebu; contains numerous Foraminifera.
Cotabato Valley near Mount Uling, Cebu; limestone.
Malbog, Alegria, Cebu; Pliocene limestone.
Limestone near oil horizon, 500 meters above sea level, Alegria,
Cebu.
Mangilao; white limestone just above coal at Carmen, Cebu.
On the road between San Fernando and Naga, Cebu; float specimen.
Limestone; specimen given me by a native woman in Toledo, Cebu;
locality unknown.
Cumajumayan Hill; Cebu. No limestone on top of this hill, but
the fossils are from a limestone formation which has since been
removed.
Upper limestone, Lantauan Ridge, Cebu. This contains the char-
acteristic alga Lithothamnium.
Travertine; in the stream in Cumajumayan Valley, Cebu.
Cabecelino Creek, Cebu.
Shale beds above the coal at Compostela, Cebu.
Cream-colored rather open limestone; Cotabato Hill, Mindanao.
This limestone is rich in fossils which are upper Miocene or
Pliocene. .
Cut in the road between Laoag and Bacarra, Ilocos Norte, Luzon.
Unconsolidated gray to white sandy marl; fossils in some cases
retain original color; very rich in perfectly preserved shells;
deposit is undoubtedly Recent.
On the beach, northeast coast of Semirara Island. Fossils evidently
weathered out of limestone. Collected by H. D. McCaskey.
Cave near the beach at Puerto Princesa; recent limestone. Collec-
tions by C. M. Weber.
ee > Lee ee
ee ee ee
VIL, A, 4 Smith: Fossil Invertebrate Fauna 253
822. This is the classic locality of Binangonan, Luzon, where von Richt-
hofen collected “Nummulites,’ but which have been found to be
Orbitoides. This is a limestone ridge surrounded by a basalt
flow about 7 kilometers from Laguna de Bay.
828. Limestone cave about 8 kilometers east of Antipolo, Luzon. This
is the upper Miocene or Pliocene limestone and is the same
formation as the Binangonan limestone.
907. West side of Aroroy, near Colorado Point, Masbate. Gray sandy
shale; Miocene.
1034. Tumaga River about 10 kilometers north of Zamboanga Peninsula,
Mindanao. Miocene shale. Vicarya callosa was found here, in-
dicating a possible occurrence of coal seams below.
1054. San Rafael, Agusan River, Mindanao; recent sandy shale deposit.
Collected by M. Goodman.
1055. Agusan River; exact location not given. Collected by M. Goodman.
1056. Agusan River; all recent shale deposits. Collected by M. Goodman.
CORRELATION OVER THE FAR EAST
The relationship between the stratigraphy of the Philippines
and the rest of the Oriental Region is shown by Table III which
will speak more convincingly than many pages of comment.
CONCLUSIONS
1. As far as we know all Philippine fossils except some radio-
larian tests are Tertiary and Recent.
2. The oldest fossils we know definitely at present are certain
radiolarian species which are almost certainly Jurassic.
3. Philippine fossils are as a rule poorly preserved, and we
have so far found very few new species.
4. The Philippine fauna does not differ essentially from that
of Java.
5. Tertiary conditions still exist in portions of the Archipelago.
6. The mica and chlorite schists may be Tertiary and are not j
necessarily ancient.
PART II. PALEONTOLOGY
LIST OF SPECIES
Conide. Fuside—Continued.
Conus sulcatus var. philippinen- Tritonidea (Pollia) ventriosa K.
sig var. Nov. Mart.
Conus gel ew Buccinids:
ie caters a viteccasha Hindsia dijki K. Mart.
Fuside. Volutidae.
Turbinella ilocana sp. nov. Voluta sp. indet.
Turbinella (Fusus) tjidamaren- Turricula jonkeri K. Mart.
sis K. Mart. Turricula bataviana K. Mart.
254
Pleurotomidz.
Turris (Pleurotoma) andaénsis
sp. nov.
Turris (Pleurotoma) carinata
Gray.
Turris (Pleurotoma) flavidula
Lam. var. sonde K. Mart.
Turris (2?) agusana sp. nov.
Nasside.
Nassa caniculata Lam.
Nassa verbeeki K. Mart.
Nassa siquijorensis A. Adams.
Strombide.
Rimella javana K. Mart.
Casside.
Cassidaria echinophora Linn. (7?)
Cassis pila Reeve.
Cassis nodulosa Gmel.
Doliide.
Pyrula (Melongena) sp.
Dolium costatum Menke.
Melaniide.
Melania laterita Lea.
Melania woodwardi K. Mart.
Naticide.
Natica globosa Chem.
Natica marochiensis Gmel.
Natica rostalina Jenk. (7)
Natica (Lunatia) sp.
Polynices (Natica) mamilla Lam.
Tritonide.
Bursa
Beck.
Turritellidz.
Turritella terebra Lam.
Turritella cingulifera Sow.
Cerithiide.
Vicarya callosa Jenk. var. sem-
peri Smith.
Cerithium (Campanile) sp.
Cerithium (Potamides) palustris
Linn.
Solenide.
Azor coarctatus Gm.
Cultellus maximus Gm.
Mytilide.
Modiolus sp.
Clementia sp.
Clementia papyracea Gray.
(Ranella) subgranosa
The Philippine Journal of Science
1913
Veneridz.
Macrocallista ventricola K. Mart.
(?)
Chione (Venus) chlorotica Phil.
Chione (Venus) pulcherrima K.
Mart.
Dosinia boettgeri K. Mart.
Pectinidz.
Pecten pallium Linn.
Pecten sulcatus Miill.
Pecten senatorius Gmel.
Chlamys (Avquipecten) (?) sp.
indet.
Spondylide.
Sporndylus sp.
Spondylus ducalis Chem. (?)
Plicatula imbricata Menke.
Lucinide.
Lucina (Codakia) sp.
Cardiide.
Cardium elongatum Brug.
Cardium flavum Linn. (7?)
Arcide.
Arca nodosa K. Mart. (7?)
Parallelodontidz.
Cucullaea holoserica Reeve (?)
Astartide.
Cardita boettgeri K. Mart.
Tridacnide.
Tridacna gigas Lam.
Ostreide.
Ostrea sp.
Alectryonia folium Linn.
Corallinacez.
Lithothamnium
Reuss.
Radiolaria.
Cenosphera affinis Hinde.
Dictyomitra tenuis Hinde.
Nummulinide.
Operculina costata d’Orb.
Orbitolites complanata Lam. (7?)
Lepidocyclina insulz-natalis
Jones et Chap.
Lepidocyclina formosa Schlumb.
(?)
Lithophylliacez.
Montlivaultia bulacana sp. nov.
Montlivaultia robusta sp. nov.
Montlivaultia cortada sp. nov.
Pattalophyllia (?) bonita sp.
nov.
ramosissimum
———
— a ee
VIll, A, 4 Smith: Fossil Invertebrate Fauna 255
Lithophylliacez-—Continued.
Caryophyllia (?) laoagana sp.
nov.
Flabellum australe Moseley (?)
Odontocyathus coloradus sp. nov.
Lophoserinz.
Cycloseris decipiens K. Mart.
Pachyseris cristata K. Mart. (?)
Ptychocyathus (?) incognitus
sp. nov.
Lithistide.
Chenendopora (?) major sp.
nov.
Madreporide.
Madrepora duncani Reuss (7)
Astreacez.
Prionastraea (?) vasta Kz.
Spatangide.
Schizaster subrhomboidalis
Herkl.
Solenoconche.
Dentalium tumidum sp. nov.
Vermetidz.
Vermetus giganteus K. Mart.
Thalassinide.
Callianassa dijki K. Mart.
DESCRIPTION OF SPECIES
GASTEROPODA
CONIDA
CONUS Linnzus
Shell. convolute, inverted, top shaped, sometimes quite cylin-
drical, spire short, conical; mouth long, narrow, without teeth
or wrinkles, possessing anterior outlet; outer lip sharp, plain,
sometimes with a gap posteriorly; operculum horny, narrow.
Conus includes 526 recent and about 160 fossil species, principally
distributed in the younger Tertiary formations. (Zittel.)
The genus Conus reaches its greatest development in the
tropics, and the most valued living species, C. gloria-maris
Hwass, was found in the Philippines. They are beach forms.
This fact indicates that the formations containing fossils of
this genus were laid down in shallow water.
Species of Conus found fossil in the Philippines.
Conus sinensis Sow. Semper collection (Leiden).
(Conch. IIl., fig. 56.)
Conus insculptus Kien. Semper collection.
(Icon. Cog. Viv., Pl. 99, fig. 2.)
Conus palembuanensis K. Mart. Semper collection.
(Foss. v. Java, Pl. II, fig. 26.)
Conus loroisti Kien. Semper collection.
(Foss. v. Java, Pl. III, fig. 52.)
Conus acutangulus Chem. (?) Bureau of Science collection.
Conus odengensis K. Mart. Bureau of Science collection.
Conus sulcatus Hwass var. philippinensis var. nov. Bureau of Science
collection.
Conus vimineus Reeve.’ Bureau of Science collection.
Conus hardi (?) Bureau of Science collection.
Conus djarianensis K. Mart. Bureau of Science collection.
Conus parvulus K. Mart. Bureau of Science collection.
256 The Philippine Journal of Science 1918
Conus sulcatus Hwass var. philippinensis var. nov. Plate II, fig. 1.
Tryon, Man. Conchol. 6, Pl. 23, figs. 79a-81;
K. Martin, Foss. v. Java, 1, n. s., Pl. I, figs. 11 and 12.
This is a very fresh looking and well preserved shell, 5 centi-
meters high and 2.5 centimeters wide. Itis very closely related to
both C. sulcatus Hwass, still living in Philippine waters, and to
the variety sonde described by Martin from Java. The form fig-
ured here has only 1 fine thread-like ridge in the main sulcations
instead of 2 or more as in the other varieties. This difference
seems scarcely important enough to warrant even a varietal
name, but one is given to show that there is a slight difference.
Locality: Punta Colorada, Aroroy, Masbate, No. 907.7°
Formation: Pliocene (?) marl.
Conus odengensis K. Mart. Plate III, fig. 2.
K. Martin, Foss. v. Java, 1, n. s., Pl. III, figs. 39-44.
The specimen figured here is a cast, and all casts are open
to doubt, but it agrees with the form C. odengensis more nearly
than with anything else it has been compared with.
Locality: Mount Mangilao, near Davao, Cebu, No. 272.
Formation: Miocene or Pliocene limestone.
Elevation: About 200 meters.
A form not greatly unlike this is C. imperialis Reeve living
in waters near Bohol, specimen in Quadras collection, Bureau
of Science, Manila.
Conus djarianensis K. Mart. Plate III, fig. 3.
K. Martin, Foss. v. Java, Pl. III, figs. 45-50.
This seems to be identical with Martin’s species. It also
resembles more or less closely C. achetinus Chem. and C. arenatus
Brug., the latter living in the seas near Marinduque Island.
Locality: Raised beach, Bongao, Sulu Archipelago, No. 970.
Formation: Recent limestone.
Elevation: 5 meters.
Conus sp. Plate III, fig. 4.
This ig a small specimen which I did not compare directly
with the Javan species, but with a figure merely. I cannot
be sure of the determination. It is about the size and shape
*° These numbers refer to the localities where the fossils were collected;
nearly all of these are shown on the locality map, Plate II.
———
VIll, A, 4 Smith: Fossil Invertebrate Fauna 257
of C. parvulus, but that species is lacking in the little tubercles
on the spire which characterize this specimen.
Locality: Near Anda Island, Pangasinan, Luzon, No. 757:
Formation: Mio-Pliocene shale.
FUSIDZ
FUSUS Lamarck
Fusus (Turbinella)
Shell spindle-shaped, mouth running forward ‘in a canal, spire
elongated, without cross furrows. Columella smooth with folds.
Some 250 recent and at least 500 fossil species. Principal
development in the Eocene and Miocene. The genus F'usus has
been so split up by modern conchologists that Lamarck’s name
has quite disappeared from the literature. (Zittel.) Subgenera
listed by Zittel,; 15.
Species of Turbinella found fossil in the Philippines.
Fusus verbeeki K. Mart.
Foss. v. Java, p. 85.
Turbinella ilocana sp. nov.
Fusus tjidamarensis K. Mart.
Foss. v. Java, n. s., Pl. XIII, figs. 199 and 200.
Turbinella ilocana sp. nov. Plate III, fig. 8.
Hornes, Foss. Mollus. des Tertiar-Beckens von Wien, PI. 31, fig. 2.
This corresponds very closely to F’. glomus Gené, but is larger
than the figured specimen of glomus. Some of the ribs in T.
ilocana seem to be double and are closer together. Length,
51 millimeters; width of last whorl, 20 millimeters.
Locality: Cut in road between Pasuquin and Laoag. Ilocos
Norte, Luzon, No. 356.
Formation: Recent marl.
Turbinella (Fusus) tjidamarensis K. Mart. Plate V, figs. 1, 2, and 3.
Foss. v. Java, Pl. XIII, figs. 199 and 200.
Fossils from the Cutch, India.
The Javan and Philippine specimens of this species differ
apparently only in the shape of the mouth opening. In the
Javan form the outer lip stands out like an ear, while in the
Philippine form it is compressed and hugs the body whorl. In
the Bureau of Science collection are 2 specimens from the same
258 The Philippine Journal of Science 1913
locality which resemble very strongly F’. nodulosus in the Indian
Tertiary.
‘Locality: Slopes of Mount Mangilao, near Davao, Cebu.
Formation: Pliocene limestone, No. 272.
Elevation: 200 meters.
TRITONIDEA Swainson
Skell oval, inflected; spire and aperture of about equal
length; surface usually spirally ribbed and transversely folded;
columella often with weak transverse folds; outer margin
thickened, crenate internally; aperture posterior with a short
canal. Tertiary and Recent. (Zittel.)
Tritonidea (Pollia) ventriosa K. Mart. Plate IV, fig. 16.
A specimen practically identical with this was figured and
described by Martin as Buccinum ventriosum.* Later he placed
it in Pollia. Dall has reverted to the earlier name for this
genus.”? ,
Locality: San Rafael, Agusan River Valley, Mindanao, No.
1054.
Formation: Recent shales.
BUCCINIDZ
HINDSIA Adams
Shell ovately fusiform; spire acuminate; whorls longitudinally
ribbed and cancellated; aperture ending anteriorly in a long
recurved canal; inner lip thin, circumscribed, transversely
corrugately plicated; outer lip grooved internally. (Zzttel.)
Hindsia dijki K. Mart. Plate IV, fig. 17.
I have several specimens of H. dijki before me, which at first
sight might be confused with H. tambacana. They show slight
variations from H. dijki, but in my opinion they are not
specifically distinct. These were compared directly with Mar-
tin’s specimens.
Locality: Cut in road between Laoag and Bacarra, Ilocos
Norte, Luzon, and the west side of Aroroy Bay, Masbate.
Formation: In (Ilocos Norte) recent sandy marl and (Mas-
bate) in gray sandy shale, probably Pliocene.
* Samml. d. geol. Reichs-mus. in Leiden, 1, 204.
2T learned this in conversation with Doctor Dall.
Se OE eee
~~ o
VIII, A, 4 Smith: Fossil Invertebrate Fauna 259
VOLUTIDZ
VOLUTA Linnzus
Last whorl very large; spire short with apex having warts
or short spines; columella, frequently also the inner lip, possessed
of several folds of which the anterior (lower) are strongest;
canal very short, bent backward, frequently only a notch; with
or without an operculum. (Zittel.)
Voluta sp. indet. Plate XV, figs. 1, 2, and 3.
Casts like these are fairly common in certain limestone hori-
zons, but it would be quite impossible to go beyond recognizing
the genus in the case of these specimens at least. By far the
greater part of the petrifactions found in the Philippines are
in about this same imperfect state of preservation.
Locality: Batan Island, southeast coast of Luzon, No. 1.
Formation: Miocene limestone.
TURRICULA Adams
Shell fusiform to elongate, oval solid; transversely ribbed,
spire high, acuminate; aperture narrow, channelled anteriorly;
columella with numerous oblique folds, the posterior plaits being
often the strongest; outer margin commonly thickened and
smooth internally. Like Mitra, however, with cross ribs. The
animals differ from each other in important characters of the
radula. According to A. Adams there are 180 recent species.
Fossils are abundant in the Tertiary. (Zittel.)
Turricula jonkeri K. Mart. Plate IV, fig. 18.
K. Martin, Foss. v. Java, Pl. XI, figs. 175-177.
The Philippine specimen of T. jonkeri in our collection is
smaller than the Javan specimens, and has one very distinct fur-
row near the top of each whorl. Inthe Javan form 3 ridges come
somewhat closer together at this groove, but there is not the
deep sharp suture which appears in the former. I do not
believe this to be a specific difference, however.
Locality: Agusan River, Mindanao, No. 1054.
Formation: Recent or Pleistocene shales.
Turricula bataviana K. Mart. Plate IV, fig. 19.
K. Martin, Foss. v. Java, Pl. XI, figs. 178 and 174.
Our specimens of this species are somewhat larger than the
Javan ones with which I compared them. Also the edges of
260 The Philippine Journal of Science 1918
all the transverse ribs in the former are smooth while in the
latter they are slightly notched. This difference probably is due
to wear.
Locality: San Rafael, Agusan River, Mindanao, No. 1054.
Formation: Recent or Pleistocene shales.
PLEUROTOMIDA
TURRIS Humph.
Spindle-shaped, long, the last whorl making up about one-half
of the whole length of shell; cana] elongated, generally straight;
inner lip smooth. The sinus in the outer lip somewhat removed
from the suture and located in a prominent roll. From the
Cretaceous to present. (Zvttel.)
Fossil species of Turris in the Philippines.
Pleurotoma gendinganensis K. Mart. Pleurotoma coronifera K. Mart.
Foss. v. Java, p. 82. Foss. v. Java, p. 38.
Pleurotoma carinata Gray. Pleurotoma neglecta K. Mart.
Foss. v. Java, p. 37. : Foss. v. Java, p. 42.
Turris (Pleurotoma) andaénsis sp. nov. Plate III, fig. 5.
A species which is superficially like the one figured here is
P. cataphracta Brose. (Foss. Wiener Beckens, Pl. 36, figs. 5
to 9.) However, on the prominent ridge or varix which follows
the whorls there are 2 small tubercles instead of 1 on cata-
phracta and in general tubercles are more abundant on the
former than on the latter. Height, 50 millimeters; width, 20
millimeters.
Locality; Anda Island, Pagasinan Province, Luzon, No. 757.
Formation: Miocene or Pliocene marl.
Turis (Pleurotoma) carinata Gray var. woodwardi. Plate V, fig. 4.
K. Martin, Foss. v. Java, Pl. VI, figs. 91-96.
This is almost identical with Javan specimens. As there is
more or less difference between the young and the adult of
some species, the minute difference in sharpness of ridges, height
of whorls, etc. may be neglected.
Locality: Cut in road between Pasuquin and Laoag, Ilocos
Norte, Luzon.
Formation: Recent sandy marl.
Turris (Pleurotoma) flavidula Lam. var. sonde K. Mart. Plate III,
fig. 7.
K. Martin, Foss. v. Java, 1, n. s., Pl. VI, figs. 102-104.
VIII, A, 4 Smith: Fossil Invertebrate Fauna 261
A perfect specimen with beautiful proportions. Possibly
slightly larger than the Javan forms. This was compared with
Martin’s figures, and not with the actual specimens as in most
cases.
Locality: Bani, Pangasinan, Luzon, No. 758.
Formation: Pliocene (?) marl.
Elevation: 50 (?) meters.
Turris (?) agusana sp. nov. Plate III, fig. 6.
This is a clean, white shell possessing almost its original
polish, but with no trace of color. The aperture is not perfect
so that it is difficult to place it exactly. I can find nothing quite
like it either in the Quadras collection or in the literature.
Although there is little trace of the byssal notch left, there is
a shallow groove just below the suture which may represent it.
The shell is 45 millimeters high and 17 millimeters wide, and
its spire is sharply acuminate making an angle of 27°. Follow-
ing the whorls are well-marked grooves about 1 millimeter
apart, and between these are very fine cross striations. The
sides of the whorls are flat.
Locality: Agusan River, Mindanao, No. 1054.
Formation: Recent or Pleistocene shale.
Elevation: About 50 meters.
NASSIDZ
NASSA Martini
Shell ovate, inflated; aperture with short, reverted canal; inner
lip callous, expanded, outer margin usually crenate internally.
Sparse in upper Cretaceous and Eocene; abundant in Miocene
and Pliocene. Over 200 living species. (Zittel.) This is a
worldwide genus in tropical seas.
Fossil species of Nassa in the Philippines.
Nassa verbeeki K. Mart. Nassa caniculata Lam.
Foss. v. Java, p. 110. Nassa siquijorensis A. Adams.
Nassa caniculata Lamarck. Plate IV, fig. 1.
Reeve, Conch. Icon., 8, Pl. III, fig. 18.
This is quite the same as Cuming’s specimens of a recent
form from the Philippines with which I compared it directly.
It also resembles N. dertonensis Bell.”*
* Sacco, Moll. Terz. del Piemonte, pt. XXX, Pl. XVI, fig. 61.
262 The Philippine Journal of Science 1913
Locality: In bank, Agusan River at San Rafael, Mindanao,
No. 1054.
Formation: Recent or Pleistocene shale.
Nassa verbeeki K. Mart. Plate IV, figs. 2, 7, 8, and 10.
K. Martin, Foss. v. Java, 1, n. s., Pl. XVII, figs. 247-255.
When I first compared the Philippine and Javan specimens
I thought that the Philippine specimens represented a new
species, but I found that in Martin’s collection there was every
variation existing among these specimens; namely, smoothness
or roughness of the first whorl, slight upward projecting point
of the lip, thickening just behind the edge of the aperture, and
breadth of body whorl.
Locality: San Rafael, Agusan River, Mindanao, No. 1054.
Formation: Recent or Pleistocene shale.
Nassa siquijorensis A. Adams. Plate IV, fig. 3.
Reeve, Conch. Icon., 8, Pl. VIII, fig. 53.
The living form was collected by Cuming on the small Island
of Siquijor, and the form shown here was compared directly
with it in the British Museum. With the exception of the some-
what more contracted aperture in the fossil specimen, there is
no essential difference between the two.
Locality: San Rafael, Agusan River, Mindanao.
STROMBIDAZ
RIMELLA Agassiz
Shell spindel-shaped; surface cancellated; edge of the outer
lip thickened, intact or notched; anterior canal short, the pos-
terior channel more or less elongated, following the whorl.
(Zittel.)
Rimella javana K. Mart. Plate IV, fig. 4.
K. Martin, Tertidrscht. auf Java (1880), Pl. IX, fig. 7.
The specimen shown on Plate IV was compared directly with
the type in Leiden from which I could not distinguish it.
There is still another specimen in the Bureau of Science
collection which, although somewhat mutilated, resembles R.
spinifera.
Locality: San Rafael, Agusan River, Mindanao.
Formation: Pleistocene.
Elevation: About 50 meters.
VII, A, 4 Smith: Fossil Invertebrate Fauna 263
CASSIDAE
CASSIDARIA Lamarck
Shell ventricose, not varicose; canal long, twisted, reverted, or
bent sidewise; inner lip greatly expanded; outer lip reflected,
often crenulate; columella border plicate. Upper Cretaceous to
Recent, maximum in the Eocene. (Zittel.)
Cassidaria echinophora Linn. (?) Plate IV, fig. 5.
Sacco, Moll. Terz. adel Piemonte, pt. XXX, Pl. XXI, fig. 3.
I have compared this with a specimen from the Astian (middle
Pliocene) of Italy, in the British Museum collection. The living
form in the same collection is different, the chief difference being
in the matter of teeth on the inner side of the lip. The prom-
inent tooth near the upper portion of the lip in the Philippine
form is lacking in the recent shell and the tubercles are more
pronounced in the former.
Locality: Cut in road between Laoag and Bacarra, Ilocos
Norte, Luzon.
Formation: Recent sandy marl.
CASSIS Lamarck
Shell ovoid, ventricose, having irregular varices; spire short,
aperture elongate; outer lip thickened, reflected, usually denti-
culate in the interior; inner lip callous, expanded, denticulate,
wrinkled, or granulate; canal very short, broad, sharply recurved,
directed upward posteriorly. Tertiary and Recent. (Zittel.)
Cassis pila Reeve. Plate V, fig. 6.
Tryon, Conchology, 7, figs. 76, 77.
The form figured here and referred to C. pila is an imperfect
cast, but sufficiently recognizable I think to be identified as this.
Locality: Constabulary Hill, in quarry at bottom of hill, Cota-
bato, Mindanao, No. 293.
Formation: Limestone.
Cassis nodulosa Gmelin. Plate V, fig. 7.
This is a very recent form, and resembles closely a specimen in
the British Museum collection marked “Her Majesty the Queen.”
Locality: Bongao, Tawi Tawi, No. 970.
Formation: Recent, raised beach.
118365——5
264 The. Philippine Journal of Science 1918
DOLIIDZ
PYRULA Lamarck
This genus, established by Lamarck for pear-shaped shells
with spires, is now broken up into a number of genera which
are distributed among the families of Fuside, Purpurids, and
Ficulide. In the paleontologic literature the collective name of
Pyrula is generally retained. The genera belonging to the Fu-
side are: Melongena, Fulgur, and Tudicla.
Melongena Schumacher
Shell thick, pear shaped; spire short; whorls possessing tu-
bercles or short spines; mouth long and oval; canal short and
_ Wide; columella smooth; outer lip plain. Tertiary and Recent.
(Zittel.)
Pyrula (Melongena) sp. Plate XIV.
This is a large imperfect cast which cannot be definitely placed.
Locality: Batan Island, southeastern coast of Luzon.
Formation: Miocene limestone.
DOLIUM Lamarck
Shell very thin, inflated; spire very short; body whorl very
large, longitudinally and spirally ribbed or cancellated; aperture
wide, oval; canal short, obliquely directed; outer lip notched
internally. Cretaceous to Recent. (Zittel.)
Dolium costatum Menke. Plate V, figs. 5 and 8.
Tryon, Conchology, 7, Pl. IV, figs. 19-23.
Philippine specimens are very similar in every respect to those
from Java, both groups of specimens being casts in a buff to
yellow marl. One Philippine specimen is very much larger than
the others and its ribs are farther apart, suggesting in general
aspect D. hochstetteri.
In many cases the difference between Dolium and Cassis is not
marked, and it also seems that they are closely related genetically.
The Javan specimens of D. costatum with nacreous outer layer
in some cases show a single fine rib between the larger ones.
This is true also in the case of some species of Cassis. This
secondary rib is not always to be seen.
The matrix of both the Javan and Philippine specimens is very
much the same, usually a buff to yellow marl.
Locality: Sibod Gulch, Naga, Cebu.
Formation: Miocene marl.
VII, A, 4 Smith: Fossil Invertebrate Fauna 265
MELANIID4
MELANIA Lamarck
Shell of various shapes, oval to turret shaped; smooth, spirally
striated, ribbed or having nodes, at times with cross ribs or rolls;
mouth always complete; columella gradually coalescing with the
outer lip. Genus widespread over the earth with the exception
of parts of North America. (Zittel.)
Melania laterita Lea. Plate IV, fig. 9.
Reeve, Conch. Icon., 12, Pl. XXIII, fig. 164.
Locality: San Rafael, Agusan River, Mindanao.
Formation: Late Recent or Pleistocene shales.
Other specimens were collected in the Pasig River, Luzon, from
mountain streams on Negros, and by Cuming. Another species
occurring with this, but not figured here, is M. denticulata.
Melania woodwardi K. Mart. Plate VI, fig. 3.
Martin, Foss. v. Java, 1, n. s., Pl. XXXVI, figs. 267-270.
This is figured here to show the general likeness between Turri-
tella, a marine form, and a fresh-water form. The fresh-water
shells are characteristically thinner shelled.
Locality: Agusan River, Mindanao, No. 1054.
Formation: Recent.
NATICIDZ
NATICA Lamarck
Shell globose, semiglobose, or ovate; lustrous, rarely spirally
striated, umbilicated or not; umbilicus when present, often par-
tially or entirely filled with callous material; aperture semi-
circular or oval; outer lip sharp; inner lip thickened by a callus.
Extremely abundant from the Trias on. (Zittel.)
Fossil species of Natica in the Philippine Islands.
Natica globosa Chem.
Natica marochiensis Gmel.
Natica rostalina Jenk. (?)
Natica globosa Chem. Plate IV, fig. 12.
Reeve, Monogr. Ranella, Pl. II, fig. 46.
The specimens of this species in the Philippine collection re-
semble the Javan forms very closely, being, perhaps, a trifle more
acuminate.
Locality: Agusan River, Mindanao, No. 1054.
Formation: Recent shales.
266 The Philippine Journal of Science 1913
Natica marochiensis Gmel.
Martin, Foss. v. Java, Pl. XXXVIII, figs. 616, and 617.
The Philippine form is larger, but in other respects, especially
the umbilicus, it is an exact duplicate of the specimen from
Java.
Locality: Agusan River, Mindanao, No. 1054.
Formation: Recent shales.
Natica rostalina Jenk. (?)
I found nothing in the Javan collection corresponding to this
save one specimen labelled N. rostalina. The suture of the
Philippine specimen is much deeper. The umbilicus is not
visible.
Locality: Cebu, white limestone cliffs, Minanga River on To-
ledo road, No. 277.
Formation: Pliocene ?
Natica (Lunatia) sp. Plate IV, fig. 13.
This may be merely a variety of Natica globosa. It is so small
and featureless that it would not be safe to refer it definitely to
any species.
Polynices (Natica) mamilla Lam. Plate IV, fig. 14.
Martin, Tertiarscht. auf Java (1880), 81.
The Philippine and Javan forms are so nearly identical that
they might very readily be confused. In some of the older
specimens from Java it was noted that the umbilicus had become
completely filled with nacreous matter.
Locality: Agusan River, Mindanao.
Formation: Recent sandy shales.
TRITONIDZA
BURSA Bolten
Shell oval or elongated, compressed front to back with 2
opposite lateral connecting varices; canal short, somewhat bent
backward. Recent and Tertiary. (Zvittel.)
Bursa (Ranella) subgranosa Beck. Plate IV, fig. 15.
Reeve, Monogr. Ranella, Pl. I, sec. 1.
The specimen in the Philippine collection differs only slightly
from both the Javan forms of this species and B. spinosa, but
is more like the former. A large number of specimens of
these two species probably would show complete gradations
VIII, A, 4 Smith: Fossil Invertebrate Fauna ~ 267
between the two. In case of some of the smaller rows of nodes
their larger or smaller size appears to be more or less fortuitous.
Locality: San Rafael, Agusan River, Mindanao, No. 1054.
Formation: Recent or Pleistocene shales.
Other Philippine species of Bursa.
Ranella spinosa Lam. Ranella raninoides K. Mart.
Foss. v. Java, p. 131. Sammi. I, p. 203.
Ramella elegans Beck. Ranella gyrina Linn.
Samml. III, p. 187 (Reichs-mus., Ranella nobilis Reeve.
Leiden).
Ranella spinosa and Ranella nobilis are in the Bureau of Science
collection, occurring in Miocene or Pliocene shales at Aroroy,
Masbate. The others of the above list are in the Semper col-
lection now in Leiden.
TURRITELLIDZ
TURRITELLA Lamarck
Shell turret shaped; whorls even or arched, longitudinally
ribbed or striated; aperture oval or rounded quadrilateral, rim
not entire, external lp turned backward and somewhat bent
outward. Trias to Recent, maximum in the Tertiary. (Zittel.)
Turritella terebra Lam. Plate VI, fig. 1.
Lamarck, Mem. Soe. his. nat. Paris (1799), 74.
This species is still abundant in Philippine waters. The
specimen figured here is really a transition form between T.
bantanensis with 3 pronounced ribs and T. terebra with 5 or 6.
However, it more closely resembles 7. terebra.
Locality: Excavations in Manila.
Formation: Alluvial sands, Recent.
Turritella cingulifera Sow. Plate VI, fig. 2.
This is much larger than the Javan specimen with which I
compared it, but it is clearly the same species.
Locality: Excavations in Manila.
Formation: Alluvial sands, Recent.
CERITHIIDA
‘VICARYA Jenkins
Shell turreted, whorls spirally marked; below the suture a
row of protuberances; canal short and bent backward; inner
lip flattened, callous; the outer lip beneath the row of spines
268 The Philippine Journal of Science 1913
has a deep broad groove, which leaves behind a sutural band
on the whorls.
Vicarya callosa Jenk. var. semperi Smith. Plate VI, figs. 4, 6, 7,
and 8.
Quart. Journ. Geol. Soc. (1864), 20, Pl. VII, fig. 5; Tertiarscht. auf
Java (1880), Pl. XI, fig. 3; Phil. Journ. Sci. (1906), 1, 628, Pl. III,
fig. 1.
Fig. 4 is a drawing of a rather imperfect specimen, but which
shows enough sculpturing to enable us easily to identify it.
This specimen is from Batangas Province, Luzon, and is
somewhat larger than those figured by Martin from Semper’s
collection (from Minanga and Dicamui Brook in northern
Luzon), but is about the size of a specimen which I saw at the
Imperial University of Tokyo. It is also about the same size
as the one figured by Martin from Java.
This species is moderately common in the Philippine coal
measure shales, being especially plentiful in the shale above
the principal coal seam on the eastern end of Batan Island,
Albay Province. It is also found in the same position in the
coal measures in Cebu and Mindanao. It is a good “indicator”
or zone fossil.
The characteristic features of all these specimens are the
flattened whorls, the row of strong spines which is found next
to the sutures, and the sigmoidal growth lines which have their
deepest incurving between the rows of spines.
This is the most important and one of the most striking
fossils to be found in the whole geological section in this part of
the world.
It occurs in Japan, the Philippines, and Java, and there is
a closely related form in India, V. verneuili D’ Arch.
Locality : Loboo River, Batangas Province, Luzon; Cebu, Batan
Island, and Mindanao.
Formation: Miocene (Gaj formation of India), shaly sand-
stone in Batangas, and in coal measure shale in the last-named
localities.
CERITHIUM Adanson
Shell turreted, without epidermis; mouth oval, elongated
anteriorly, with well-developed canal, with generally a short
furrow posteriorly; operculum oval or semicircular with little
VIII, A, 4 Smith: Fossil Invertebrate Fauna 269
spiral coils. The oldest Cerithtum occurs in the Alpine Trias.
The principal development is in the Eocene. (Zittel.)
Cerithium (Campanile) sp. Plate VI, fig. 5.
Cf. P. Oppenheim, Die Eocainfauna des Monte Postale bei Bolea im
Veronesichen, Paleontographica, 43, Pl. XVI.
The fragment figured here is not exactly comparable to any-
thing I have seen in any of the collections of Leiden or London,
but is not greatly unlike some of the big campaniles of the
Edward’s Eocene collection in the British Museum. It is also
like C. vicentinum Bay, or it might be compared with Pyrazisinus
haitrensis Dall.
There is only one specimen in the Bureau of Science collection.
There is a form, Cerithium nodulosum, living to-day in Philippine
waters which is closely related to this fossil species, but in each
of these species there is to be noted a little different alignment
of tubercles or some other minor differences. If the specimen
were more perfect I might venture to place it in some particular
species, but for the present I shall be content with simply giving
a figure of it.
Locality: Mount Mangilao, Danao, Cebu, No. 272.
Formation: Miocene limestone.
Potamides Brongniart
Shell turreted, with brown epidermis; mouth opening forward
with weak canal or only a small conduit; operculum circular,
multispiral. Brackish or fresh-water forms. (Zittel.)
Cerithium (Potamides) palustris Linn. Plate VI, fig. 9.
Martin, Foss. v. Java, Pl. XXXII, fig. 478.
This species inhabits only brackish water. The specimen
figured here is smaller and more poorly preserved than the Javan
specimens, but there can be little doubt that they are all the
same species.
Other species in the Philippine collection are P. noetlingi K.
Mart, P. babylonicus (?) K. Mart. and P. herklotsi K. Mart.
Potamides palustris and P. herklotst were found in coal measure
shales with Vicarya callosa in the Tumaga River, near Zam-
boanga, Mindanao.
Formation: Miocene shale.
270 The Philippine Journal of Science 1913
LAMELLIBRANCHIATA
SOLENIDZA
AZOR Gray
Diagonally elongated; beak almost central; upper and lower
margins straight and parallel; the two hinge teeth of the right
valve very close, those of the left farther apart, the posterior
tooth frequently stunted; the ligament nymphs wide, inflated;
anterior muscle impression elongated, posterior pear shaped;
surface marked by sharp lines. Cretaceous to Recent. (Zittel.)
Azor coarctatus Gm. Plate VII, fig. 1.
Tagelus (Solen) coarctatus Gm.
Linn. Syst. Nat. ed. 18 (1790), 1, 3227.
This form seems to be identical with Tagelus coarctatus col-
lected by Cuming at Calaumana, Luzon. This species was first
found near Naples and was figured in Reeve’s monograph.
The shell is oblong, pale, fulvous, compound, covered with a
wrinkled epidermis, narrowed in the middle, smooth, rather
truncated, and open at each end; dorsal margin somewhat sloped.
This is also very like Psammosolen coarctatus Gm. from the
Vienna Basin.
Another specimen in the Bureau of Science collection, but not
figured here, corresponds fairly well in external appearance to
Tagelus caribbeus Lam.
Locality: San Rafael, Agusan River, Mindanao, No. 1054.
Formation: Recent shale.
Recently I found in the upper (Pliocene) limestone, Bondoc
Peninsula, Tayabas Province, Luzon, a specimen—little more
than an impression of one valve—of an Azor, about 25 centi-
meters long and 10 centimeters high. This is the largest speci-
men of this, living or fossil, I have ever seen.
CULTELLUS Schumacher
Shell narrow, strongly elongated, oval, compressed; lower
margin curved, beak near the anterior margin; hinge teeth 1:2;
anterior muscle impression round, posterior oval longitudinally ;
pallial sinus very wide, but short. Tertiary and Recent.
(Zittel.)
VIII, A, 4 Smith: Fossil Invertebrate Fauna 271
Cultellus maximus Gm. Plate VII, fig. 2.
This is a very fresh looking specimen which appears to have
been covered with mud for only a very short time. This species
is still living.
Locality: San Rafael, Agusan River, Mindanao, No. 1054.
Formation: Recent or Pleistocene shale.
MYTILIDZA
MODIOLUS Lamarck
Distinguished from Mytilus by the long trapezoidal or oval
shape, by the slightly narrowed and rounded anterior portion,
and by the weak beak lying somewhat behind the anterior edge.
(Zittel.)
Modiolus sp. Plate VII, fig. 3.
This specimen, except for a little distortion and one or two
cracks, is excellently preserved. Both valves are preserved, but
slightly separated by the bluish white shale matrix. The sur-
faces of the valves retain their original color and nacreous ap-
pearance. I have no doubt but that this is a well-known form,
but in the absence of adequate literature I shall refrain from at-
taching a specific name to it. The specimen is about 6.5 centi-
meters long. With the exception of the fine growth lines it has
no sculpture.
Locality: Unknown (from the Spanish régime).
Formation: Shale, Recent?
CLEMENTIA Gray
Shell subtrigonal, transversely oval, inequilateral, white, slen-
der, fragile; the hinge bearing 3 cardinal teeth upon each valve,
the 2 anterior ones simple, vertical, and the posterior one bifid
on the right side, the anterior is simple and the 2 posterior oblique
on the left side; the ligament sunken; the interior edge of the
valves simple, pallial sinus deep, ascendant. (Fischer.)
Clementia sp. Plate VII, fig. 4.
The specimen shown here, while fairly perfect, is only a cast
so I am not able to make any specific determination.
Locality: Unknown, probably Cebu or Panay (from the
Spanish régime).
Formation: Limestone.
272 The Philippine Journal of Science 1918
Clementia papyracea Gray. Plate VII, fig. 5.
It is very difficult to tell whether this is a Clementia or a
Cytherea from the cast. The Philippine forms resemble the
above in many respects—shape, sculpture, ete.
Clementia is a recent genus according to Zittel, and, therefore,
either it has a longer vertical range or these forms should not
properly be referred to this genus.
Another internal cast is shown in Plate VIII, fig. 3.
Locality: About 0.5 kilometer west of the Tribunal, Baguio,
Mountain Province, Luzon.
Formation: Tuffaceous sandstone.
Elevation: Nearly 1,500 meters.
VENERIDAE
MACROCALLISTA Meek
(Cytherea)
External form and curve of the shell the same as in Venus,
edges smooth; hinge with 3 dividing, frequently cleft teeth and
in the left valve beneath the lunule a fourth, generally recumbent,
anterior tooth, which corresponds to a long groove in the right
valve; sometimes also there is a lateral tooth situated farther to
the rear; pallial sinus large, triangular or tongue-shaped, some-
times quite lacking. This genus contains over 150 recent and
at least as many fossil species which are widely distributed
from the Jura to the older Tertiary. (Zittel.)
Macrocallista ventricola K. Mart. (?). Plate VII, fig. 6.
Martin, Tertiarscht. auf Java (1880), Pl. XVI, fig. 10.
This form resembles exteriorly C. ventricola described from
the Tertiary of Java and it is also very similar to Meretrix sub-
pellucida found in Luzon waters by Cuming.
Locality: Agusan River, Mindanao.
Formation: Recent deposits.
CHIONE Gray
(Venus)
Shell oval, roundish to triangular or heart-shaped, thick,
smooth, or lined with ribs, striations, furrows, leaves, etc.; edges
of shell finely crenulated, seldom smooth; a lunule usually is
present; hinge area wide with 3 strong, diverging hinge teeth
in each valve; ligament prominent; pallial sinus short angular.
(Zittel.)
VIII, A, 4 Smith: Fossil Invertebrate Fauna 273
Chione (Venus) chlorotica Phil. Plate VII, figs. 7 and 8.
Save for a slight difference in color which may be due to
age or inclosing material these forms are identical with the
Javan forms. Forms very closely allied to this, if not the
same form, are living in Philippine waters to-day.
Locality: Agusan River, Mindanao, No. 1054.
Formation: Recent.
Chione (Venus) pulcherrima K. Mart. Plate VIII, fig. 1.
Samml. d. geol. Reichs-mus. in Leiden (1891-1906), 1, n. s., Pl. XIII,
fig. 47.
The form shown here may be a variety, for while the sculpture
corresponds pretty well with the Javan form the latter is longer
and not so high and perhaps slightly thinner. It also cor-
responds fairly well with V. granosa from the Cutch, India.
Locality:. Opan, Mactan Island, about 3 meters above sea
level, No. 275.
Formation: Pliocene or Pleistocene reef.
DOSINIA Scopoli
Shell circular, compressed, concentrically striated or grooved,
with deep lunule under the beaks; hinge teeth 3, the right
posterior and the anterior left are cleft; edges smooth, pallial
sinus deep, ascendant pointed. About 100 recent species, fossils
abundant in the Miocene and Pliocene. (Zittel.)
Dosinia boettgeri K. Mart. Plate VIII, fig. 2.
Tertiarscht. auf Java (1880), Pl. XVI, fig. 4.
This is a rather young form, but not essentially different
from the Javan species. These forms are casts and therefore
allowance must be made for the difficulties in making exact
determinations.
Locality: One-half kilometer west of the city hall, Baguio,
Mountain Province, No. 41.
Formation: A very friable, reddish colored, tuffaceous sand-
stone; altitude, 1,500 meters.
PECTINIDA&
PECTEN Klein
Shell round or higher than long, equivalved and apparently
equilateral; free; upper surface mostly radially ribbed or
striated; the anterior ears somewhat larger than the posterior,
having on the right valve a deep byssal notch; hinge line straight,
274 The Philippine Journal of Science 1913
the inner ligament in a central triangular hole just beneath the
projecting beaks which touch one another; muscle impression
large and subcentral. (Zittel.)
Species of Pecten known from the Philippines.
Pecten fricatum Rv. Pecten sulcatus Mill.
Pecten senatorius Gmel. Pecten subarcuatus Bttg.
Pecten leopardus Rv. Pecten reticulatus Rv.
Pecten solaris Rv. Pecten pallium Linn.
None of these is mentioned in Martin’s list in the appendix
to Becker’s report, and only one, P. leopardus, is given in Hi-
dalgo’s list of living species in the Philippines.
Pecten pallium Linn. Plate IX, fig. 6.
Martin, Tertiarscht. auf Java (1880), Pl. XX, fig. 10.
The form here shown is not exactly the same as P. solaris
figured by Reeve. The ears are partly worn off the Philippine
form, and the secondary crenulations or small ribs are lacking
in solaris. In the Quadras collection of living shells I find a
pecten with no specific name from Guam Island, one of the Ma-
rianne group. This shell is about the same size as the fossil form
shown here, and has practically the same crenulated ribs as well
as the same number. The living shell is strongly mottled red,
brown, and white.
I have concluded, however, that this form is essentially the
same as P. pallium described by K. Martin from the Tertiary
of Java, though his specimen has one or: two fewer ribs (a
younger specimen, perhaps) and shows one ear missing.
Plate X, fig. 1, shows a possible variety of the same species.
Locality: Near Danao, Cebu, No. 272.
Formation: Miocene limestone.
Pecten sulcatus Miill. Plate IX, fig. 7.
Miiller, Zool. Dan. Prod. (1776), 248.
This form, although somewhat worn, is so closely like P. sul-
catus that it is here referred to that species. The fossil has the
same number of ribs as the living form in the Quadras collection.
There is a minor difference, however, namely the distance
between the ribs. This may be accounted for by wear. The
two forms are of about the same size.
Locality: Talamban near Panoypoy, Cebu.
Formation: Mio-Pliocene, upper coral limestone.
meee
nae 4 >
VIII, A, 4 Smith: Fossil Invertebrate Fauna 2795
Pecten senatorius Gmel.
Martin, Tertiarscht. auf Java (1880), Pl. XX, fig. 11.
At the time the plates for this paper were being drawn no
good specimens of this form existed in the Bureau of Science
collection, but since then several good specimens have been
obtained from the “Upper Limestone” of Bondoc Peninsula,
Tayabas, Luzon, which certainly belong to this species.
An imperfect specimen was also found in the Mio-Pliocene
limestone near Danao, Cebu.
CHLAMYS Bolten
(Aiquipecten)
Shell somewhat inequivalved, broadly rounded, anterior ears
generally somewhat larger; outer surface radially striated or
ribbed; ribs scaly or cross striated. From the Trias to Recent.
(Zittel.)
Chlamys (Aiquipecten) (?) sp. indet. Plate VIII, fig. 4.
F. Sacco, Moll. Terz. del Piemonte, Pl. XXIV, fig. 1; and Pl. VII,
sheen Ee
This is an incomplete specimen, the ears of which are entirely
missing. The nearest forms, which I have been able to find
to which it bears any resemblance whatever, are A. mioalternans
Sacco and A. northamptoni Micht. in the Pliocene of Italy. I
must say that I do not see much resemblance between this Philip-
pine specimen and any species belonging to the genus Chlamys.
Locality: Liguan, Batan Island, southeast coast of Luzon,
No. 1.
Formation: Upper limestone; Miocene or Pliocene.
SPONDYLIDA
SPONDYLUS Linnzus
Inequivalved, irregular, with the right valve attached, radially
ribbed, spiny, or foliated; beaks unequal, in addition ears on
each side; lower shell with a 3-cornered area in the middle of
which for the most part is a row of pits. The straight hinge
line bears on each shell 2 very strongly curved teeth which fit
into the corresponding holes of the opposite valve; between
those there is a pit for the inner row. The muscle impression
is doubled, in old individuals, serrated.
The numerous recent species are best developed in the tropics
and in the temperate zones, and are especially characterized by
276 The Philippine Journal of Science 1913
their splendid ornamentation and striking colors. The oldest
fossil species are small, thin shelled, and have little ornamenta-
tion. (Zittel.)
Spondylus sp. Plate VIII, fig. 7.
The form here shown is only an internal cast, and therefore
I am unable to place it specifically. It is marked by 4 very
strong and prominent ribs which extend downward into spines.
Locality: Unknown.
Formation: Limestone.
Spondylus ducalis Chem. (?) Plate X, figs. 3 and 4.
Mus. Bolten (2), 1798, 194.
This and the above are two specimens which belonged to ihe
Spanish Mining Bureau, the labels of which were lost so that we
know nothing definite about the locality or the horizon from
which they came, except that they came from a limestone
formation.
Spondylus ducalis is still living in Philippine waters on the
coasts of Luzon, Cebu, and Mindanao.
The fossil shown here is flatter than S. ducalis and more worn.
The flatness of the smaller valve may be due to compression or
may be natural.
PLICATULA Lamarck
Shell irregular, flat or considerably arched with the beak
of the right valve attached; smooth or wrinkled; hinge area
indistinguishable, the ligament internal between two or more
diverging ridge-like hinge teeth; the muscle simple and excentric.
Numerous fossil species from the Trias on, as well as about
10 living. (Zittel.)
Plicatula imbricata Menke. Plate X, fig. 6.
Sowerby, Plicatula 6 and 15-18.
Cuming collected this species on the beach of Corregidor Island
at the entrance to Manila Bay.
Locality: Sea cliff near Puerto Princesa, Palawan, No. 779.
‘Formation: Recently elevated limestone.
LUCINIDA
LUCINA Bruguiére
Shell more or less circular or lens shaped, compressed or bulg-
ing; the posterior side often has a furrow extending from the
back to the posterior margin; lunule generally present; ligament
exterior, frequently deeply sunken; hinge variable, generally
VIL, A,4 Smith: Fossil Invertebrate Fauna 277
2 hinge teeth and 2 lateral teeth in each valve; frequently the
lateral teeth are obliterated, sometimes also one or both of the
hinge teeth; anterior muscle impression large, narrow, elongated
toward the middle of the shell; posterior one oval, close to
the margin; pallial line without indentation; inner surface inside
the pallial line rough, frequently with a prominent furrow. One
hundred living and at least 300 fossil species. (Zittel.)
Lucina (Codakia) sp. Plate VIII, fig. 5.
Cf. Proc. Malacolog. Soc., 3.
The species which I have been able to locate having the
greatest resemblance to this form is L. semperiana Issel from
the Andaman Islands. I do not see enough difference to lead
me to place it elsewhere, nor do I feel sure enough of the
diagnosis definitely to cail it by this name.
Locality: Batan Island, southeastern Luzon, No. 4.
Formation: Miocene.
CARDIIDZ
CARDIUM Linnzus
Shell inflated heart-shaped, sometimes narrow or longitud-
inally oval, closed or somewhat gaping; outer surface radially
ribbed or striated, the ribs frequently possessing nodes or
tubercles, edges crimped or toothed; hinge teeth 1, 2, 1:1, 2, 1;
hinge and lateral teeth in their development somewhat weak.
Two hundred recent species and from 300 to 400 fossil species.
(Zittel.)
Cardium elongatum Brug. Plate VIII, fig. 6.
Ency. Mith. (Vers.) (1), 1789, 228.
The cast shown here is from the old Spanish Mining Bureau
collection. Nothing is known either as to its locality or the
formation it came from save that it must have been a limestone.
It represents a young form probably.
This species is living in the waters near Panay and Jolo.
Cardium flavum Linn. (?) Plate IX, fig. 1.
Syst. Nat. ed. 10 (1758), 363; Reeve, Mon. fig. 68.
This form is another of a collection of relics from the Spanish
régime, and nothing is known as to its locality. It is from a
limestone formation. This species, if it is flavum, is still living
in Philippine waters as indicated by Hidalgo.**
“Catalogo de los Moluscos Testdceos de las Islas Filipinas. Madrid
(1905), 344.
278 The Philippine Journal of Science 1918
I judge from the nature of the petrefaction that it came from
the Miocene-Pliocene limestone of Cebu or the same horizon
on some other island, most probably Panay, as Abella did a
great deal of his geological work on that island. This author
mentions having found several species of Cardium.” .
ARCIDA
ARCA Lamarck
Shell obliquely elongated, sides unequal, valves equal, more or
less 4-sided, upper surface generally radially ribbed or striated,
borders smooth or crenulated; beak forward of the center of the
shell; through a more or less high, plane, rhombic area are
“V-shaped or bow-shaped furrows, separated from one another,
for the insertion of the ligaments. The ligament covers the
whole or a great part of the hinge area. Hinge line straight;
teeth numerous, apparently of the same size, set diagonally to
the hinge line and more or less parallel to each other. The
numerous little cross teeth, perhaps, originate from two long
drawn out ridge-like hinge teeth. The pallial line is simple, the
two muscle impressions are comparatively large. (Zittel.)
Arca nodosa K. Mart. (?) Plate IX, fig. 2.
Tertidrscht. auf Java (1880), Pl. XVIII, fig. 12.
The form shown here is closely related to Arca nodosa,
although it does not show much development of nodes. It may
be a variety or a young specimen.
A good specimen of this species was found recently on Bondoc
Peninsula too late to be figured here.
Locality: San Rafael, Agusan River, Mindanao.
Formation: Recent shales in river bank.
Another species, which is given in Martin’s list of the Semper
collection, is A. granosa Linn. This has also been found recently
in Bondoc Peninsula, Tayabas, Luzon.
The living fauna of the Philippines contains a great number
of species of Arca, some of which are 5 or more centimeters in
length.
PARALLELODONTIDA®
CUCULLAEA Lamarck
Shell rhombic or trapezoidal, highly arched; beak separated
by a wide hinge area; hinge line straight, in the middle little
* Descripcioén fisica, geoldgica y minera en bosquejo de la Isla de Panay.
Manila (1890), 138.
ae ee
Vill, A, 4 Smith: Fossil Invertebrate Fauna 279
cross teeth; laterally from 2 to 5 large ridge-like teeth parallel to
the hinge line. The posterior muscle impression:is frequently
affixed to one or more strongly protruding thin plates. (Zittel.)
Cucullaea holoserica Rv. (?) Plate IX, figs. 4 and 5.
The form here shown is another one of those left from the
old Spanish collection and to which there is no label attached.
It is also a cast, and therefore little that is definite can be said
about it.
Locality: Either Cebu or Panay.
Formation: Limestone.
ASTARTID®
CARDITA Bruguiére
Shell oblate and Raided: very unequally sided, radially ribbed,
edges toothed or crenulated; beak wide and thrust forward, liga-
ment external; teeth 1:2 diverging and unequal. In addition
there is a swelling-like process posteriorly developed. The
muscle impression is strongly developed. From the Trias to the
present. (Zittel.) :
Cardita boettgeri K. Mart. Plate IX, fig. 3.
Tertiarscht. auf Java (1880), Pl. XVII, fig. 10.
This specimen is somewhat worn so that the little nodes on
the ribs do not show any longer. I compared it directly with
the forms in Martin’s Javan collection, and this Philippine form
is a trifle smaller and has thicker ribs, but SEES is quite
the same.
Locality: Puerto Princesa, Palawan, No. 778.
Formation: Recent.
TRIDACNIDA®
TRIDACNA Bruguiére
Shell massive, 3-sided, with radial ribs, which have scaly
leaves; margins deeply notched, the anterior side below the beak
possessing a cleft for the byssus; hinge on either side with a
recumbent hinge tooth and a moderately thick lateral tooth
similarly situated. Recent and Miocene. wa Sona reach
colossal size. (Zittel.)
The genus is common both fossil and living in the Philippines.
One individual is reported to have measured 3 meters in length.
I have seen one specimen 1 meter long.
118365——6
280 The Philippine Journal of Science : 1913
Tridacna gigas Lam. Plate XVI.
Mem. Soc. H. N. Paris (1799), 86.
This is only a fragment of an internal cast, but it is sufficient
for determination. The elevated reef limestones of the Philip-
pines inclose many fragments and some fairly perfect specimens
of this extraordinary shell. The piece shown here represents
a Shell of about 25 centimeters’ length, a young individual.
OSTREIDA
OSTREA Linnzus
Shell irregular, concentrically leaved or with large radial ribs
and folds, arched, frequently compressed, margins simple, entire;
hinge line toothless; beak frequently drawn out, straight with
a hinge furrow across it on the underside. Six subgenera
including Ostrea. Alectryonia in one of these. Both valves with
strong ribs, or folds, shell margins undulating or zigzag shaped.
From the Trias on. (Zittel.)
Ostrea sp. Plate X, fig. 7.
This is a more or less characterless form which may he entirely
normal or some freak form. It may or may not be a new
species. If a new species were erected for every queer shape
found in the genus Ostrea, the number would be legion.
Locality: Talamban near Panoypoy, Cebu, No. 274.
Formation: Mio-Pliocene limestone.
ALECTRYONIA Fischer
Shell distorted by early adherance to other objects, mono-
noyarian, the anterior adductor absent; edentulous, or with
obscure schizodont dentition, dimyarian when young, the foot
obsolete or absent in the adult; left valve attached to roots or
branches by clasping shelly processes; both valves with strong,
often divaricate folds and unduluate margins. Trias to Recent.
(Zittel.)
Alectryonia folium Linn. Plate X, fig. 5.
Linnezus, Syst. Nat. ed. 10 (1758), 699.
Neither this genus nor species to my knowledge has heen
reportéd from the waters of the Philippines. It does not appear
in the Hidalgo catalogue.
Locality: Sea cliff near Puerto Princesa, Palawan, No. 779.
Formation: Recent.
VIII, A, 4 Smith: Fossil Invertebrate Fauna 231
THALLOPHYTA
CORALLINACEA&
LITHOTHAMNIUM Philippi
The thallus of Lithothamnium grows attached to the face of
a rock or other foundation, and forms a hard, stony mass, assum-
ing various coralline shapes. The exposed face may have the
form of numerous short branches, or an irregular warty surface.
In section the lower part of the thallus is seen to be made up
of rows of cells radiating from a central point, and the upper
portion consists of vertical and horizontal rows of cells, the whole
body is divided up into a large number of small cells by anticlinal
and periclinal walls, and possesses an evident cellular, as distinct
from a tubular, structure. Conceptacles containing reproductive
organs are either sunk in the thallus or project above the surface.
(Seward.)
Lithothamnium ramosissimum Reuss. Plate XI, fig. 2.
Nat. Abhandl. Haidinger (1848), 2, pt. 1, 29, Pl. III, figs. 10 and 11;
Journ. Coll. Sci., Imp. Univ. Tokyo (1902), 17, art. 6, Pl. I, fig. 8.
The photomicrograph is from a thin section of the same lime-
stone as that shown in fig. 1.
This form is widespread in the Miocene limestones in all
parts of the Philippines as well as in adjacent islands outside
the Archipelago. It is a typical “leit-fossil’ or zone fossil
characteristic of the middle limestone of the upper part of the
Lower Miocene.
‘Locality: Lantauan Ridge, near Danao, Cebu, No. 286.
Formation: Limestone.
RHIZOPODA
RADIOLARIA
CENOSPHZERA Ehrenburg
The test is a simple sphere without radial spines. The
rounded outlines of forms of this genus are very common in
all the radiolarian rocks of Borneo, but in most all traces of
the structure of the test have disappeared. (Hinde.?*)
* Reprint from Molengraaff’s Borneo. Leiden (1899), 10.
932 The Philippine Journal of Science 1913
Cenosphera affinis Hinde. Plate XX, figs. 1 and 2.
Hinde, Descript. Foss. Radiolaria from rocks of central Borneo, ap-
pendix I in Molengraaff’s Borneo (1899), Pl. I, fig. 7.
These 2 figures are photomicrographs of a section of an old
slate from Bulacan Province found in 1912. by, F. A. Dalburg.
They show many individual Radiolaria, but only 2 or 3 specimens
which can be plainly identified. The spherical form I have
referred to C. affinis. The magnifications in the two figures
are 100 and 200 diameters, respectively. In this specimen we
find only the structure of the shell, the interior being completely
taken up with a filling of cryptocrystalline silica.
DICTYOMITRA Zittel
The latticed test is conical or cylindrical without horn, and
with an open basal aperture. The constrictions are horizontal.
(Hinde.)
Dictyomitra tenuis Hinde. Plate XX, figs. 1 and 2.
Foss. Radiolaria from Central Borneo (1899), Pl. IV, fig. 15.
The oval-shaped section in these figures is thought to be a
section of a form belonging to this species. These forms are
all so generally devoid of any special character that there is
reason for some latitude in their determination.
In Plate XII, fig. 1, is shown a section of a jasper from Ilocos
Norte, Luzon, collected by me in 1906. I called attention to the
resemblance of this specimen to the radiolarian cherts of Cali-
fornia.27 Since that time I have learned both from conversations
with Dr. K. Martin in Leiden and from recent literature that
similar jaspers and cherts have been found in Borneo, Java, and
the Moluccas ?* and that they are there referred provisionally to
the Jurassic.
In the Ilocos Norte jasper no distinct radiolarian characters
could be made out, only small roundish areas filled with crypto-
crystalline silica were visible.
Similar ancient-looking rocks have been found on Panay, on
Balabac, and in Pangasinan Province, Luzon, but sections of
the rocks collected by Dalburg in the Eastern Cordillera of
Luzon were the first to show any determinable specimens.
." This Journal, Sec. A (1907), 2, 158.
* Martin, Reisen in den Molukken. Leiden (1908), Geolog. Theil, Pl. VI,
fig. 5. ‘ .
VI, A, 4 Smith: Fossil Invertebrate Fauna 283
FORAMINIFERA
NUMMULINIDZ —
OPERCULINA d’ Orbigny
Shell typically complanate and planospiral with rs a Fae if
the convolutions visible; the earlier whorls more or less embrac-
ing; interseptal and marginal canals conspicuously developed.
Lower Cretaceous to Recent. (Chapman.)
Operculina costata d’Orb. Plate XIII, fig. 1. 4
Ann. sci. nat. (1826), 7, 281; Phil. Journ. Sci., Sec. D (1914y; ¢ 6, 56.
This form is found in great numbers in the limestone cliffs
along the Toledo road, Cebu, No. 277, about 3 kilometers west
of Naga on the banks of the Minanga River. The formation
is the upper limestone which dips gently to the southeast to
the sea. Specimens in the Bureau of Science collection vary
from 2 to 6 millimeters along the longest diameter.
ORBITOLITES Lamarck
~f
Test discoidal, sometimes undulate or rarely sinous; growth
either spiral (nonembracing) just. at the commencement, or
with one or more inflated, primordial chambers; subsequently.
cyclical; chambers more or less regularly divided into. chamber-
lets. Upper Cretaceous to Recent. (Chapman.) ;
Orbitclites complanata Lam. (?) Plate XIII, figs. 2, 3, and 4.
_ Phil. Trans. Roy. Soc. (1856), 224, Pls. V-IX. :
The forms here shown apparently have the internal structure
of this species, certainly in external appearance they are quite
similar. They vary from 7 to 10 millimeters in bad sh and
are less than a millimeter in thickness.
These were found by H. D. McCaskey some > years ago on the
beach of Semirara Island. He reported that they occurred
there in great numbers, but was unable to say whether they
had weathered out of a limestone or were recent forms. I am
inclined to think they are very recent, although I am aware
that the species goes back to the Cretaceous.
LEPIDOCYCLINA Giimbel
Median plane composed of chamberlets arranged in regular
annuli around a distinct central chamber or chambers; thickened
on either side by layers of flattened chamberlets more or less
284 The Philippine Journal of Science 1913
irregularly disposed. The chief subgeneric types of Orbitoides
are based on the appearance of the chamberlets of the median
layer.
The genus Lepidocyclina has lozenge-shaped or spatulate-
formed chamberlets. They occur in the Upper Cretaceous. the
Oligocene, and the Miocene. (Chapman.)
Plate XI, fig. 1, is a photomicrograph of a thin section of the
orbitoidal limestone on Lantauan Ridge about 12 kilometers west
of Danao, Cebu. The horizon is probably uppermost Miocene.
Douvillé 2? has recognized the following species in sections of
Philippine material which I submitted to him.
Lepidocyclina insulz-natalis J. et Ch. Lepidocyclina smithi Douvillé.
Lepidocyclina richthofeni Smith. Lepidocyclina verbeeki Newt. et Holl.
Lepidocyclina formosa Schlumb. Lepidocyclina inflata Provale.
Lepidocyclina inermis Douvillé. Lepidocyclina cf. marginata Mich.
I shall figure only two species here.
Lepidocyclina insule-natalis Jones et Chap. Plate XIII, figs. 6
and 7.
Monograph Christmas Island. London (1900), Pl. XX, fig. 5.
Samm. d. geol. Reichs-mus. in Leiden (1888-1902), I, 6, 128.
These are very much enlarged drawings of the swollen central
portion of this species. These pea-like swellings from which
the surrounding wing-like parts have been worn away are more
common than the whole specimens.
Figs. 13, 14, 15, and 16 are drawings of various fragments
of the same. These were all found lying loose on the surface
of the small hill in the lower Kahumayhumayan Valley in Cebu.
The original containing-limestone has been removed, and the
underlying rock was found to be coal measure shale. I feel
convinced that these forms were weathered out of a limestone
which lay stratigraphically below that on the neighboring hill
summits.
Similar forms have been found in Java and Christmas Island,
and doubtless they are pretty generally distributed in this region.
Those from Christmas Island have been determined by Chapman
as L. insulz-natalis, though Douvillé figures practically the same
thing as L. richthofeni Sm. This last name, however, was given
by me, at an earlier date, to an entirely different form of which
the chief outward character was its more bulging and rounded
shape.
>This Journal, Sec. D (1911), 6, 71-74.
VII, A, 4 Smith: Fossil Invertebrate Fauna 285
Lepidocyclina formosa Schlumb. (?) Plate XIII, figs. 8, 9, 11,
and 12.
Sammi. d. geol. Reichs-mus. in Leiden (1900), I, 6, Pl. VII, figs. 1-3,
251; Phil. Journ. Sci., Sec. D (1911), 6, 72, Pl. D. figs. 2-5.
Similar forms havé been described and figured by Douvillé.
Plate XIII, fig. 5, shows a fragment of orbitoidal and coralline
limestone from Guila-Guila in Cebu, illustrating the charac-
teristic appearance of this rock and the abundance of the re-
mains therein.
COELENTERATA
LITHOPHYLLIACEA
MONTLIVAULTIA Lamouroux
Free, pedunculate, or attached by a wide base, cylindrical,
circular, or oval shaped; epitheca thick, but fragile and often
rubbed away; septa numerous, wide, regularly toothed; columella
lacking; cross plates strong and numerous. Common in the
Jura, not so well developed in the Trias, Cretaceous, and Tertiary.
(Zittel.)
Montlivaultia bulacana sp. nov. Plate XVII, figs. 1 and 3.
These two specimens though differing considerably in size
and shape are referred to the same species as it is thought
that the specimen shown in fig. 3 is somewhat distorted. The
specimens are 6 and 10 centimeters long and 3.5 and 4.5 centi-
meters wide, respectively. They were pedunculate. The septe
are on the average 1 millimeter apart, and are apparently parallel
from the base to the edge of the calyx. At intervals, which
are not constant, there are lines perpendicular to the septe
running around the calyx which may denote horizontal tabule.
These forms roughly simulate Streptolasma from the Silurian,
but in the latter the septe diverge fan-like from a median line.
Locality: San Miguel de Mayumo, Bulacan, Luzon, No. 189.
Formation: Limestone.
One of these forms is not greatly unlike Turbinolia hippuriti-
formis Michelin,®° which occurs in the cretaceous of France.
® Zoophyta Iconica. Paris, 287, Pls. 65-67. Compare, also, The fossil
corals and Alcyonaria of Sind, Mem. Geol. Surv. India, 2, Pl. V, fig. 9.
286 The Philippine Journal of Science Le Atos
Montlivaultia robusta sp. nov. Plate XVII, fig. 6.
This specimen differs from the other two in being more robust
and having a larger. base. +a
Locality: San Miguel de Mayumo; Bulacan, Luzon.
Formation: Limestone. ;
All of these specimens are in outward appearance. somewhat
like montlivaultias from the nummulitic.of India, Lukkee, south-
ern Indus Range, and now in the British Museum.
Montlivaultia cortada sp. nov. Plate XVIII, fig. 1.
This species is very different from those already shown. It is
quite stumpy in appearance, but has all the generic characters
of Montlivaultia. It is pedunculate like the others shown. It ~
is a trifle wider at the top than it is long, the length being 2
centimeters. The base is small, and the sides make an angle of
about 75°.
Locality: Beach at Caracaran, Batan Island, southeastern Lu-
zon, No. 2.
Formation: Shale, probably Miocene.
PATTALOPHYLLIA d’Ach.
Circular, short attachment, somewhat compressed laterally;
calyx elliptical; wall naked, covered with fine ribs; septa
numerous, serrate; columella lamellar-like or rudimentary, sur-
rounded by a manifold circle of long, ragged rods. Eocene.
(Zittel.)
Pattalophyllia (?) bonita sp. nov. Plate XVIII, figs. 4 and 5.
EK. Osassco, Paleontographica italica, 8, 99, Pl. I, figs. 3 and 3b. bees
Geol. Surv. India, ser. XIV, I, 2, Pl. "Xx, figs. 1-3.
Calix almost circular in plan, inverted shallow cone. Dag
sinus where columella should be. Height, 1 centimeter; diam-
eter of crown of calyx, 2.5 centimeters.
This specimen resembles a form under the name - Calyptraea
rugosa Noetling from the Miocene of Burma. The name Calyp-
traea, however, according to Zittel has already been used for
one of the Platypoda.
It is also very similar to Trochocyathus nummiformis Duncan
from the Tertiary deposits of the Sind, India. The Philippine
form is deeper and has an elliptical hollow in the center, features
which readily distinguish it from the Indian species.
The closest resemblance, however, is to the figures in Osassco’s
VII, A, 4 Smith: Fossil Invertebrate Fauna 287
work, so that the a form might also be referred to
P. cyclolitoides. > -
Locality: Barrio Meola near ae Cebu, No. 272...
Formation: Miocene limestone.
CARYOPHYLLIA Stokes
Circular, with attached, spread out base; calix circular;
columella bundle shaped, consisting of little twisted rods; septa
wide and projecting; ribs simple; pale, wide, throughout most
of their length; free, Cretaceous, Tertiary, living. (Zittel.)
_ Caryophyllia (?) lacagana sp. nov. Plate XVIII, figs. 2 and 3.
Foss. Corals and Alcyonaria of Sind, Pl. I, figs. 2 and 3. Pal. Indica, 1.
The specimen here shown more nearly resembles C. compressa
Duncan than anything I have been able to find in the literature.
It differs a good deal in shape, but this may be due to distortion
or partial mutilation of the specimen.
The columella is not visible in the Philippine form so that
I cannot refer it to the genus Caryophyllia with certainty. It
seems to be decidedly more curved than the Indian form, and on
the basis of these differences I am giving it a specific name.
Length, 17 millimeters; width at widest part of the calyx, 14
millimeters.
Locality: Gt in road near Laoag, Ilocos Norte, Luzon, No.
356. .
meio: sates or Recent. marl.
TURBINOLIDE
FLABELLUM Lesson
Sraight; compressed; free or fixed; columella rudimentary;
septa numerous, not projecting; wall with epitheca and covered
with spines and ridges. Tertiary to Recent. (Zittel.)
Flabellum australe Moseley (?) Plate XVIII, fig. 7.
Challenger Reports, Zool. (1881), 2, 173, Pl. VII, figs. 4, 5.
The forms here shown resemble fairly closely in general ap-
pearance those figured in the Challenger Reports. However,
there are differences to be noted. The Philippine form shows a
smaller number of septa, and the 2 sharp end edges make a wider
angle with the base than in F. australe. These differences in my
opinion are not enough to warrant calling this more than a variety
of F’. australe.
*
288 The Philippine Journal of Science 1913
There are some specimens in the Bureau of Science collection
so broken that the columella, which is not visible in the entire
specimens, is visible nearer the base.
Locality: West side of Aroroy Bay near Point Colorado, Mas-
bate, No. 588.
Formation: Mio-Pliocene shale.
This species has been found living at depths varying from
shallow water to 1,500 fathoms.
The specimen shown on Plate XII, fig. 10, is also a Flabellum,
but it is too small and pe: a specimen to be specifically
determined.
ODONTOCYATHUS Moseley
Corallum with a fasicular columella and 3 crowns of pali, free
but with a minute scar of former attachment, in the form of a
deep saucer, with straight sloping sides and a broad flat base
composed of fused radiating tuberculate spines which project
like the spokes of a wheel all round the base of the wall.
(Moseley.)
Odontocyathus coloradus sp. nov. Plate XVIII, fig. 8.
This species is essentially the same as O. coronatus Moseley
save for one striking difference, the possession of 6, instead of
12, spines projecting from the base. This may be fortuitous, but
I am inclined to think not. The exterior wall is smooth and more
rounded in the Philippine form. Diameter of calix, 25 milli-
meters; height, 15 millimeters.
Locality: Point Colorado, Aroroy Bay, Masbate, No. 588.
Formation: Miocene or Pliocene shale.
LOPHOSERINZ2&
CYCLOSERIS Edwards et Haime
Free, disk shaped, circular; wall horizontal, naked with fine
granulated ribs, septa numerous, finely toothed on the upper edge,
the smaller ones intergrown on the inner edges with the larger.
Cretaceous, Tertiary, and Recent.
Cycloseris decipiens K. Mart. Plate XVII, fig. 5.
Tertiarscht. auf Java (1880), 146, Pl. XXV, fig. 3-6.
The specimen shown here is more perfect than the one figured
by Martin and has a hole in the center, which is entirely filled up
in the Javan form, otherwise the two are very nearly identical.
I frequently have found this form on dead reefs along the
coasts, and it is my impression that the species is still liv-
VIII, A, 4 Smith: Fossil Invertebrate Fauna 289
ing, although it may have another name. Closely allied, but
smaller, forms have been found at over 1,500 meters’ elevation at
Baguio, Luzon.
Locality: Ilaga River, Batangas, No. 24.
Formation: Miocene or Pliocene limestone.
PACHYSERIS Edwards et Haime
(Undaria)
Stock attached, leafy; calices arranged in simple rows sepa-
rated by comb-like ridges, the rows completely coalescing; septa
fine, crowded together ; columella warty, well developed. Eocene,
Oligocene, and Recent. (Zittel.)
Pachyseris cristata K. Mart. (?) Plate XVIII, fig. 9.
Tertiarscht. auf Java (1880), 145, Pl. XXVI, fig. 8.
This is more like P. cristata than any other of the Javan species
with which I have compared it. The Philippine specimens show
much more irregularity in the ridges, and the septa appear to be
somewhat finer.
Locality: Barrio Mesaba, Danao, Cebu, No. 272.
Formation: Miocene limestone.
PTYCHOCYATHUS (7?)
Ptychocyathus (7?) incognitus sp.nov. Plate XVIII, fig. 10.
In this specimen, the stock consists of two long calices joined
by the coalescing of the epitheca of the walls. The calices are
circular in section. At the top they measure in diameter about
2 centimeters, and they taper almost to a point. The walls are
about 3 millimeters in thickness, and strongly corrugated with
deep V-shaped grooves which run the length of the corallite.
Length of the specimen 7 centimeters. Nothing of the internal
structure can be made out as it is filled with recrystallized
calcium carbonate.
Locality: Unknown. Spanish collection.
Formation: Limestone.
SPONGIA®
LITHISTIDA
CHENENDOPORA Lamouroux
Beaker, funnel or cup shaped, thick walled, generally with
stem; inner side with small sunken osculis from which simple,
generally bent, canals penetrate deeply the thick wall. The
canals take a more downward inclination, and extend as vertical
290 The Philippine Journal of Science 1918
tubes in the stem. The surface is covered with fine pores or
krinkled integument. Skeleton consists of gnarled, branching,
warty protuberances possessing little lithistid bodies. (Zittel.)
Chenendopora (?) major sp. nov. Plate XVII, fig. 2.
Michelin, Iconographie Zodphytologique, 324, Pl. 77, fig. 13a.
I am unable, owing to the state of the petrifaction of this
specimen, to say definitely in what genus it should be placed. It
is unlike any thing in either the British Museum or the Leiden
collections. It may be a Cellepora as it is superficially not unlike
illustrations of Cellepora cucullina Mich. The surface under a
hand lens is seen to be perforated by innumerable minute pores.
The figure is reduced to one-fourth actual size.
Locality: Liguan, Batan Island, southeastern Luzon, No. 1.
Formation: Miocene limestone.
MADREPORIDAX 4
; MADREPORA Linneeus
Stock branching, bundle shaped, or lobulated, cobuba ae
small cells lying in a spongy net-like cenenchym; calix prominent
(especially in the young) with thick edge; septa not projecting;
visceral cavity divided into halves by 2 septa, opposite and touch-
ing one another on the inner edges; columella lacking. Tertiary
and Recent. (Zittel.)
This is the principal reef-building coral of the present time,
but is not common in the Tertiary except in the tropics.
Madrepora duncani Reuss. (?) Plate XVIII, fig. 6.
Tertiarscht. auf Java (1880), Plate XXV, fig. 11.
The polyp cavities are larger in this specimen than in Martin’s
Javan form and are slightly farther apart. These differences do
not seem to be of specific value, and the state of the specimens
does not justify any discrimination.
Locality: Barrio Mesaba, near Danao, Cebu, No. 272,
Formation: Miocene limestone.
ASTREACEZA
PRIONASTRAEA Edwards et Haime
Stock convex or uneven, walls commonly with thin epitheca;
bud submarginal, besides calycinal union; cells closely crowded,
prismatic, walls united interiorly above, separated below; calyx
polygonal, deep,. with simple borders; columella spongy; septa
thin, close, granulated, and serrate, the largest teeth in the
neighborhood of the centrum. Tertiary and Recent. (Zittel.)
VIII, A, 4 Smith: Fossil Invertebrate’ Fauna 291
Prionastraea (2) vasta Klz. Plate XVII, fig. 4.
Die Korallthiere des Rothen Meeres—Klunziger, Pl. IV, fig. 8.
This is not an especially good specimen on which to base any
comparisons, but most of our fossil corals are in no better con-
dition. I have referred this to the above species for the reason
that it looks more like the illustrations of this species than any
others which I had access to. I am inclined to question the
genus because of the arrangement of the septa, which should be
thin and closer together than are those in this specimen.
Locality: Caracaran River, Batan Island, southeastern Luzon,
yee tet ad eh
Formation: Limestone.
HYDROID ZOOPHYTES (?) Plate XIX, fig. 6.
It is not clear just what these specimens are. An examination
by a specialist is needed definitely to identify these low forms
which are on the borderland between plants and animals. They
are abundant in the uppermost limestones of parts of Moun-
tain Province of Luzon.
Locality: On the ridge west of Mount Mirador, Baguio, Moun-
tain Province, Luzon, No. 45.
Formation: Pliocene (?) limestone.
ECHINODERMATA
ECHINOIDEA
SPATANGIDE
SCHIZASTER Agassiz
Periproct excentric, posterior; ambulacra in unequal pairs, -
the anterior pair strong and directed forward, somewhat bent
and nearer the groove of the unpaired ambulacrum, the latter
deep and grooved along the edges; the double pores of the ante-
rior ambulacrum crowded and numerous. Principal develop-
ment in the Tertiary, seldom living. (Zittel.)
‘Schizaster subrhomboidalis Herkl. Plate XIX, fig. 1.
Tertiarscht. auf Java (1880), Anhang 5..
The specimen figured here, although not a perfect one, due to
some distortion and a hard encrusting matrix, answers in general
the description of this species, although I have not compared it
with any specimen or drawing. After the drawings for this
plate were completed several very perfect specimens of this
species were collected from the Miocene of Bondoc Peninsula,
292 The. Philippine Journal of Science 1913
Tayabas Province, Luzon. These are all quite like those de-
scribed by Martin from Java.
Locality: White cliffs on Minanga River, Cebu, No. 277.
Formation: Mio-Pliocene limestone.
SCAPHOPODA
SOLENOCONCH 42
DENTALIUM Linnzus
Shell tube shaped, elongated, conical, symmetrical, somewhat
bowed, gradually tapering toward the posterior end; open at
both ends; exterior surface longitudinally striated, ribbed, or
smooth; anterior opening simple not constricted, posterior small.
Numerous, mostly large, species occur in the Miocene and Plio-
cene. (Zittel.)
Dentalium tumidum sp. nov. Plate XIX, fig. 2.
The fragment figured here is only about 2 centimeters long,
but it is believed that it is sufficient to show the characters of
the species. The unusual cross-section showing the lateral bulg-
ing and thickening of the walls is apparently quite unique. I
have been unable to locate any specimen or illustration of any
form just like it, so I have given it the specific name twmidum to
note this prominent character.
This specimen is longitudinally striated like many other species
of Dentalium. At the widest part the diameter is 12 millimeters;
along the shorter diameter, 9 millimeters. The shell tapers
gradually as in other species of the genus.
Locality: Agusan River, Mindanao, No. 1054.
Formation: Pleistocene or Recent shales.
PLATYPODA
VERMETIDA
VERMETUS Adanson
Shell usually attached, irregularly tubular, internally vitreous,
and often with septa. Carboniferous (?) to Recent. Abundant
in the Tertiary. (Zittel.)
Vermetus giganteus K. Mart. Plate XIX, fig. 5.
Tertidrscht. auf Java (1880), 78, Pl. XIV, fig. 15.
An almost identical form from Java is figured by Martin under
the name of Septarea arenaria Linn., but in the text he calls it
V. giganteus n. sp.
VIII, A, 4 Smith: Fossil Invertebrate Fauna 2938
These tubular forms are so characterless, especially in the
fossil state, that it is particularly difficult to establish new species
among them.
Locality: Barrio of Mesaba, near Danao, Cebu.
Formation: Miocene limestone.
ARTHROPODA
- THALASSINIDAs
CALLIANASSA Leach
Body with the exception of the claws soft skinned; cephalo-
thorax small, compressed, abdomen very long and narrow, first
segment thin and short; caudal fin large; the claws of the first
pair of legs large and unequal, laterally much flattened, the
sharp edges set with fine serrations; movable finger joined to
the propodite and surrounded on both sides by a collar-shaped
process (“ball and socket’ joint); carpodite straight, united
with the propodite, of like shape and width as this, but shorter
and rounded and tapered posteriorly; the rest of the parts of
the claws markedly narrower and smaller. By the equal develop-
ment of the carpo- and propodite the claws of Callianassa are
distinguished from those of other crustacea. Recent and fossil
from the Juraon. (Zittel.)
Callianassa dijki K. Mart. Plate XIX, figs. 3 and 4.
These were compared directly with specimens in the Leiden
collection of Javan fossils and found to be quite the same. The
two parts shown here are propodites; that is, the joints of the
claw next to the movable finger or pincer.
I have never found any other parts of this animal save the
two last joints of the claw. They are quite common in Cebu in
the shale just above the large Compostela coal seam.
Locality: Old Compostela coal mines, Mount Licos, Cebu, No.
289.
Formation: Miocene shale.
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IpEM. The essential features of the geology of the Philippine Islands.
Phil. Journ. Sci., Sec. A (1910), 5, 307-348, 6 pls., 4 figs.
IpEM. Geological reconnaissance of Mindanao and Sulu: III. General
and economic geology. Phil. Journ. Sci., Sec. A (1911), 6, 359-395,
5 pls., 1 map, 1 fig.
SMITH, W. D., and EDDINGFIELD, F. T. Additional notes on the economic
geology of the Baguio mineral district. Phil. Journ. Sct., Sec. A
(1911), 6, 429-447, 3 pls., 1 map, 2 figs.
Tertiary and Upper Cretaceous Fauna of Western India. Mem. Geol. Surv.
India. Paleontologia Indica. Calcutta (1871-86), XIV, 1.
Tryon. Manual of Conchology. Philadelphia (1879-1898), I, 17 vols.
Woops. Paleontology (Invertebrate). Cambridge (England) (1902).
VERBEEK and FENNEMA. Description Géologique de Java et Madoura.
Amsterdam (1896), 2 vols.
ZITTEL. Eastman. Textbook of Paleontology. New York (1900), 1.
Ip—eEM. Handbuch der Paleontologie. Munich (1876-1880), 1 and 2.
1183657
eet seas
ors
ee
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age
ILLUSTRATIONS
Plates 8, 7, 8, 18, and 19 are from drawings by P. Moskaira and G. Gomez; Plates 4, 5, 6, 9,
and 10 are from drawings by G. Gomez; Plate 13 is from drawings by P. Moskaira; Plates
11, 12, and 20 are from photomicrographs by Charles Martin; Plates 14 to 17 are from
photographs by E. Cortes.
PLATE. I
Generalized geological map of the Philippine Islands.
PLATE II
Map of the Philippine Islands showing fossil localities.
PLATE IIT
Fic. 1. Conus sulcatus Brug.. var. philippinensis var. nov.
2. Conus odengensis K. Mart.
3. Conus djarianensis K. Mart.
4. Conus sp.
5. Turris (Pleurotoma) andaénsis sp. nov.
6. Turris (2?) agusana sp. nov.
7. Turris (Pleurotoma) flavidula Lam. var. sonde K. Mart.
8. Turbinella ilocana sp. nov.
PuaTe IV
Fic. 1. Nassa caniculata Lamarck.
1
2. Nassa verbeeki K. Mart.
3. Nassa siquijorensis A. Adams.
4. Rimella javana K. Mart.
5. Cassidaria echinophora Linn. (?)
6. Nassa caniculata Lamarck.
7. Nassa verbeeki K. Mart.
8. Nassa verbeeki K. Mart.
9. Melania laterita Lea.
10. Nassa verbeeki K. Mart.
11. Nassa sp. indet.
12. Natica globosa Chem.
13. Natica (Lunatia) sp.
14. Polynices (Natica) mamiilla Lamarck.
15. Bursa (Ranella) subgranosa Beck.
16. Tritonidea (Pollia) ventriosa K. Mart.
17. Hindsia dijki K. Mart.
18. Turricula jonkeri K. Mart.
19. Turricula bataviana K. Mart.
297
'
298
The Philippine Journal of Science
PLATE V
Figs. 1 to 3. Turbinella tjidamarensis K. Mart.
Fie.
F1G.
Fie.
Fie.
Fie.
4.
5
6.
7
8
ANnNNP wn eH COND OR wD
AGT PON
Turris (Pleurotoma) carinata Gray var. woodwardi.
. Dolium costatum Menke.
Cassis pila Reeve.
. Cassis nodulosa Gmel.
. Dolium costatum Menke.
PLaTE VI
. Turritella terebra Lam.
. Turritella cingulifera Sow.
. Melania woodwardi K. Mart.
. Vicarya callosa Jenk. var. semperi Smith.
. Cerithium (Campanile) sp.
and 7. Vicarya callosa Jenk. var. semperi Smith.
Vicarya callosa Jenk. var. semperi Smith, internal cast.
. Cerithium (Potamides) palustris Linn.
. Vicarya callosa Jenk.
Pate VII
. Azor coarctatus Gmel.
. Cultellus maximus Gmel.
. Modiolus sp.
. Clementia sp.
Clementia papyracea Gray.
. Macrocallista ventricola K. Mart. (?)
. Chione (Venus) chlorotica Phil.
. Chione (Venus) chlorotica Phil., interior.
PLATE VIII
. Chione (Venus) pulcherrima K. Mart.
. Dosinia boettgeri K. Mart.
. Clementia (7), internal cast.
. Chlamys (Avquipecten) (?) sp. indet.
. Lucina (Codakia) sp.
. Cardium elongatum Brug.
. Spondylus sp., internal cast.
PLATE IX
. Cardium flavum Linn. (?)
. Arca nodosa K. Mart. (?)
. Cardita boettgeri K. Mart.
. Cucullaea holoserica Reeve (7), cast.
. Same as fig. 4, end view.
. Pecten pallium Linn.
. Pecten sulcatus Mill.
1913
VIII, A, 4 Smith: Fossil Invertebrate Fauna 299
PLATE X
Fig. 1. Pecten (Chlamys) sp.
A coralline form, undetermined.
. Spondylus ducalis Chem. (?)
. Spondylus ducalis Chem. (?), lower value.
. Alectryonia folium Linn.
. Plicatula imbricata Menke. -
. Ostrea sp.
AS oP ooh ee
PLATE XI
Fic. 1. Orbitoidal limestone, Cebu.
2. Lithothamnium ramosissimum Reuss.
PLATE XII
Fig. 1. Section of radiolarian chert from near Nagpartian, Ilocos Norte,
Luzon.
2. Foraminiferal limestone, Batan Island.
PLATE XIII
Fic. 1. Operculina costata d’Orbigny.
2. Orbitolites complanata Lam. :
Fics. 3 and 4. Orbitolites, sections, much enlarged.
Fic. 5. Orbitoidal and coralline limestone.
Figs. 6 and 7. Lepidocyclina insulz-natalis Jones et Chap., central part.
Fic. 8. Lepidocyclina formosa Schlm. (7?)
9. Lepidocyclina formosa Schlm. (?), detail of the surface, much
enlarged.
10. Flabellum sp.
Fics. 11 and 12. Lepidocyclina formosa Schlm. (?)
13 to 16. Lepidocyclina insulx-natalis Jones et Chap.
17 and 18. Portions of radiolarian tests.
PLATE XIV
Pyrula (Melongena) sp. indet.
PLATE XV
Figs. 1 to 3. Voluta sp. indet.
PLATE XVI
Tridacna gigas Lamarck.
PLATE XVII
Fig. 1. Montlivaultia bulacana sp. nov.
2. Chenendopora (?) major sp. nov.
3. Montlivaultia bulacana sp. nov.
4. Prionastraea (?) vasta Klz.
5. Cycloseris decipiens K. Mart.
6
. Montlivaultia robusta sp. nov.
300 The Philippine Journal of Science
PLATE XVIII
Fig. 1. Montlivaultia cortada sp. nov.
Figs. 2 and 3. Caryophyllia (?) laoagana sp. nov.
4 and 5. Pattalophyllia (?) bonita sp. nov.
Fic. 6. Madrepora duncani Reuss (?)
7. Flabellum australe Moseley (?)
8. Odontocyathus coloradus sp. nov.
9. Pachyseris cristata K. Mart. (?)
10. Ptychocyathus (?) incognitus sp. nov.
PLATE XIX
Fig. 1. Schizaster subrhomboidalis Herkl.
2. Dentalium tumidum sp. nov.
Fies. 3 and 4. Callianassa dijki K. Mart.
Fic. 5. Vermetus giganteus K. Mart.
6. Hydroid zodphytes (?) in limestone block.
PLATE XX
Fig. 1. Section of old “slate” (?) containing Radiolaria.
2. The same specimen as that in fig. 1. 200.
< 100.
1913
“SGNV1S! ANIddITIHd SHL 40 dVW 1WVOID010SD GSZINVYANSD ‘1 3LV4d
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‘y ON ‘V ‘IITA “10g “NunOf “‘IIHgG] : [‘VNOAV GLVUEILYGAN] Tissog : HLM
Ssura: Fossm INVERTEBRATE FAUNA.]
GENERALIZED GEOLOGICAL MAP
OF THE
PHILIPPINE ISLANDS
Made under the Direction of
Warren BD. Smith
from surveys by members of the
Division of Mines, Bureau of Science.
Manila P/.
1913
MANILA
| Ais Masheiro Det
Alluvial and Tuff. Recent
littoral. voleanics.
(Prin. Journ. Scr, VIII, A, No. a
ma
Pre-Tertiary Metamorphic.
sediments
and doubtful
rocks.
PLATE I. GENERALIZED GEOLOGICAL MAP OF THE PHILIPPINE ISLANDS.
Plutonic
and older
extrusives.
‘
Be i > 8 " eX ~ v
- mM -
oer emer atime tient Se he ae n RTT RE NI nS ar Sahn dN amine
c . 4
.
i
7
SmitH: Fosst, INVERTEBRATE FAUNA. ] [Pum. Journ. Sor., VIII, A, No. 4.
5
QBasuvaly ISLANDS
7
Ovrnvce
®,
YY
Cogayanes Is.
Cavill 1 F
y6-Bataha
SEA
124°
PLATE II. THE PHILIPPINE ISLANDS SHOWING FOSSIL LOCALITIES.
:
- a
. cS . :
. 3
Ec rf
rt ane ba ane ‘
ro
ae
er)
oe
- Ss bs
ch » is ey
P %
”
. J ‘
s “
i
~ Se
CAITLLAG 2 annual & maid
a
(tt
hess
SmitH: Fossit INVERTEBRATE FAUNA. ] [Puit. Journ. Sct., VIII, A, No. 4.
PLATE Ill.
Fig. 1. Conus sulcatus Brug. var. philippinensis var. nov. 2. Conus odengensis K. Mart. 3.
Conus djarianensis K. Mart. 4. Conus sp. 5. Turris (Pleurotoma) andaensis sp. nov.
6. Turris (?) agusana sp. nov. 7. Turris flavidula Lam. var. sonde K. Mart. 8. Turbi-
nella ilocana sp. nov.
SmitH: Fossih INVERTEBRATE FAUNA. ] [PuiL. Journ. Scr., VIII, A, No. 4.
PLATE IV.
Fig. 1. Nassa caniculata Lamarck. 3. Nassa siquijorensis A. Adams. 4. Rimella javana K. Mart.
5. Cassidaria echinophora Linn. (?) 6. Nassa caniculata Lamarck. 2, 7, &. Nassa verbeeki
K. Mart. 9. Melanea laterita Lea. 10. Nassa verbeeki. 11. Nassa sp. indet. 12. Natica
globosa Chem. 13. Natica (Lunatia) sp. 14. Polynices (Natica) mamilla Lam. 15. Bursa
(Ranella) subgranosa Beck. 16. Tritonidea ventriosa K. Mart. 17. Hindsia dijki K. Mart.
18. Turricula jonkeri K. Mart. 19. Turricula bataviana K. Mart.
SmitH: Foss INVERTEBRATE FAUNA. ] [Puiu. Journ. Scr., VIII, A, No. 4.
PLATE V.
Fig. 1-3. Turbinella tjidamarensis K. Mart. 4. Turris carinata Gray var. woodwardi. 5. Dolium
costatum Menke. 6. Cassis pila Reeve. 7. Cassis nodulosa Gmelin. 8. Dolium costatum
Menke.
“es
SmitH: Fossit INVERTEBRATE FAUNA. ]
[PuIL. Journ. Scr., VIII, A, No. 4.
PLATE VI.
Fig. 1. Turritella terebra Lam. 2. Turritella cingulifera Sow. 3. Melania woodwardi K. Mart.
4. Vicarya callosa Jenk. var. semperi Smith. 5. Cerithium (Campanile) sp. 6, 7. Vicarya
callosa Jenk. var. semperi Smith.
8. Vicarya callosa Jenk. var. semperi Smith, internal cast.
9. Cerithium (Potamides) palustris Linn. 10. Vicarya callosa Jenk.
SmitH: Fosstt INVERTEBRATE FAUNA. ] [PHIL. Journ. Sci., VIII, A, No. 4.
PLATE VII.
Fig. 1. Azor coarctatus Gmelin. 2. Cultellus maximus Gmelin. 3. Modiolus sp. 4. Clementia
sp. 5. Clementia papyracea Gray. 6. Macrocallista ventricola K. Mart. (?) 7. Chione
chlorotica Phil. 8. Chione chlorotica Phil., interior.
ey! ieee ee a.
¥ ; 1 ber! ; eae sali ne
SmitH: Fosstt INVERTEBRATE FAUNA. |] [Puit. Journ. Scr., VIII, A, No. 4.
PLATE VIII.
Fig. 1. Chione (Venus) pulcherrima K. Mart. 2. Dosinia boettgeri K. Mart. 3. Clementia (?),
internal cast. 4. Indeterminate, cf. Chlamys (A-quipecten). 5. Lucina sp. 6. Cardium
elongatum Brug. 7. Spondylus sp., internal cast.
SmitH: Fossit INVERTEBRATE FAUNA. ] [Puit. Journ. Sct., VIII, A, No. 4.
PLATE IX.
Fig. 1. Cardium flavum Linn. (?) 2. Arca nodosa K. Mart. (?) 3. Cardita boettgeri K. Mart.
4. Cucullaea holoserica Reeve (?), cast. 5. Same as fig. 4, end view. 6. Pecten pallium
Reeve. 7. Pecten sulcatus Mill.
SmitH: Fossit INVERTEBRATE FAUNA.] {Puit. Journ. Sct., VIII, A, No. 4.
PLATE X.
Fig. 1. Pecten (Chlamys) sp. 2. A coralline form, undetermined. 3. Spondylus ducalis
Chem. (?) 4. Spondylus ducalis Chem. (?), lower value. 5. Alectryonia folium Linn.
6. Plicatula imbricata Menke. 7. Ostrea sp.
.
§
. 4 4
é C3 =)
SmiTtH: FosstL INVERTEBRATE FAUNA. ]
Si
rr4
¥
;
Fig. 1. Orbitoidal limestone, Cebu.
Fig. 2.
Lithothamnium ramosissimum Reuss.
PLATE XI.
(Pui. Journ. Scr., VIII, A, No.
SmitH: Fosst INVERTEBRATE FAUNA.] [Puin. Journ. Scr., VIII, A, No.
Fig. 1. Section of radiolarian chert from near Nagpartian, Ilocos Norte. Luzon.
Fig. 2. Foraminiferal limestone, Batan Island.
PLATE XIil.
SmitH: Fosst INVERTEBRATE FAUNA. ] [Puit. Journ. Scr., VIII, A, No. 4.
age
PLATE XIill.
Fig. 1. Operculina costata d’Orbigny. 2. Orbitolites complanata Lam. 3, 4. Sections of the
same much enlarged. 5. Orbitoidal and coralline limestone. 6, 7. Lepidocyclina insule-
natalis Jones et Chap., central part. §&. Lepidocyclina formosa Schlm. (?) 9. Lepido-
cyclina formosa Schlm. (?), detail of the surface, much enlarged. 10. Flabellum sp. 11,
12. Lepidocyclina formosa Schlm. (?) 13-16. Lepidocyclina insule-natalis Jones et Chap.
17, 18. Portions of radiolarian tests.
SmitH: Fossit INVERTEBRATE FAUNA. ] [Puit. Journ. Scr., VIII, A, No.
PLATE XIV. PYRULA (MELONGENA) SP. INDET.
S
“AX ALVId
; *yopul “ds eynjoA “¢-T ‘sBI4
7 ON ‘V ‘IITA “log “Nuno “11H g] ['VNOVY GivadatyaAN] TIssoq : HLS
OYVANVI SYDID VNOVGINL “IAX 3LV1d
"7 “ON ‘V ‘IITA “10S “Nunopr “lIHg] [VNOV. FLVudaLYGANT TIssoq : HLINS
[PuIL. Journ. Scr., VIII, A, No. 4. -
SmITH: FossiIL INVERTEBRATE FAUNA. ]
PLATE XVII
3. Montlivaultia
6.
2. Chenendopora (?) major sp. nov.
4. Prionastraea vasta Klz.
Fig. 1. Montlivaultia bulacana sp. nov.
Montlivaultia
Cycloseris decipiens K. Mart.
5
bulacana.
robusta sp. nov.
SmitH: FosstL INVERTEBRATE FAUNA. ] [Puru. Journ. Scr., VIII, A, No. 4.
PLATE XVIII.
Fig. 1. Montlivaultia cortada sp. nov. 2, 3. Caryophyllia (2?) laoagana sp. nov. 4, 5. Pat-
talophyllia (?) bonita so. nov. 6. Madrepora duncani Reuss. (?) 7. Flabellum australe
Moseley (?) 8. Odontocyathus coloradus sp. nov. 9. Pachyseris cristata K. Mart. (?)
10. Ptychocyathus (?) incognitus sp. nov.
SmitH: Fosst INVERTEBRATE FAUNA. ] (Pum. Journ. Scr., VIII, A, No. 4.
PLATE XIX.
Fig. 1. Schizaster subrhomboidalis Herkl. 2. Dentalium tumidum sp. nov. 3, 4. Callianassa
dijki K. Mart. 5. Vermetus giganteus K. Mart. 6. Hydroid zodphytes (?) in limestone
block.
SmitH: FossIt INVERTEBRATE FAUNA. ] [Pui. Journ. Sct., VIII, A, No. 4.
Fig. 1. Section of old “slate” (?) containing Radiolaria. >< 100.
Fig. 2. The same specimen as that in fig. 1. X 200.
PLATE XX.
BOTANY.
a FLORA OF MANILA
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THE PHILIPPINE
JOURNAL OF SCIENCE
A. CHEMICAL AND GEOLOGICAL SCIENCES
AND THE INDUSTRIES
VoL. VIII OCTOBER, 1913 . No. 5
THE GEOLOGY AND PETROLEUM RESOURCES OF THE SOUTH:
ERN PART OF BONDOC PENINSULA, TAYABAS
PROVINCE, P. I.
By WALLACE E. PRATT AND WARREN D. SMITH
(From the Division of Mines, Bureau of Science, Manila, P. I.)
Ten plates, 1 text figure, and 1 map
CONTENTS
INTRODUCTION. GEOLOGy—Continued.
General. Stratigraphy—Continued.
Previous knowledge of the region Vigo shale.
and sources of information. Voleanic agglomerate.
Scope of the present work. Structure.
Methods of field work. General.
GEOGRAPHY. Unconformities,
Situation. Central anticline.
Transportation. Region north of Central an-
Climate and vegetation. ticline.
Population. Malipa anticline.
GEOLOGY. Bato anticline.
General statement. Ayoni anticline,
Physiography. Cudiapi syncline.
Orography. - Maglihi anticline.
Hydrography. Banaba monocline.
Topographic control. Geologic history. | :
Stratigraphy. OCCURRENCE OF THE PETROLEUM.
Table of stratigraphy. PHYSICAL AND CHEMICAL PROPERTIES
General geologic sections. OF THE PETROLEUM.
Alluvium and travertine. ORIGIN AND PROBABLE QUANTITY OF
Littoral deposits and recent THE PETROLEUM.
coral reefs. AREAS TO BE PROSPECTED.
Malumbang series. CONCLUSIONS. iy
Canguinsa sandstone.
INTRODUCTION
GENERAL
The existence of petroleum seeps on the lower end of Bondoc
Peninsula, especially on Bahay River, was known among the
natives at least, during the Spanish régime, but no steps were
122679 301
f "Stikug \
% :
( APRS lem )
Won .
“tional Muse
Keessniran
Ce
802 The Philippine Journal of Science 1913
taken to explore the region, and no mention of petroleum in Tay-
abas is found in the records of the Spanish mining bureau.
Soon after American occupation, however, prospectors reported
oil from Bondoc Peninsula, and the field began to receive at-
tention. E. W. McDaniel, 8. W. Tilden, and the late Olney Bon-
dourant were among the earliest prospectors to locate petroleum
placer claims in Tayabas. Samples of the petroleum were sub-
mitted to the Bureau of Government Laboratories (now Bureau
of Science) in 1903.
A shallow well was sunk on Bahay River in 1906 by the Tay-
abas Mutual Oil Association, with E. W. McDaniel as manay-
ing director. It is stated that 46 gallons of oil were obtained
from this well in one day. The well was sunk ‘‘to a depth of
127 feet using a 32 by 23 inch by 3-foot bit operated by a hand
power springpole and duplex block attachment.’ Another well,
23 meters deep, was sunk on Malipa Creek by Mr. E. J. Cooke
and likewise is reported to have encountered oil.
Gradually, business firms in Manila became interested in the
field, and the area over which claims were located constantly grew
larger. Castle Bros. Wolf & Sons (now Pacific Commercial
Company) acquired a number of claims on Bahay River, and,
about the time of the publication by the Bureau of Science of
a report: on the physical and chemical nature of the petroleum
from the well drilled by Mr. McDaniel, this firm organized the
Bahay Valley Oil Company and started to sink a deep well.
The new well (Bahay 2) was located on Bahay River within
50 meters of the old well (Bahay 1), and was drilled by
Mr. O. A. Leary. The well reached a depth of less than 100
meters, and obtained no more oil than the old well.
With the beginning of drilling by the Bahay Valley Oil Com-
pany, in 1910, interest in the Tayabas field reached fever heat,
and claims were staked far and wide, but no further exploration
was undertaken. Since that time most of the locators have
merely awaited developments.
PREVIOUS KNOWLEDGE OF THE REGION AND SOURCES OF INFORMATION
The earliest published reference to petroleum in Tayabas is an
anonymous article? dealing with the activity of the Tayabas
Mutual Oil Association in 1906. A short discussion of the oc-
currence of petroleum in the Philippines by Smith* contains
* Richmond, Geo. F., This Journal, Sec. A (1910), 5, 1.
* Oil fields of Tayabas, Far Eastern Rev. (1906), 3, 102.
* Ibid. (1907), 3, 9.
VIIL, A, 5 Pratt and Smith: Petroleum Resources 303
a general statement concerning Bondoc Peninsula. Later in
the same year another article‘ on the Tayabas oil fields was
published.
Richmond’s® investigation of the physical and chemical
properties of several samples from Bahay 1 well was cited
above. Geo. I. Adams, formerly a geologist in the Bureau of
Science, spent two weeks on Bondoc Peninsula in 1909, and his
observations were included in a geologic reconnaissance of
southeastern Luzon,® together with the results of a few days
additional field work by the authors of that paper.
In January, 1911, F. T. Eddingfield and Wallace E. Pratt spent
two weeks in a geologic investigation of the southern part of
Bondoc Peninsula, and a short discussion based on this work
was published later in that year.’
During the summer of 1912, Wallace E. Pratt and F. A. Dal-
burg were engaged for nearly three months in geologic and
topographic field work on Bondoc Peninsula. The results of this
work were confirmed and amplified in three weeks of field work
by Warren D. Smith and Wallace E. Pratt in February, 1913.
These two periods of field work constitute the basis of this report,
although the results of previous field work have been drawn
upon freely and have facilitated the work.
SCOPE OF THE PRESENT WORK
- The time spent in the field would scarcely permit of the detailed
study of the area covered—700 square kilometers—even if the
country were easily traversed and the geology clearly defined.
As it is, the lack of an accurate map, the absence of trails, the
prevalence of jungle along the streams, and the heavy growth of
cogon and talahib*® have made it impossible to include detailed
or complete information in this report. The vegetation usually
conceals the geologic relations, and often renders impossible
a proper examination of places where precise information is
important. The mere physical effort of cutting through a jungle
or of “breaking trail” in the open, where the process involved
is one of literally burrowing through the tall rank grass, fre-
“Ibid. (1907), 4, 19.
° Loe. cit.
* Adams, Geo. I., and Pratt, Wallace E., This Journal, Sec. A (1911), 6,
473. Adams’s report also appeared as Bureau of Science press bulletin 2
which was printed in Philippine Resources (1909), 1, 19, together with The
Oilfields of Tayabas, a descriptive article by H. C. Hosty.
"Eddingfield, F. T., Min. Resources P. I. for 1910, Bur. Sci. (1911) 64.
*Cogon, Imperata cylindrica Beauv.; talahib, Saccharum spontaneum
Linn.
804 The Philippine Journal of Science 1918
quently leaves the observer inefficient through exhaustion before
his day’s work is fairly begun.
If the petroleum resources are developed, it is anticipated that
the additional and more accurate data which will become avail-
able as the jungle is cleared away and deep wells are drilled will
modify, or perhaps reverse, some of the conclusions of this pre-
liminary report. However, the present work should serve as a
basis for future investigation.
METHODS OF FIELD WORK
Field work on Bondoc Peninsula requires complete camp equip-
ment and the importation of all supplies from Manila. Moving
camp—a frequent task because of the limited area to which oper-
ations from each center are necessarily confined—involves pack-
ing everything on the backs of carriers, except along the coast
where small boats can be employed. The carabao, which is
used to a small extent as a pack animal by the native, is not
efficient in the interior, because water in quantity for its require-
ments is not usually available.
The geologic and topographic mapping, which is embodied in
the map accompanying this report, was executed in large part
with improved compasses, known as pocket transits, during the
main period of field work. The coast line and the elevations of —
the principal points, the altitudes of which could be determined
by triangulation from the sea, are taken from a coast survey by
the Bureau of Coast and Geodetic Survey. Upon this base is
plotted a triangulation survey which established the relative
locations of a number of points between Mount Maglihi and
Mount Cambagaco, made by Mr. Dalburg, using a standard
surveying transit. A stadia traverse by Mr. W. D. Buxton, of
the Bureau of Lands, from the town of Bondoc, via Bacau, to the
mouth of Bahay River and the small number of public land sur-
veys in the region are likewise included. For the rest, compass
surveys along the principal trails and stream lines—the distances
being paced—with vertical angle calculations and aneroid barom-
eter readings for elevations were made to serve.
The measurements and observations involved in defining the
stratigraphy and the geologic structure were made a part of the
compass traverses, data of this sort being most readily obtained
along water courses. It is recognized that the reliability of
stratigraphic and structural determinations made from measure-
ments along streams has been questioned by eminent geologists,
and the objection may be admitted, but the fact remains that
usually in the tropics the only clue to the nature of the rocks
beneath the surface débris is to be obtained in the streams.
~~ a a a
VIII, A, 5 Pratt and Smith: Petroleum Resources 805
Even in stream beds, geological observations are generally con-
fined to sections where active erosion is in progress. Where
limestone forms a part of the rock series, as in Tayabas, the uni-
versal deposition of travertine by flowing water is another factor
which tends to conceal the geologic relations.
The best criterion of the degree of accuracy which should be
accorded to this report is to be gained from a consideration of
the relative precision of the field methods employed. In one
sense, the closely determined elevations usually required for the
proper correlation of deep-well records were not essential to this
preliminary work in as much as no deep wells have been drilled
in the area described. Owing to the lack of deep wells, on the
other hand, the degree of conformity between surface and under-
ground strata in their structural relations and thicknesses is
unknown, and the structure recorded may not be that of the
deep-lying formations.
GEOGRAPHY
The established native usage is followed in this paper for
place names, the names of natural features, rivers, mountains,
etc. Where words have been passed upon by the United States
Geographic Board, the accepted spelling is adopted.
SITUATION
The area over which oil seeps are known to occur in Tayabas,
as shown on the accompanying map, includes that part of Bon-
doc Peninsula south of the towns of Catanauan and San Nar-
ciso, or approximately the southern half of the peninsula. The
territory mapped has an average width of 17 kilometers, is 50
kilometers long, and contains an area of 700 square kilometers.
Bondoc Peninsula marks the southern termination of the East-
ern Cordillera of Luzon. It is a long, narrow strip of land pro-
truding to the south-southeast from the southern coast of the
mainland of Luzon. The parallel of 13 degrees and 30 minutes
of north latitude and the meridian of 122 degrees and 30 min-
utes of east longitude pass through the region in which the
oil seeps occur. The principal towns at which steamers touch,
Catanauan and Mulanay on the west coast, are about 320 kilo-
meters (sailing distance) from Manila. The position of Bon-
doc Peninsula with reference to the other parts of the Philippine
Archipelago is shown on the index map.
TRANSPORTATION
The only access to the lower part of Bondoc Peninsula at
present is by steamship. Several small boats touch at Catana-
uan irregularly, averaging once a week, while the same boats
306 The Philippine Journal of Science 1918
stop at Mulanay somewhat less frequently. The nearest railroad
station is at Lucena, about 70 kilometers northeast of Catana-
uan. None of the rivers in the oil field are navigable. No
improved roads have been built on the peninsula; there are poor
trails between Catanauan and Mulanay, Mulanay and San Narci-
so, Mulanay and Bondoc, and between Bondoc and San Andres.
A few of the smaller outlying villages are connected by trails,
but these are used so little that they are not kept open and are
generally hard to follow. The principal trails are indicated on
the map.
CLIMATE AND VEGETATION
The months of March, April, and May constitute the dry sea-
son, and are the best months for field work on the peninsula.
The rains begin in June, and continue regularly through July
and August. During the other months of the year the rain-
fall is intermediate between that of the dry season and that
of the wet season. The Weather Bureau has no station in
this region, and consequently exact meteorologic data are not
available.
The more precipitous valleys and the mountainous regions are
wooded. Parts of the woods are good forest and fairly open,
but a large area has been cut over by the natives and is now
an impassible jungle of undergrowth. The country of inter-
mediate elevation is usually not wooded, but is covered with a
rank growth of cogon. Mangrove swamps are encountered near
the mouths of some of the rivers and on other areas of low
ground along the coasts.
POPULATION
In 1903 the total population in the area shown on the map
was 10,088. More than 40 per cent of this number lived in the
municipality of Catanauan. Bondoc and San Narciso, which
were listed as municipalities in the census of 1903, subsequently
fell to the rank of barrios, although the latter again has been
made a municipality within the last year. The population is
little if any greater, and it may be slightly less, than in 1903.
Coconut growing is the main resource of the region. Small
herds of cattle are encountered in the interior, but the number
is far less than the available grazing territory could support.
There are limited areas suitable for the cultivation of rice at a
number of places, but here again the opportunity is not generally
improved. A natural asset of the country is the buri palm which
grows without cultivation everywhere. From it the native se-
cures the material for his house and for the manufacture of
mats and bags—a household industry. His shoes are of buri
VIII, A, 5 Pratt and Smith: Petroleum Resources 307
bark, and in times of want the wood of the tree is ground into
buri flour which feeds his family.
It may be anticipated that labor will be scarce should this field
become active and that the efficiency of the local supply will be
low.
GEOLOGY
GENERAL STATEMENT
Bondoc Peninsula is made up almost entirely of sedimentary
rocks, and, if the regions of more recent sedimentary material,
such as the alluvium and raised shore deposits of the central
plain of Luzon and the volcanic tuff of southwestern Luzon, be
excepted, is one of the largest areas in the Philippines where the
rocks are essentially sedimentary and not seriously affected
by intrusion or vulcanism.
The series is principally shale and sandstone, with subordinate
thicknesses of limestone in the higher portion. The youngest
beds, disregarding the recent unconformable deposits, are Plio-
cene limestones, while the oldest rocks encountered are lower
Miocene or Oligocene shales. The measured sections show an
aggregate thickness of from 1,700 to 1,800 meters, and the base
of the shale series is not exposed. Possible repetition of beds
through minor faulting may make the apparent thickness greater
than the actual. The strata have been forced into folds along
lines trending approximately parallel to the axis of the penin-
sula; namely, north-northwest and south-southeast. The folding
has resulted in a principal anticline along the central portion of
the peninsula, separated by wide shallow synclines from subor-
dinate, more or less parallel, anticlines near the coasts on each
side. This simple structure is complicated by the presence of
minor folds approximately at right angles to the general trend.
The limestone at the top of the series has been folded in general
conformity with the lowest shale, so that the major lines of
structure are common to the entire stratigraphic column. The
anticlines of the folds are sharp, but the occurrence of extensive
faulting is not established.
PHYSIOGRAPHY
Excluding San Narciso Peninsula, the lower part of Bondoc
Peninsula may be considered as a single geographic and oro-
graphic province. The outline is regular, with the lateral coast
lines parallel, and the width maintained fairly constant to the
extreme end. The coasts swing to the west as the southern end
of the peninsula is approached, giving the southern portion of
the field an almost north and south axis, while farther north
8308 The Philippine Journal of Science 1918
the axis trends north-northwest and south-southeast. Pusgo
Bay, lying between San Narciso Peninsula and the mainland,
is the largest coastal indentation. San Narciso Peninsula is
remarkably similar in form and contour to the larger parent
mass.
OROGRAPHY
The surface of Bondoc Peninsula rises from the seashore on
both sides to a generally high, but dissected, interior. Before
erosion became effective, the peninsula must have had a flattened,
arch-like cross section. Through erosion, however, a great deal
of the material of the former arch has been removed, the relative
proportion which remains varying locally. In the northern
part of the field, but little of the old surface is left—a ridge of
tilted beds dipping toward the sea along the lateral coasts rep-
resents the lower part of the sides of the arch, while the highest
elevations, farther inland, lie just below the former surface of
the crown portion. Farther south erosion is not so far advanced
and the larger part of the crown remains as a high interior
plateau, incised by deep cafions.
From San Narciso south along the eastern coast the coastal
ridge continues unbroken to the mouth of Vigo River, which cuts
through it between the peaks of Cambagaco (elevation, 300
meters) on the north and Dagmit (elevation, 350 meters) on
the south. South of Mount Dagmit, the ridge is continuous to
Bahay River, which like the Vigo empties into the sea through
a narrow steep-walled valley. South of Bahay River the crest
of the ridge is broken by the valleys of several small streams
which flow across it, and the elevation decreases; although Mount
Maglihi, one of the southernmost peaks, is 390 meters high and
is mountainous in aspect.
On the western coast, the marginal hills are lower (elevation,
from 100 to 200 meters), the chain contains no conspicuous
peaks, and the ridge is generally less prominent than the eastern
coastal ridge.
In the central portion of the peninsula, the dissected plateau
is formed by Cudiapi Range (highest elevation, 448 meters) on
the north, with Balinsog Hill (elevation, 394 meters), Malum-
bang Plain (elevation, 250 to 270 meters), Mount Malasimbahan
(elevation, 360 meters), Mount Anuing (elevation, 350 meters),
Mount Banaba (elevation, 355 meters), and their environs mak-
ing up the southeastern portion. South of Cudiapi Range and
west of Mount Banaba, the high tableland persists across Pina-
malijuan Plain to the vicinity of Tala and Sili. On the north
this interior plateau drops abruptly to the low-lying valleys of
VIII, A, 5 Pratt and Smith: Petroleum Resources 309
Matataja and Vigo Rivers and is separated from the coastal
ridges on both sides by other erosional valleys. To the south-
east the plateau is not perfectly detached from the coastal ridge,
the intermediate valleys being shallow.
The southern termination of the interior plateau is at some
distance from the seashore, and a strip of low ground, several
kilometers wide, intervenes between it and Bondoc Head (ele-
vation, 392 meters)—a conspicuous landmark for navigators
rounding the southern point of the peninsula.
Mount Maclayao, 398 meters in height, is the most prominent
elevation in the north-central part of the field. It is really a part
of the west coast ridge, although it extends eastward into the
interior, and forms an area of high ground common to the head-
waters of the main drainage systems north of the plateau region.
HYDROGRAPHY
The main streams debouching upon the lateral coasts are con-
fined in comparatively narrow valleys near their mouths. Where
erosion is well developed, their middle courses are meandering
and are bordered by wide flat terraces of alluvium. The main
lines of flow follow the trend of the peninsula, so that streams
working back from the east and west coasts attain relatively
short lengths in the direction of their lower courses, but develop
their principal tributaries at right angles on each side, draining
long strips of territory to the northwest and southeast. Vigo
River, for example, flows almost east into the sea at its mouth;
but its largest affluent, Malipa Creek, flows north for a distance
greater than the length of the Vigo below the junction of the
two. 'Tagatay River, or the upper part of the Vigo, flows south-
east for a distance equal to the length of the lower east-flowing
portion of the stream, and other large tributaries come into
Vigo River from the northwest.
Pagsanhan and Talisay Rivers, which empty into the sea on
the southern coast, flow throughout their lengths in compara-
tively straight lines. Talisay, or Malumbang River, and Silon-
guin, or Canguinsa River,’ are remarkable in having no important
tributaries. In the plateau region these rivers and the Amoguis
branch of Pagsanhan River flow through narrow cafions. Bahay
River also has a deeply eroded valley, but has developed large
tributaries.
Ayoni, Matataha, and Mulanay Rivers are formed of several
*In the native usage a river assumes the name applied to the locality
through which it flows; consequently the same river may have several
different names.
310 The Philippine Journal of Science 1913
affluents of nearly equal importance which unite in one stream
as they approach the western coast. The Ajus, farther north,
is like the Vigo in the orientation of its branches. Guinhalinan
River, which is one of the largest rivers on Bondoc Peninsula,
consists of two principal tributaries coming together from almost
exactly opposite directions. Its south fork heads in the north-
eastern part of the area mapped, and flows north-northwest for
a distance of 15 kilometers where it meets the north fork, which
comes an equal distance from the north-northwest. From the
point of confluence the merged streams flow eastward into Ragay
Gulf, a distance of 5 kilometers. Thus, the main drainage of
Guinhalinan River is af right angles to the course of, and about
six times as long as, the principal stream.
TOPOGRAPHIC CONTROL
The general alignment of the water courses parallel to the
trend of the peninsula and the relatively short stream lines at
right angles to this trend—an extreme example of which has
been cited in the case of Guinhalinan River—are obviously due to
the contro] exercised by the prevailing strike of the rock strata.
Not only has the strike of the inclined beds affected in this
manner the alignment of the rivers, but the structure has in-
fluenced the relative positions of the main valleys and uplands.
Thus, the valleys find their greatest development in, or near, the
crests of anticlines; while the higher elevations occur in synclinal
troughs, on the limbs of the anticlines, or in regions where the
folding has not been severe (see geologic sections).
The upper courses of Vigo, Matataha, and Canguinsa Rivers
all lie in the crest portion of the Central anticline. The lower
part of Vigo River has cut through the ridge bordering the east
coast along the axis of a small anticline, and Silonguin River
has followed a similar line of cross structure. At the mouth
of Mulanay River, likewise, the beds strike east-northeast and
are steeply inclined, although only the southern limb of this
possible cross anticline has been proved. The high areas in
Cudiapi Range and in Bondoc Head represent synclines, while
the plateau to the south and southeast of Canguinsa River oc-
cupies a region which has not been greatly disturbed in the
process of folding. The ridge on each of the lateral coasts
consists of strata lying well down in the limbs of the general
arch of the peninsula, with Mount Maclayao near the western
coast, marking also the southern limb of the cross flexure at the
mouth of Mulanay River. i
It is believed that the processes which resulted in the folded
condition of the strata were initiated prior to the emergence of
VIII, A, 5 Pratt and Smith: Petroleum Resources 811
Bondoc Peninsula above sea level. Probably the elevation is
due, in part at least, to the folding and the main folds were out-
lined in the original land surface. If this theory is correct, the
early water courses must have occupied the structural troughs
or synclines. As folding progressed the anticlines became very
acute, and their position must have been marked by extensive
local shattering of the nonyielding limestone and calcareous sand-
stone in the upper part of the stratigraphic column. The syn-
clines, on the other hand, were left in broad gentle folds not
sufficiently pronounced to break the strata. Obviously, these
conditions would tend to hasten the progress of erosion along
the anticlinal zones; valleys probably formed on the anticlines
and developed with greater rapidity than was possible in the
synclines. Consequently, the synclines were soon deprived of
their streams through the piracy of the anticlinal drainage,
and the translation of the main water courses from synclines to
erosional valleys on the anticlines was accomplished.
There is a striking contrast between the low hills and wide
valleys, which are found in regions where the soft shale in the
lower part of the stratigraphic column has been exposed to ero-
sion over large areas, and the steep-walled valleys and the general
youthful appearance of the topography in parts of the field where
the upper formations have been preserved. Once these pro-
tecting rocks are removed, the shale yields readily to the cutting
action of the run-off and relatively mature land forms result.
It is probable that rivers emptying into the sea upon the lateral
coasts and gradually working inland along the lines of cross
structure have captured drainage, which previously had followed
the general strike of the formations. An apparent example of
a stream so captured is Canguinsa River, which probably at one
time flowed south into Amoguis River.
STRATIGRAPHY
Table of stratigraphy.—Table I shows the stratigraphic and
age relations of the rocks in the area under discussion. Tables
II and III with similar data for the largest producing oil fields
near the Philippine Archipelago are inserted for comparison.?°
Table II represents the Echigo field in Japan, and Table III"
the Moera Enim field in southern Sumatra.
* Tki, Tounenaka, Preliminary notes on the geology of the Echigo oil field,
Mem. Imp. Geol. Surv. Japan (1910), No. 2, 29.
“Tobler, Aug., Topographische und Geologische Beschreibung der Pe-
troleum Gebiete bei Moera Enim (Siid Sumatra). Tidschrift van het
Kominklijk Nederlandsch Aardrijkskundig Genootschap. (1906) Tweede
Serie, 23, No. 2, 199.
1918
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TABLE II.—Stratigraphy of the Echigo oil field, Echigo, Japan, according
to T. Iki.
Series. Character.
Recent. 2.225 3 eee ee Alluvium; clay, sand, and gravel
Pleistocene2s-.25--2se2=— .--| Diluvium; ancient river terraces
Pleistocene or Pliocene__.___.----| Unconsolidated clay, sand, and gravel
Pliocene 22.22 2see eee Clayey shale, sandstone and conglomerate, and
lignite beds.
Miocene 222-20 eee eee Gray sandy shale and subordinate layers of sand-
stone in which oil exists. <A bed of fossiliferous
limestone in this stage contains Lithothamnium
ramosissimum Reuss. Shale is locally petrol-
iferous. Interbedded andesitic agglomerate.
Black hard shale grading upward into gray sand-
stone. Interbedded andesitic agglomerate.
Miocene? (Lowest beds Eocene?) _|;Black shale with thin beds of bluish sandstone
and thick beds of white or bluish tuff sandstone
which is oil bearing.
Thickness.
1, 800+
VIII, A, 5 Pratt and Smith: Petroleum Resources 315
TABLE III.—Stratigraphy of the Moera Enim oil field in southern Sumatra
according to Aug. Tobler.
Series. Character, Thickness.
Recent and younger Pleistocene_| River alluvium, most recent tuff deposits, terra- |__..-_______
ces, ete.
Older Pleistocene_______________- Tuff and agglomerate, older terraces, etc. Effu- |----..--_-_-
sive rocks locally.
(OMAP ON Lo ee os ep Ee Ce 2 a eS ae ai! Gee a PR En eo er lb SESE re ene
Upper Palembang formation. Tuff, sandstone, 830
and conglomerate. Fresh-water forms in the
lower, well-bedded part, silicified wood. Sub-
BiGioe Qe ee Nee aérial and lacrustine origin. Effusive rocks lo-
cally.
Middle Palembang formation. Marl and marly 650
sandstones. Bedded sandstones and unbedded
clays with lignite beds. Estuary formation.
Important oil horizon.
Middle___-_- Lower Palembang formation. Shale and fine-
grained sandstone. Marine fossils. Volcanic
Miocene ---_-____--- material, mar], and local coral reefs. Important
oil horizon.
Lower --_--- Shale with interbedded limestone and calcareous
sandstone. Locally, clastic sediments, conglom-
, erate, tuff, agglomerate, sandstone, and marl.
Marine formation. Doubtful oil horizon.
Tneonformity....-.- ---..-.-+---- JA EBIOIG SIEISIVE TOCKA a) ones cn) oe ee ees
StaretV: Orbitoidal limestones-2- o-222— 2 ---se2-] ects eee
Stage III. Bedded marl and fossiliferous lime-
stone. Petroleum bearing?
Marl with leaf impressions and fossil fish scales ___|___...___-__
ea II. Clay, shale, and thin beds of coal____-___|______--_--.
1, 100+
Mliporenete = ene wanes eens
ID UCT a et Oe Se ee oes
StageI. Breccia and conglomerate. Coal bearing-|_.--.-------
BOIS LIC MOTE S LAUR LING PETE DON ete ee a tele oe a eee
| and diorite intrusions.
General geologic sections—An adequate description of the
individual stages is made difficult by the irregularity and varia-
bility of the upper strata. The limestones and calcareous sand-
stone of the Malumbang series are especially troublesome in this
respect and cannot be sharply defined. In reality all the strata
above the Vigo shale might be described as one formation—
massive sandy clay at the base, grading upward into sandstone
and limestone. Thus defined, the formation has a thickness of
about 250 meters.
816 The Philippine Journal of Science 1918
As a preface to the discussion of the separate formations,
general geologic sections obtained in different parts of the region
will be recorded. It should be remembered that the thicknesses
assigned to the various formations are estiniates only, and are
not based upon accurate data.
In the latitude of Matataha and Vigo Rivers a thickness of
the Vigo shale greater than is exposed elsewhere is encountered
in the limbs of the Central anticline near the middle of the
peninsula. ‘Toward the coasts on either side the upper forma-
tions appear overlying the Vigo shale. The section through the
rocks east of the anticlinal axis is shown in Table IV.
TABLE IV.—Geologic section from the seacoast westward through Cam-
bagaco Ridge and Vigo Valley to the axis of the Central anticline.
Approxi-
Formation. Description. mate thick-
ness.
Meters.
Recent: 2422 7.323 eee eee Raised coral reefsand alluvium. Coastal plain_-_--- 10
Wneonformiby es eas a a ee ae Se eee ee eae |
Upper limestone. Coralline; eastern slope of Cam- 30
bagaco Ridge; thick bedded to massive; dip 30°
northeast.
Malumbang series ___.__...-__--- Cudiapisandstone. Bedded, yellow to brown sand- 40
stone; calcareous and of medium-grain size; local
crossbedding; summit of Mount Cambagaco.
Lower limestone; gray to white; thick bedded or 20
massive; locally concretionary; dip 45° northeast.
Gray clayey sandstone, usually bedded; west slope 70
of Cambagaco Ridge.
Sandy massive clay; blue to gray in color: close 80
Canguinsalsandstone eee jointed in some exposures; dip 30° to 40° (north of
Vigo River to northeast, south of Vigo River to
southeast); abundant fossils in parts of base;
a single outcrop of volcanic agglomerate inter-
bedded (?) in base on Vigo River at the mouth of
Bagacay Creek. ;
Wnconformitysese ne ee eee Abrupt increase in the angle of dip; western base |------------
of Cambagaco Ridge.
Bacau stage. Grayish blue to black shale; fine 100
grained and bedded; dip 60° to 80° east-north-
east; traces of oil and inflammablegas. Volcan-
ic agglomerate and massive andesite (flow?), a
single outcrop on Tangob Creek; included in shale.
Shale interbedded with sandy shale and occasional |------------
layers of sandstone, all thin bedded; strikes in
various directions, dips usually steep; nearer axis
of anticline, dips become uniform 55° to 65° east-
northeast. Vertical in axis; base not exposed.
b Regular strata east of the anticlinal axis prob-
Vigo shaleic: toe 526 222 5 eee
ably at least 800 meters thick.
VII, A, 5 Pratt and Smith: Petroleum Resources 317
On Dumalog Creek (Table XIII) north of the line of the
section in Table IV, sandstone and conglomeratic sandstone occur
above the Bacau stage of the Vigo shale apparently bedded in
conformity with the shale below them, and a small outcrop of
voleanic agglomerate is found at an apparently lower horizon
in the Vigo shale than that of the agglomerate on Tangob Creek.
The Vigo shale appears to undergo a change in character from
east to west in that the upper beds become more sandy. This
lateral transition from shale to sandstone is revealed by com-
paring Table V, which is a section of the western limb of the
Central anticline, exposed in Matataha River, with Table IV.
The Canguinsa sandstone is not well exposed along the western
coast, and cannot be separated sharply from the Vigo shale. The
evidence of unconformity at the base of the Canguinsa sandstone
which was noted in Table IV does not appear in the Matataha
River section.
TABLE V.—Geologic section along Matataha River from the western coast
to the axis of the Central anticline.
EMCtes waded CP
Avoror- |
Formation. y Description. imate
thickness.
Meters.
Malumbang series______________- Lower limestone, yellow to white coralline lime- 30
stone overlying sandy, bedded limestone; dip 35°
southwest.
Canguinsa sandstone-____-_-.-_-- Concealedtintervale-.<52~ ee 238 eS ee 50
Canguinsa sandstone, Vigo
TUSUG Sec. See ee eee eee ae Interbedded sandstone, sandy shale, and shale with 250
occasional conglomeratic sandstone beds with
small pebbles of diorite, andesite, etc.; gray to
brown or yellow; almost horizontal in Mount
Cancalao.
Blue to black shale (Bacau stage?); traces of in- 20
flammable gas; base of Mount Cancalao. |
Sandstone and shale interbedded, dip southwest, 800
FS SN ee eee eee increasing toward the east up to 25°.
Thin-bedded shale, sandy shale, and sandstone,
general color brown or yellow; dip west-south-
west increasing toward the east from 25° to 70°;
strata vertical in axis of anticline.
The upper formations are exposed in section eee the crest of
the Central anticline in the valley of upper Canguinsa River
while the Vigo shale is uncovered in scattered outcrops only.
The section in Table VI was obtained in Balinsog Hill and the
eastern wall of the valley of Canguinsa River. Table VII shows
122679——2
318 The Philippine Journal of Science 1913
the relations in the opposite (western) limb of the anticline
observed in the western slope of South Cudiapi Mountain and
the western wall of Canguinsa River valley along Amuntay
Creek. Table VIII is a section in the eastern limb at Bacau.
TABLE VI.—Geologic section from the summit of Balinsog Hill downward
to the bed of Canguinsa River.
Approx-
Formation. Description. imate
thickness.
| Meters.
\(Upper limestone. Coralline, massive, yellow to 20
white limestone; not present except in rem-
; || nants on Balinsog Hill, but found on neigh-
Malumbang series ______-___-_-__- boring hills.
Cudiapisandstone. Bedded, brown to yellow, cal- 100
careous sandstone; alternate beds of different
|| thicknesses; dip 15° eastward.
| Lower limestone? Concealed or Jacking ....- eee
Gray calcareous sandstone; bedded, dip slight 100
to eastward.
Gray medium-grained sandstone with abundant 10
sandstone concretions.
| Gray sandy clay, massive; fossiliferous -___-_------ i 20
Wriconformity? =. 2 host EB a A A we sc eR pe a eee |_2
Wire shsles< 22:28 eter et ee | Bacau stage. Blue to black thin-bedded shale;
| occasional outcrops only.
Canguinsa sandstone -___________ |
|
TABLE VII.—Geologic section down the east slope of South Cudiapi Mountain
along Amuntay Creek to upper Canguinsa River.
| ise. Appr. |
Formation. Description. imate
thickness.
Meters.
| (Upper limestone? Not present; removed by ero- |------------
sion?
} Cudiapi sandstone. Yellow to brown calcareous 80
Maltonbare nevica toe aaa / sandstone, bedded; medium-grain size; summit
of South Cudiapi Mountain.
||Lower limestone. Yellow to white coralline lime- 20
stone exposed at base of peak of South Cudiapi
|| Mountain.
\{Imperfectly bedded, gray to yellow calcareous 60
Gaipdud adeue eee |] sandstone; dip to westward.
Gray to light blue sandy clay; compact and jointed; 100
| not bedded; fossiliferous.
Unconformity? _-.-=:---------.. ee
Migojshale:- 4457s. five Bacau stage. Occasional outcrops only, along Bese=2=a2=>-
Canguinsa River; blue to black, thin-bedded
shale; dips steep to east and west. |
fovea
VIM, A, 5 Pratt and Smith: Petroleum Resources 319
TABLE VIII.—Geologic section in the eastern wall of Canguinsa Valley at
Bacau; from the rim of the valley to the bed of the river.
Approx-
Formation. Description. imate
thickness,
Meters.
Upper limestone; yellow to. white coralline and 80
sandy limestone, imperfectly bedded; dip 15° to
25° northeast.
Cudiapi sandstone; calcareous, medium-grained 80
sandstone; alternate beds of different thick-
_ nesses; dip 15° to 45° northeast.
Malumbang series---------------
Lower limestone; coralline; poor exposures, not 20
certainly in place.
Canguinsa sandstone_-_---_-___--_- Gray sandstone, jointed and clayey; exposures poor _ 100
lelnconsormitycabraupucnanwe in |o- eee eek ee wee en NSN eee ec oe ese eee
angle of dip.
Bacau stage; blue to black petroliferous shale, 30
petroleum seep; bedding is indistinct and appear-
ance massive; fine-grained clay shale with
v irregular, subordinate sandy zones; dip 55° east-
Wigoiphalest= see. nn
northeast.
Thin-bedded blue to black shale; occasional layers |------------
of sandstone; dip 60° east-northeast; outcrops in
| stream floor.
Above the Vigo shale in the western wall of Canguinsa Valley
at Bacau there are about 100 meters of clayey gray sandstone.
About 1 kilometer farther to the northwest the Lower limestone
occurs above this sandstone.
The section in Table IX represents the eastern face of South
Cudiapi Mountain down to Cauayan Creek. The rocks here dip
eastward at low angles, lying in the western limb of the Ayoni
anticline.
TABLE IX.—Geologic section down the western slope of South Cudiapi
Mountain to Cauayan Creek.
H soe |
Formation. : Description. ; imate
thickness.
Meters.
Upper limestone; not present; removed by erosion?_ |_-.---------
Cudiapi sandstone; yellow to brown calcareous 80
Malumbang series...........---- sandstone; bedded, medium-grain size; summit of
South Cudiapi Mountain.
Lower limestone; yellow to white coralline lime- 20
stone.
Canguinsa sandstone_____.-____- Gray clayey sandstone; bedded and calcareous in 170
upper portion; massive, sandy fossiliferous clay
at base.
UE TCOME OPIN Gye oa sae Se ol ee eee ne EON Cae Ae deen Mie rh no IES
Wirotshalet: orcad: oe eee Bacau stage; blue to black thin-bedded shale, traces
of inflammable gas; occasional exposures only.
320 The Philippine Journal of Science 1913
The lower part of Bahay River, where it cuts through the
eastern limb of the Maglihi anticline to the eastern coast, exposes
the section recorded in Table X.
TABLE X.—Geologic section on the lower part of Bahay River; from the
mouth of the river inland.
Approx-
Formation. Description. imate
thickness.
Meters.
Recent 2.-2<2553 = eee Yellow to brown raised coral reefs and coral sand; 10
coastal plain.
Unconformity. .- = 2-25-35 = 502 be ee I apie i a a
Upper limestone; coralline; dip 30° northeast; 15
Malumbang series. ..-2---9--=--- east slope of the ridge near coast.
Cudiapi sandstone? ~}eoneeatea interval __...-.-.- 100
Lower limestone ?___-
Canguinsa sandstone__-_-_-_---- Gray, bedded, clayey sandstone; dip 35° north- 140
east.
Gravel or conglomerate, sandy matrix, large 5
pebbles of diorite, quartz, crystalline orbitoidal
Canguinsa sandstone? _____------ limestone, etc.
||Coralline limestone grading into calcareous sand- 8
stone at base; dip 45° northeast.
Mnconformity? } 1. = ete es ee Bee ee ee
Sandstone and shale, irregular thin beds; small 10
| Viso'shale? shes tes 5.5 2 tees | seams of lignite; dip 55° northeast.
| Sandy blue clay ‘2-2: )..25. 5.22222 8. ttt ee ee 3
Brown coarse-grained sandstone, thick bedded 10
to massive; carbonized leaf impressions.
\Blue to black carbonaceous shale; sandy; base |------_-._--
not exposed; dip 55° northeast; occasional out-
| crops only; 1,500 meters northwest of the line
of this section at about this horizon oil seeps
from Bacau stage of Vigo shale on Milipilijuan
Creek and at a somewhat greater distance
southeast at Bahay, oil seeps from a con-
cealed formation. |
Wico shale - 226° Stare ee ae
———. <=<-,..-=.- - *.- ™
> 2 oe
= es ee
oe es
VIII, A, 5 Pratt and Smith: Petroleum Resources 821
The gravel and coralline limestone between the Vigo shale
proper and the Canguinsa sandstone in the foregoing section
are unusual and their correlation is doubtful. It should be
stated that the character of the gravel and the relations of its
occurrence allay any suspicion that it is a recent, superimposed
deposit.
Near Mount Morabi in the eastern limb of the Maglihi anticline,
south of Bahay, the section shown in Table XI was obtained.
TABLE XI.—Geologic section in the vicinity of Mount Morabi; from the
coast at San Andres to the summit of thé mountain.
Approx-
Formation. Description. imate
thickness.
|
| Meters.
FPP Ont ncees oh Oheetns. tNisue t's Yellow to brown, coralline, sandy limestone, lies 10
nearly horizontal; narrow coastal plain, vicinity
of San Andres.
Upper limestone, coralline -----_------------------- 15
: .|Cudiapi sandstone. Bedded calcareous sandstone. 30
Malumbang series-_---- .--------- ) Dip 30° east.
||Lower limestone, coralline to sandy---------------- 30
Bedded, gray, caleareous sandstone; dip 55° east: 50
| east face of Mount Maglihi and Mount Morabi.
|| Yellow to white limestone with abundant coarse 5
sand, locally small pebbles of diorite and |.
: , '| quartz, large lepidocyclinas; dips steeply to east,
Canguinsa sandstone----------- vertical and even overturned to west; summits
of Mount Maglihi and Mount Morabi.
_|Gray calcareous sandstone, bedded; west face of 20
|| Mount Maglihi.
Clayey, massive sandstone; valley west of Mount 40
Maglihi.
MOI TICPOIPEODID EY ieee ace te Se el Sh ee er ee ye i a ol pe RR UR oe ee a
Mura stini@s sa 2ee ee sea Bacau stage; bedded blue to gray shale with |_--__-------
F sandstone. Occasional outcrops in Canibo Creek; |
steep dips to east and west, thickness of afew me-
ters only exposed; oil seep at Banco; salt water in
Maalat Creek. :
322 The Philippine Journal of Science 1918
A final section obtained at the village of Cubcub (outside the
area mapped), about 15 kilometers northwest of San Narciso,
is shown in Table XII.
TABLE XII.—Geologic section on Guinhalinan River in the vicinity of
Cubcub, Peris.
i Approx-
Formation. Description. imate
thickness.
Meters.
Upper limestone; coralline; isolated patches only; 10
summit of Mount Bogas.
Malumbang series-_-__-_---------- Cudiapi sandstone; bedded, calcareous, fossilif- 80
erous; toward base, clayey.
Lower limestone? Concealed or lacking -.-...-.---|------------
Canguinsa sandstone--_-_-_-__--_-- Gray, sandy clay, massive and fossiliferous. 100
Tinaplaca Creek.
Brown coarse-grained sandstone; traces of in- 8
flammable gas. Tinalpaca Creek.
Thin-bedded shale with occasional sandstone beds; 600+-
Tinaplaca Creek, Pigsaan Creek and Guinhal-
inan River at Cubcub. Extensive exposure at ’
Cubcub; in upper part, sandstone beds 10 centi-
meters to 1 meter thick with blue to gray, fine-
grained, thin-bedded shale and brown, sandy
shale; farther down in series fewer sandstone
beds, more sandy shale in thin beds alternating
with shale of finer grain. Strata lie inclined at
an angle of 80° and show subordinate buckling in
lower part of series; thickness in continuous ex-
posure, 250 meters; indicated additional thick-
ness, 350 meters; base not exposed.
Alluvium and travertine.—Recent alluvium is found along
the valleys of Pagsanhan, Vigo, Mulanay, and Ayoni Rivers.
It occurs near the mouth of the Pagsanhan, but on the other
rivers it is most extensive along the middle courses above the
gaps through which these rivers enter the sea. The material
consists of clay and sand with subordinate quantities of sand-
stone and limestone gravel. Fresh-water shells and occasionally
pieces of wood partly carbonized are found in the alluvium. The
river terraces usually rise less than 6 meters above the level of
the stream.
Travertine is also deposited by running water throughout
Bondoc Peninsula and is of more general distribution than
alluvium, although as a geologic formation it is subordinate.
The salts of calcium which are deposited as travertine are leached
from the limestone and calcareous sandstone strata, usually by
surface waters. Deposits from springs are exceptional. As is
Vigo shale22:_2.--- 222
VII, A, 5 Pratt and Smith: Petroleum Resources 323
usual with travertine deposited by streams, the formation is
most extensive over faces of waterfalls where beautiful rounded
terraces often develop; but wherever the streams flow rapidly
enough to break into ripples, travertine is precipitated abun-
dantly, and even in still water a veneer of travertine covers the
whole stream floor.
Where the flow is rapid, the travertine is eventually built
up so as to raise the stream level. As soon as the travertine
forms a barrier in this way it accelerates its own growth and
ultimately becomes a natural dam. Stream ponding is thus
developed, or the water may be diverted to a new channel ad-
jacent to the old bed. A curious interpretation of this phe-
nomenon has grown up among some of the prospectors familiar
with the Tayabas field. As it is commonly expressed: “Where
a river dams itself up, you are close to oil.”” A possible slight
basis for this belief may be found in the fact that the petro-
liferous or carbonaceous beds precipitate the calcareous salts
from the water, and are usually coated with travertine in con-
sequence. However, since decomposing vegetable matter, such
as fallen leaves and twigs, and evaporation from the surface
of the water are active precipitating agents, this rule of thumb
method of prospecting leaves much to be desired. On the other
hand, the travertine seriously retards geologic study in that it
often conceals the formations along the streams where they
would otherwise be open to examination.
Littoral deposits and recent coral reefs.—Narrow coastal
plains, composed mainly of raised coral reefs, occur at intervals,
bordering the peninsula. Clay, sand, and other shore materials
are intermingled with the corals in varying degrees. The result
is a yellow to white, heterogeneous, unconsolidated formation
without distinct or regular bedding planes, which is generally
youthful in aspect. Shells and fragments of coral closely related
to species that are to be found alive in the adjacent seas are
prominent constituents of the rock. The disintegration product
is a brownish yellow sandy clay which generally covers the
ground surface.
These deposits lie nearly horizontal and are found from sea
level to an elevation of at least 15 meters. The coastal plain
between the mouth of Ajus River and Catanauan attains a
greater elevation than 15 meters, but here, as well as elsewhere,
it is difficult to delimit the raised reefs from the older coralline
limestone. Numerous small areas of mangrove-covered littoral
‘deposits are to be seen farther south along this coast. On the
324 The Philippine Journal of Science 1918
west coast, the formation is to be found in the region of Mi-
najero Bay and north beyond San Andres. Between the mouths
of Bahay and Vigo Rivers and farther north near San Narciso,
the vicinity of the coast line is made up of littoral deposits.
At various places over the surface of the littoral formation
shells were observed which probably represent the molluscan
fauna existing when the benches were below sea level. All the
species identified are still living, and many of them are edible.
Numerous deserted kitchen middens are encountered near the
coast, and it is possible that some of the shells collected came
from these middens and do not represent the formation upon
which they were found.
The genera and species noted are as follows (Plate I):
Spondylus. Potamides sp.
Conus flavidus Lamarck. Voluta sp.
Trochus fenestratus Gmel. Natica sp.
Arca cecillei Phil. (?) Crista pectinata Linn.
Astralium stellare Gmel. Strombus canarium Linn.
Cerithium nodulosum Brug. Telescopium telescopium Linn.
Cerithium jenkinsi K. Mart. (?)
Malumbang series——The Malumbang series at the top of the
column of folded strata consists of the Cudiapi sandstone, which
is generally, but not invariably, included between limestones.
The limestones are sandy and at many places are either missing
or cannot be distinguished from the sandstone which is usually
calcareous. They are brownish yellow to white, and generally
massive or in thick poorly defined beds. Locally, and usually
in the sandy facies, the limestone is bedded, the individual layers
averaging from 15 to 30 centimeters thick.
The Upper limestone is generally coralline, although the tran-
sition between it and the calcareous sandstone below is gradual.
At places on the coast where it is not highly inclined, it cannot
be delimited from the recently raised reefs. In representative
exposures it shows a thickness of about 30 meters.
The Cudiapi sandstone is named from a type occurrence in
the summit of South Cudiapi Mountain. In many places it
exhibits alternate beds of different thicknesses; the thinner beds
are more calcareous and harder than the intervening thicker
beds, and are more resistant to weathering so that the outcrops
are characterized by the protruding edges of the thin beds.
Where the Lower limestone is missing, the Cudiapi sandstone
cannot be separated sharply from the underlying Canguinsa
sandstone. The estimated thickness of the Cudiapi sandstone °
VILL, A, 5 Pratt and Smith: Petroleum Resources 325
ranges from 40 to 135 meters. The exposure on the summit of
South Cudiapi Mountain is about 80 meters thick.
The Lower limestone is generally less than 20 meters thick.
It is harder and more compact than the Upper limestone, and
is more frequently bedded. In other respects, the limestones
of the two horizons are similar and hardly to be distinguished.
On Mount Cambagaco, in the stratigraphic position of the
Lower limestone, a rock of unusual appearance is to be seen.
It is composed mainly of limestone concretions, 1 centimeter or
more in diameter, which have a concentric structure. The con-
cretions lie close together in a cement which is also calcareous,
giving the rocks a magnified odlitic texture. This particular
variety of the Lower limestone was not observed outside the
one vicinity near Mount Cambagaco.
The Malumbang series attains its greatest development in the
vicinity of Malumbang Plain extending north beyond Balinsog
Hill, south through Mount Banaba and Mount Guinamuan, and
southwest to Tala and Sili with a detached area farther south on
top of Bondoc Head (see geologic map). The lower two members
are found in the Cudiapi Range, while the ridge along the east
coast consists of a single limestone (Lower?) overlying the Vigo
shale with a concealed interval between. San Narciso Peninsula
is covered by the Upper limestone.
All three horizons in the Malumbang series are fossiliferous.
Fossils were collected at two places on the hills at the northern
edge of Malumbang Plain, which are capped by the Upper lime-
stone. Specimens from fossil locality 61 were obtained on the
hills north of Mount Anuing near the eastern rim of Canguinsa
River valley at Bacau, and others (fossil locality 63) were found
on the hills immediately to the east on the northern border on
Malumbang Plain. The Upper limestone in this vicinity is
sandy, and grades imperceptibly into the Cudiapi sandstone bhe-
low it. The fossils are embedded in sandy, calcareous material
which might be designated either as sandstone or limestone.
Fossils collected at locality 61.
Pecten senatorius Gmel. + Conus indet.
Pecten leopardus (?) Reeve. Olivia indet.
Cytherea indet, : - Strombus labiosus Gray. +
Cardium indet. Melania sp.
Schizaster subrhomboidalis Herkl. Dosinia sp.
Xenophora dunkeri K. Mart. (7) Lagenum multiforme K. Mart. var.
’ Turbo indet. tayabum var. nov.
826 The Philippine Journal of Science 1913
Fossils collected at locality 63.
Conus indet. Turbo borneénsis (?) Bttg.
Pecten senatorius Gmel. + Trochus sp.
Mitra indet. Bulla ampulla Linn. +
Xenophora indet. Oliva indet.
Spondylus imperialis Chem. + Pattalophyllia sp. +
Operculina costata d’Orb. + Cycloseries sp.
Of the determinable fossils in these and the following lists,
those which represent living species are indicated by a plus sign.
Fossils were obtained from the Cudiapi sandstone at three
different places, as follows: (1) Fossil locality 65, calcareous
sandstone immediately beneath the Upper limestone in the hills
north of Malumbang Plain, adjacent to fossil locality 61; (2)
fossil locality 4, calcareous sandstone beneath the Upper lime-
stone about 450 meters south of Balinsog Hill, at an elevation
of 360 meters; (3) fossil locality 13, sandstone, at an elevation
of 270 meters on the high ground between Apad and Milipilijuan
Creeks, affluents of the Bahay River. The Upper limestone does
not occur over the sandstone at this place, but the sandstone
itself is very calcareous.
The fossils from the Cudiapi sandstone were determined as
follows: °
From fossil locality 65.
Pecten sp. Dosinia sp.
Schizaster subrhomboidalis Herkl.
From fossil locality 4.
Turbo sp. indet. Pleurotoma sp. indet.
Nassa sp. indet. Melania sp. indet.
Fusus sp. indet.
From fossil locality 13.
Clementia sp. indet. Cerithium herklotsi K. Mart.
Xenophora dunkeri K. Mart. Pleurotoma tjemoroénsis K. Mart.
Ostrea orientalis Chem. (?) + Pleurotoma carinata Gray. +
Pecten senatorius Gmel. +
Fossils from limestone at a horizon corresponding stratigraph-
ically with that of the Lower limestone were collected at three
localities, namely: Fossil locality 44, at the mouth of Ayoni River;
fossil locality 59, on a prominent hill (elevation, 250 meters)
2 kilometers west of Tala; and fossil locality 25, near Tambo,
a barrio of San Narciso. However, as’ will appear in the dis-
cussion of the field relations at these localities, only the last group
in the foregoing list represents certainly the Lower limestone;
the fossils from the other localities may belong to either the
Upper or Lower limestone.
On the north side of Ayoni River near its mouth, fossils were
VIIL, A, 5 Pratt and Smith: Petroleum Resources 327
found in the limestone which forms the ridge along the western
coast of the peninsula.
Fossils collected at locality 44.
Cypraea sp. indet. - Cerithium sp. indet.; large internal
Arca nodosa K. Mart. (7?) cast.
Schizaster sp.
Along the western coast from Ayoni north to Catanauan, this
limestone is found in the coastal ridge, and occurs conformably
only a short distance above beds which clearly belong to the Vigo
shale. A short distance inland from Ayoni similar limestone
occurs above the Canguinsa sandstone, and is overlain at places
by the Cudiapi sandstone. This relation suggests that the lime-
stone at Ayoni is the Lower limestone, but the evidence is not
conclusive and either limestone horizon may be represented by
the fossils from this locality.
Fossils collected at locality 59.
Pyrula gigas K. Mart. Pecten leopardus K. Mart.
Balanus sp.
The limestone in which these fossils were found occurs on the
top of a hill; below the limestone, with a concealed interval
between, the Canguinsa sandstone was observed. The thick-
ness of the concealed beds is hardly great enough to include
the Cudiapi sandstone and the Lower limestone in their usual
thicknesses. The fossils, therefore, are assigned to the Lower
limestone, although they may represent the Upper limestone
instead.
A sample of limestone (fossil locality 25), which certainly
came from the Lower limestone horizon, was collected near the
Cabongahan-San Narciso trail at an elevation of 180 meters, on
the east side of the ridge extending northwest from Mount Cam-
bagaco. Thin sections of this rock show small fragments of
limestone and the well-known alga, Lithothamniwm ramosissi-
mum Reuss, intermingled in a cement of calcite.
Plates II and III are photographs of typical fossils from the
Malumbang series. Plate II represents the Upper limestone and ~
the Cudiapi sandstone, while Plate III shows fossils from the
Lower (?) limestone.
The most conclusive evidence as to the age of the Malumbang
series is found in the Lower limestone, which, on the basis of the
fossil Lithothamnium ramosissimum Reuss (fossil locality 25)
may be assigned to the Miocene. The upper beds in the series
are apparently as young as the upper Miocene or the Pliocene.
The formation is similar to the “étage marneux’”’ which Ver-
328 The Philippine Journal of Science 1913
beek"? assigns to the middle stage of the upper Tertiary for Java,
and describes as follows:
IX. Middle stage of the upper Tertiary.
Formations called the marl stage. Middle and upper Miocene
Abundant marl and marly sandstones. highest beds in part Plio-
Less abundant sandstone and shale with} cene.
some calcareous beds.
* * * JX The second stage or the middle Neo-Tertiary stage m:,
probably contains at a slightly lesser depth than the lower division, some
beds of Middle and Neo-Miocene and even Pliocene age, which cannot
always be distinguished in the field and are called by us the “marl stage”
on account of the principal rock. One finds here, besides some calcareous
sandstones with numerous marine shells, beds of conglomerates and breccias
(much less than in the stage M), then some shales, noncalcareous sand-
stones and calcareous beds, the last named having occasionally orbitoides
with spatula shaped chambers (lepidocyclines) * * *.
The Cudiapi sandstone, the principal rock in the Malumbang
series, might be called a marly sandstone, and the limestones
are likewise often sandy or clayey. Shale is not present, but
some exposures of the Cudiapi sandstone are argillaceous.
No indications of petroleum have been observed in the Malum-
bang series. It is above the horizon at which oil seeps occur,
and bears on the possible petroleum industry only in the fact
that it must be drilled through before the petroliferous zones
can be explored in parts of the promising territory.
Canguinsa-sandstone.—The Canguinsa sandstone is a close-
grained, gray or blue rock to which the term sandstone applies
ina general way. It is distinguished from the Cudiapi sandstone
by its massive or less perfectly bedded appearance and by the
considerable proportion of clay which characterizes it. The
upper portion is usually a soft, clayey sandstone, imperfectly
bedded and occasionally close jointed. This sandstone is calca-
reous, and several exposures on the upper part of the Canguinsa
River are concretionary. The concretions are aligned so as to
lend a bedded appearance to the exposure. The concretionary
sandstone was not observed to be of general distribution.
Toward the base of the formation either a typical sandstone
or an indurated massive or jointed clay is encountered. Both
sandstone and clay occur in heavy banks from 3 to 6 meters thick,
and both are slightly calcareous. The sandstone facies in the
basal portion is deep blue on fresh exposure, but weathered sur-
faces are gray or brown. Ordinarily, it is of medium-grain
size, and shows little evidence of bedding. The clay is also blue
“Verbeek and Fennema, Description Géologique de Java et Madoura.
Amsterdam (1896), 1, 38, 41.
Vu, A, 5 Pratt and Smith: Petroleum Resources 829
when freshly exposed, and becomes gray upon weathering; it is
fine and compact, but not bedded. Some of the rocks which have
been classed as marl in Java and Sumatra are probably similar
to the slightly calcareous clayey zone in the Canguinsa sandstone.
The clay and sandstone banks in the base of the formation are
fossiliferous and sometimes contain myriads of small shells. The
fossils are often greasy and appear to be well preserved, but in
reality they are very fragile, and can be removed entire only
with care.
In the section on lower Bahay River, the Canguinsa sandstone
includes a few meters of limestone and conglomerate. On Mount
Maglihi and Mount Morabi limestone which contains coarse sand
and small pebbles of diorite, quartz, and andesite is present in
the Canguinsa sandstone, but no conglomerate was observed.
In the lower part of the gorge on Canguinsa River, also, a sub-
ordinate thickness ef limestone was found in the Canguinsa
sandstone. ;
Volcanic agglomerate, with some appearance of bedding, out-
crops at the junction of Bagacay Creek and Vigo River in the
base of the Canguinsa sandstone, or possibly between it and the
underlying formation. The outcrop is of limited extent, and is
the only instance of volcanic rocks above the Vigo shale.
The thickness of the Canguinsa sandstone varies from 50 to
160 meters. Although it occurs unconformably over the Vigo
_ Shale, the contact between the two formations is found always
near the same horizon in the Vigo shale, and the base of the
Canguinsa sandstone serves as a datum for rough correlation.
The Canguinsa sandstone is not encountered in large areas,
but occurs in steep slopes along streams where it has been pro-
tected from erosion by the overlying Malumbang series. It is
exposed at the surface or overlain by patches of the Lower lime-
stone, in parts of Malipa Creek valley, and is prominent among
the rocks of the Cambagaco-Dagmit ridge along the eastern
coast. On the western coast it is little in evidence, although it
occurs in the western slope of South Cudiapi Mountain. Calca-
reous sandstone and limestone, overlying Vigo shale and conse-
quently referred to the Canguinsa formation, cap a ridge between
two branches af Mulanay River in the northern part of the field.
Pieces of agglomerate, in which, among other constituents, peb-
bles of schist were noted, are found.in this vicinity, and are pro-
bably to be referred to the voleanic agglomerate horizon.
Two groups of fossils from the Canguinsa sandstone proper
(fossil localities 7 and 12) ; and fossils from the included lime-
stone beds on Mount Morabi (fossil locality 62) and Mount Mag-
830 The Philippine Journal of Science 1913
lihi (fossil locality 67) have been studied; photographs of some
of the specimens appear on Plate IV.
Fossils were found in the Canguinsa sandstone on Amuntay
Creek (affluent of Canguinsa River) at an elevation of 150
meters. Here the Canguinsa sandstone is about 160 meters
thick (see geological section, Table VII). The fossils were
found about 40 meters above the base of the formation in tough
jointed gray clay. They include:
Fossils collected at locality 7.
Pecten fricatum Rv. + Dosinia sp. indet.
Pecten sp. Pleurotoma suturalis Gray (?)+
Pecten senatorius Gmel. +
The following fossils were collected from a clayey, blue sand-
stone in the base of the Canguinsa immediately above the Vigo
shale on the upper part of Tangob Creek, about 50 meters north-
east of the main occurrence of voleanic agglomerate shown on
the geologic map.
Fossils collected at locality 12.
Strombus canarium Linn. Pattalophyllia sp.
Conus ornatissimus K. Mart. Septarea arenaria Lam. +-
Corbula socialis K. Mart. Mitra javana K. Mart.
Cypraea erosa Linn. + Natica mamilla Linn. +
Hindsia sp. Ranella sp.
Pleurotoma flavidula Lam.
A microscopic section through a specimen of the limestone
occurring in the Canguinsa sandstone on Mount Maglihi (fossil .
locality 67) showed it to be made up of fragments of sandstone,
quartz, and limestone in a calcareous cement and to ‘contain
Foraminifera with lozenge-shaped cells, probably of the genus
Lepidocyclina. The limestone from Mount Morabi (fossil local-
ity 62) contains Cycloclypeus communis K. Martin, which repre-
sents the middle Miocene, and large lepidocyclinas some of which
are 45 millimeters in diameter and 5 millimeters broad in the
thickened central portion. Lepidocyclina richthofeni Smith was
identified among these. This species has been referred by Dou-
villé ** to the lower Miocene.
No definite age determinations can be made from the fossils
in the Canguinsa sandstone proper. The fossils in the included
limestone, however, are well known and have been used in cor-
relation by various authorities. From their presence it is con-
cluded that the Canguinsa ‘sandstone should be placed in the
middle Miocene, extending, perhaps, into the lower Miocene.
The Canguinsa sandstone occurs immediately above the prin-
* Compt. rend. Soc. géol. de France (1909), 14, 130.
VII, A, 5 Pratt and Smith: Petroleum Resources 831
cipal known oil horizon. It is not porous enough to afford a -
reservoir in which oil might accumulate, and no oil has been
observed in it. Because of its compact nature on the other hand,
it would tend to confine any oil collecting below it. At several
promising drilling sites the Canguinsa sandstone must be drilled
through before the petroleum zone is encountered.
Vigo shale.-—The base of the Canguinsa sandstone is marked
by an unconformity, which is partly of a mechanical nature, but
may represent also a period during which the underlying forma-
tion, the Vigo shale, was subjected to erosion. The subject of
unconformities is discussed in connection with the geologic struc-
ture, page 337.
The Vigo shale is the most extensive and the most uniform
series in the stratigraphic column of Bondoc Peninsula. The
beds belonging to this formation, although they are closely re-
lated in type to some of the overlying beds, constitute a separate
stratigraphic division which is readily distinguished.
The type exposures in the valley of Vigo River consist of fine-
grained shale and sandy shale interstratified in thin regular beds
from 5 to 10 centimeters in thickness. Occasional beds of sand-
stone occur varying from 10 centimeters to 1 meter in thickness.
The fine-grained shale is gray, blue, or black, and is made up
almost entirely of clay. The sandstone is gray or brown, and
consists of uniform,medium-sized, not completely rounded grains
of quartz, diorite, andesite, and metamorphic rocks. The sandy
shale is yellow or brown and of intermediate composition.
There is an apparent transition from east to west in the
character of the Vigo shale. In the eastern limb of the Central
anticline, exposed in the valley of Vigo River, the formation is
predominately shale throughout, sandstone occurring only at in-
tervals. In the western limb shale predominates in the exposure
near the axis only, that is, the lower part of the series. Farther
to the west the sandstone beds increase in number,. until in the
upper horizons they become more prominent than the shale.
The grain-size likewise increases in the upper beds, and small
pebbles occur, forming layers of sandy conglomerate.
The blue or black, fine-grained shale in the Vigo formation
usually emits a slight odor of light oils upon fresh fracture, and
in some outcrops is highly petroliferous. The material loses this
odor and assumes a light gray color after it has been exposed to
the air and has become thoroughly dry. The petroliferous shale
forms a loosely defined stage in the upper part of the Vigo, which
will be referred to as the Bacau stage, although it cannot bé
sharply delimited.
332 The Philippine Journal of Science 1913
The Bacau stage contains fewer beds of sandstone than the
Vigo shale proper, and the bedding planes are often less distinct;
thus, exposures at Bacau and Sili have the appearance of massive
banks of compact, hardened clay, which are sandy in subordinate,
irregular zones only. To material of this character the ordinary
definition of shale which stipulates a fissile or laminated texture
does not apply strictly, but the term is convenient and, employed
in a broad sense, is preferable to “clay” or ‘“‘clay-shale” in de-
scribing the rocks in the Bacau stage. The shale weathers into
concretion-like ellipsoidal pieces from which concentric layers
split off, and break into small fragments with conchoidal surfaces.
The manner of weathering distinguishes the petroliferous beds
from other fine-grained layers in the Vigo which are fissile and
split into flakes upon disintegration.
Beds analogous in character to those in the Bacau stage are
found throughout the Vigo shale, but the Bacau stage proper
appears to be confined to a zone from 50 to 75 meters thick in
the upper portion. In the eastern half of the field, the Canguinsa
sandstone overlies the Bacau stage in a majority of exposures.
Occasionally (section on Dumalog Creek, Table XIII, page 333;
and on Bahay River, Table X, page 320), sandstone and fine
conglomerate, which are evidently a part of the Vigo series,
occur above the Bacau stage. In the western part of the penin-
sula sandy conglomerate is found near the top of the Vigo forma-
tion. These overlying beds may be always present above the
Bacau stage, but concealed generally by an overlap of the un-
conformable Canguinsa sandstone. The sandstone and conglom-
erate in the upper part of the Vigo shale are generally micaceous,
and show many carbonized leaf-impressions. In the south-
western part of the field, large pieces of silicified wood were ob-
served in the conglomerate, and on Bunsaua Creek a bed of
lignite 20 centimeters thick occurs in the shale below this horizon.
Two exposures of andesitic agglomerate were encountered
which appear to be in the Vigo shale—one at the head of Tangob
Creek, north of Cabongahan, and the other on Dumalog Creek
at the head of Guinhalinan River. The Tangob exposure is
in the upper part of the series, a few meters below the Canguinsa
sandstone; while the outcrop on Dumalog Creek appears to be
considerably lower in the Vigo shale, several hundred meters
below the base of the Canguinsa sandstone. Elsewhere, no ag-
glomerate was noted except as float, and it is not certain that
the Dumalog agglomerate is in place.
- The thickness of the Vigo shale is unknown. An apparent
thickness of about 1,400 meters is revealed in the Matataha
VIIL, A, 5 Pratt and Smith: Petrolewm Resources 833
River section, the section on Malipa Creek in the southern limb
of the Malipa anticline shows 800 meters of Vigo shale, and the
section on Guinhalinan River indicates 600 meters. None of
these sections exposes the base of the formation. The apparent
thickness of the sections as measured along the outcrop may be
in excess of the actual thickness as a result of superficial expan-
sion of the beds or of the repetition of beds from faulting or close
folding.
As is indicated on the geologic map, the Vigo shale is promi-
nent in the north-central portion of the field. A smaller area
is exposed along the southwestern coast. The deeper valleys
have uncovered Vigo shale in other parts of the peninsula.
A small number of fossils were observed in the lower part of
the Vigo, and the shale in the Bacau stage and the overlying con-
glomeratic sandstone are fossiliferous. 'The specimens are frag-
ile and upon removal disintegrate readily, in a manner that
suggests the effects of calcination. Frequently they are envel-
oped in a film of oil or grease as are the shells in the clay beds
of the Canguinsa sandstone.
At fossil locality 11 on Dumalog Creek, fossils were found in
bedded blue-black shale which is placed in the Bacau stage of
the Vigo. This locality is on the trail from San Narciso to Mu-
lanay on the west slope of Cambagaco Ridge at an elevation of
130 meters.
The stratigraphic relations are shown in Table XIII.
TABLE XIII.—Geologic section downstream on Dumalog Creek.
Fossil locality 11.
| Formation. Description. Thickness.
Meters.
Malumbang series and Can-| In the east slope and the crest of Cambagaco 200
guinsa sandstone. Ridge, limestone and sandstones are encountered
in obscure relations. The general dip is east-
ward at an angle of about 30°.
‘Gray to brown sandstone and fine conglomerate. 10
Strike, north 50° west; dip, northeast, 45°.
Black laminated clay or shale. Carbonized leaf- 20
impressions and lenses of ‘lignite, 5 millimeters
thick.
Maisonphalescs525_ Ss shes bd 2 Gray to brown sandstones, massive, coarse grained _ 10
Bacau stage; thin-bedded shale with subordinate 50
sandstone beds; dip 65° northeast; fossils found
in the shale beds.
Goncealedianterval oo. 2-2" ee 22 5 Eire 400
Volcanic agglomerate, a single small outcrop in |-_-----------
thin-bedded shale and sandstone.
122679——3
834 The Philippine Journal of Science 1913
Among the fossils collected the following were identified.
Fossils collected at locality 11.
Conus loroisii Kien. + Tapes rimosa Phil. +
Pyrula sp. Conus striatellus Jenk.
Arca sp. Conus hochstetteri K. Mart.
Natica sp. indet. Fusus sp. indet.
In a specimen of the conglomeratic sandstone which occurs
in the upper part of the Vigo shale in Matataha Vailey one
species of Mitra and one of Pyrula were noted. Globigerina
(Plate V) was found in the Vigo shale, more abundantly in the
Bacau stage.
The general aspect of the fossils in the Bacau stage of the
Vigo shale is very similar to that of the fossils in the base of the
Canguinsa sandstone (Plate IV). The age. of the beds is not
fixed definitely, but the fresh appearance of the shells and the
number of species still living make it improbable that they rep-
resent a period earlier than the Miocene. The base of the series
may be as old as the Oligocene.
The Vigo shale includes all the known petroliferous horizons
in this field. Seeps of petroleum and inflammable gas occur in
the Bacau stage, generally within a few meters below the base
of the Canguinsa sandstone; on Malipa Creek, however, traces
of oil and gas are observed with 250 meters of Vigo shale
exposed above them. The occurrence of petroleum is discussed
on page 349.
As to the character of the rocks which occur below the Vigo
shale, there is little evidence. The shale may rest directly upon
the basal diorite which is cited by Becker** as probably the
oldest formation in the Philippine stratigraphic column, or upon
a sedimentary series older than the Vigo shale. Elsewhere in
the Philippines, Miocene shale has been found in some cases to
overlie Eocene shale and limestone, in others to rest immediately
upon a base of older igneous rocks, and rarely to be underlain
by older “slates” which are probably of Jurassic age.
At Peris, about 25 kilometers northwest of San Narciso, the
common basal diorite occurs, overlain unconformably by the
Cudiapi sandstone. Toward the south, successively older forma-
tions, down to and including the Vigo shale, at least, undoubtedly
overlap the diorite base just as the Cudiapi sandstone does at
Peris. Possibly sedimentary rocks older than the Vigo shale
intervene between it and the lowest parts of the diorite floor.
“ Becker, G. F., 21st Ann. Rep. U.S. Geol. Surv., 1899-1900, pt. III
(1901), 24 of reprint.
VIII, A, 5 Pratt and Smith: Petroleum Resources 335
Volcanic agglomerate——In the northeastern part of the area
shown on the map several exposures of andesitic agglomerate
were encountered. Two outcrops were found at different hori-
zons in the Vigo shale and one in the base of the Canguinsa
sandstone.
The most extensive outcrop is a conical hill about 1 hectare
in area and 50 meters high. The form is not unlike that of
an old volcanic plug, but may be due entirely to the work of
erosion. The material is principally agglomerate; but appar-
ently massive andesite is to be seen in the central part of the
exposure, while an intermediate zone consists of andesite in which
the fragments occur in a stony crystalline matrix. The other
exposures are also conical in form, but are much smaller and
consist entirely of agglomerate, angular fragments of andesite,
varying in weight from a fraction of a kilogram to 10 kilograms,
embedded closely in andesitic tuff. There is a suggestion of
bedding in the agglomerate in the base of the Canguinsa sand-
stone on Vigo River. The outcrops are gray to dark brown,
and are weathered in a manner that leaves the fragments pro-
truding irregularly from the matrix. The agglomerate appears
to be interbedded in the shale, but the contacts are obscure and
it is not certain that it does not lie upon an eroded surface
of shale.
Near the village of Bato, bowlders of fragmental rocks, prob-
ably volcanic agglomerate, were observed in which sedimentary
types—sandstone and shale—are most prominent, but are ac-
companied by andesite. A thin section of fragmental andesite
from this agglomerate was examined under the microscope. The
texture is decidedly porphyritic with a large proportion of pheno-
crysts, consisting of dark green to brown hornblende and plagio-
clase feldspar crystals. In the subordinate groundmass oc-
casional crystals and fragments of magnetite are scattered.
The petrographic character indicates an extrusive, certainly not
a plutonic and probably not an intrusive, rock. A more homo-
geneous specimen of andesite taken from the main exposure on
Tangob Creek shows similar characteristics. It is porphyritic,
one of the hornblende phenocrysts measuring more than 1 centi-
meter in length. The hornblende crystals are more abundant
than in the previously described rock, and show well-defined
reaction rims.
The several outcrops of volcanic agglomerate occur along a
line roughly parallel to the general strike of the sedimentary
beds. They are of small area, the distances between them are
relatively great, and there is little reason to believe that they
836 The Philippine Journal of Science 1913
represent a continuous formation. The fact that parts of the
formation are typical agglomerate with a tuffaceous matrix makes
it very improbable that these outcrops represent an intrusion.
The material appears to be clearly of volcanic origin and to
consist principally of fragmental ejecta. Whether each outcrop
represents a center of local effusion, or is the remnant of a
larger sheet of agglomerate which came from a distance and
was interbedded in the shale, cannot be decided without further
investigation. i
The importance of the igneous rocks relative to the accumula-
tion of petroleum is problematical. Traces of oil and gas are
found in the shale on Tangob Creek adjacent to the largest
outcrop of agglomerate. If the observed outcrops mark local
centers of extrusion, then the beds stratigraphically below them
must be pierced and more or less broken by the volcanic vents
from which the agglomerate was thrown out. In the light of
drilling experience in most large oil fields this condition prob-
ably would be looked upon with disfavor. However, iit is well
known that large flows of oil have been obtained in Mexico near
volcanic rocks which have come up through sedimentary beds,
and it has been suggested ** that the vulcanism has supplied the
conditions necessary for the accumulation of the petroleum.
Thus, even if the agglomerate in Tayabas has been extruded
locally, it should not condemn any part of the field, and may
have had a desirable effect.
If the agglomerate has not been extruded locally but has been
thrown out from a distant center, its presence probably has little
bearing on the question of petroleum exploitation. It is con-
ceivable, of course, that an impervious sheet of interbedded
agglomerate might influence the accumulation of any petroleum
in the rocks below it, but the data available do not warrant any
procedure based on this possibility.
On the whole, in view of their limited extent and of their
probable extrusive origin, it may be concluded that the igneous
rocks have no important bearing, either favorable or unfavorable,
on the possibilities of this oil field.
STRUCTURE
General.—Bondoc Peninsula occupies a geanticlinal zone in
the folded strata of southern Luzon and the adjacent islands.
Ragay Gulf, lying east of the peninsula and between it and the
larger peninsula of southeastern Luzon, probably occupies an
* Garfias, V. R., Journ. Geol. (1912), 20, 2, 666.
VII, A, 5 Pratt and Smith: Petroleum Resources 337
adjacent geosyncline. The elevation of Bondoc Peninsula above
sea level is due, in part at least, to its anticlinal structure.
In the general arch which the strata form across the width
of the peninsula there are minor undulations which have been
studied as individual folds. Among these folds the anticlines
are more sharply defined, and hence more easily traced, than
the synclines. Because of this and of their probably greater
importance in connection with petroleum accumulation the anti-
clines have received more attention than the synclines. In con-
nection with the discussion of the structure reference should
be made to the geologic sections shown on the map.
Confusing irregularity is encountered in the strikes and dips
of the Vigo shale in parts of the field, particularly in the upper
valley of Mulanay River and in a small area north of Cabon-
gahan. At the latter place along small streams, outcrop after
outcrop was examined, the strikes and dips of which are utterly
at variance, even when all but the most reliable-appearing expo-
sures are ignored. Because of this fact, the structural relations
have proved locally undeterminable.
The Vigo shale is a thinly laminated and nonfrangible for-
mation which would scarcely be maintained as a competent arch
in folding, but probably would break and move upon itself where
the strains were most severe, leaving the strata in confused
disorder at these points. In the crest region of the Central
anticline the shale is much disturbed, and extreme confusion in
the attitude of the beds is encountered near the intersection of
this fold with the minor cross anticlines, while the strikes are
regular and uniform only in the limbs or far down in the core
of the anticline. The squeezing and distortion, due to close
folding in a formation structurally incompetent, together with
superficial displacement and caving due to erosion, are probably
the main causes of the observed irregularity in the Vigo shale.
Unconformities.—In addition to the unconformity at the base
of the recent deposits on Bondoc Peninsula there is considerable
discordance between the Canguinsa sandstone and the Vigo
shale. No exposures were found showing an eroded surface of
the Vigo shale beneath the Canguinsa sandstone, but in regions
where the inclination of the beds is steep an abrupt increase in
the angle of dip is apparent on passing from the higher to the
lower formation, although the strike remains more or less
constant.
The change in the degree of inclination of the two formations
is best illustrated by the conditions on the upper part of Malipa
Creek where steeply dipping Vigo shale is overlain by almost
338 The Philippine Journal of Science 1913
horizontal Canguinsa sandstone. Similar relations are to be
observed along the western base of Mount Cambabaco.
Overlap on the part of the Canguinsa sandstone, which would
be expected if this member were laid down upon the truncated
edges of the Vigo shale, is not very extensive. At a number of
places the Canguinsa sandstone is encountered above approxi-
mately the same horizon in the Bacau stage of the Vigo shale.
Elsewhere, as is shown in the section on Dumalog Creek, page
333, and the section on Guinhalinan River, page 322, more or
less sandstone or sandstone and fine conglomerate, bedded con-
formably with the Vigo shale, intervene between the Bacau
stage and the Canguinsa sandstone.
The volcanic agglomerate might be taken as evidence of a
distinct break in the process of sedimentation if it occurred
uniformly between the discordant members, but the outcrops
do not appear to lie along the unconformity nor to be confined
to a single horizon. It is possible, however, that more detailed
work would show that the agglomerate does occur along the
unconformity, and thus indicate a decided break between the
Vigo shale and the overlying formations. In the data at hand,
however, the overlap of the Canguinsa sandstone and the steeper
dips in the Vigo shale are the principal evidences of unconformity.
If the steeper angle of dip in the Vigo shale, as compared
with the overlying formations, is accounted for by assuming that
the later rocks were laid down on an eroded surface of previously
folded Vigo shale and were themselves thrown into folds sub-
sequently, two periods of folding are involved with a remarkable
coincidence in the position and trend of the later folds along
the axes previously established in the Vigo shale. A theory of
a single period of folding is simpler and is in accord with the
observations in the field, if mechanical unconformity, resulting
from the different frangibility of the Vigo shale and the over-
lying formations, be admitted as adequate to account for the
overlap of the Canguinsa sandstone and the lesser inclination
in the beds above the Vigo. On the other hand, there is evidence
in the sandstones and conglomerates immediately above the
Bacau stage that the seas became very shallow before the dep-
osition of the Canguinsa sandstone began, and it is possible
that the Vigo shale emerged from the sea and became subject
to erosion, although positive evidence of erosion is lacking. The
fossils in the two formations indicate that there was no great
interval of time between them.
Whether the unconformity is one of erosion or of mechanical
discordance only, the Canguinsa sandstone appears to overlap
VIII, A, 5 Pratt and Smith: Petroleum Resources 339
the Vigo shale, and this is of practical importance in that the
overlap may conceal petroliferous members of the Vigo shale
above the Bacau stage. The conclusions in this report regarding
the general lines of structure—the position of the main anticlines
etc.—are to a degree independent of the unconformity, since
the larger folds are approximately coincident above and below
the discordance.
Central anticline.—The principal structural feature of Bondoc
Peninsula is the series of folds whose trend conforms roughly to
that of the peninsula. These folds are made up of broad shallow
synclines and narrow acute anticlines. Subordinate anticlines
occur near both lateral coasts, and a larger anticline designated
as the Centra] anticline marks the axis of the peninsula.
The Central anticline is asymmetric in that the eastern limb
is more highly inclined than the western. The fold is sharp,
especially in the lower strata which are vertical along the axis,
and about 25 kilometers in length. The general strike of the
axis—north 30° west—is not maintained with absolute uniform-
ity, but becomes almost north and south toward the southern
end of the peninsula. A general southerly plunge of the anti-
clinal axis is indicated by the fact that, from north to south
along the axis, beds successively higher in the stratigraphic
column are encountered at the same elevation.
In the northern part of the field the axis coincides with the
summit of the low divide between Sibuyanin and Vigo Rivers.
From this point it follows more or less closely a straight line
south-southeast as far as Cuyocuyo Creek. Farther south the
crest of the fold appears to coincide with the upper part of
Canguinsa River, so that south of Cuyocuyo Creek the axis
must trend about north and south. Beyond Bacau, the sharp
fold dies out, and was not certainly identified farther south;
although the gentle overturn of the strata, indicated in the
western part of Amoguis Valley, probably marks its con-
tinuation. ° North from the divide between Matataha and Si-
buyanin Rivers the Central anticline can be traced as far as
the eastern slope of Mount Maclayao. In Mount Maclayao, Vigo
shale is encountered, striking east-northeast and dipping steeply
to the south, and at the intersection of this line of strike with
the Central anticline the identity of the latter is lost in a con-
fusion of varying strikes and dips.
In the axial portion of the fold at the head of Sibuyanin
River, vertically dipping beds of Vigo shale are exposed. In
the western limb the dip decreases rapidly, and within a few
hundred meters to the west-southwest of the axis it amounts
340 ; The Philippine Journal of Science 1913
to only 45°, while 2 kilometers from the axis the dip—west-
southwest—is as low as from 15° to 20°. Still farther west the
beds lie horizontal in the syncline between the Central anticline
and the Ayoni anticline. In the opposite or eastern limb a dip of
from 55° to 65° to the east-northeast persists for a distance
of 1 kilometer to the eastward from the axis. Farther east,
the relations are uncertain and are discussed in connection with
the Malipa anticline (page 342).
To the south the western limb can be identified in the beds
exposed along the eastern slope of Cudiapi Range. The upper
part of the Vigo shale, which outcrops along Cambagnaon and
Cuyocuyo Creeks, dips from 25° to 30° to the west-southwest;
but the beds lower in the formation and nearer the axis of the
anticline are steeper, dipping from 60° to 70°. The Canguinsa
sandstone which has been removed by erosion farther north re-
appears in Cudiapi Range, overlying the Vigo shale and dipping
His of
fntichne
Fic. 1. Diagrammatic section across axis of central anticline in the
upper valley of Malipa Creek. (a) Canguinsa sandstone; (b)
Vigo shale; (c) concealed.
at low angles to the west-southwest. In the eastern limb of
the fold in this vicinity the Canguinsa sandstone is encountered
very close to the axis dipping gently to the eastward. The
nearest exposures of the underlying Vigo shale are vertical, or
dip at high angles to the east in the axial portion of the fold.
There appears to be insufficient room between the axis and the
Canguinsa sandstone in the eastern limb for a thickness of Vigo
shale equivalent to that exposed in the western limb. The rela-
tions are shown in text fig. 1.
Possibly faulting has occurred in the plane of the axis as a
result of sharp folding, and the western limb has been thrust
upward along the fault. Such a condition would explain the po-
sition of the lower part of the Vigo shale in the western limb
so nearly in contact with Canguinsa sandstone in the eastern
limb.
In the headwaters of Canguinsa River an exposure of Vigo
VII, A, 5 Pratt and Smith: Petroleum Resources 841
shale was observed dipping 45° to the westward, the later for-
mations lying above it and dipping in the same general direction
at a lesser angle. South of Balinsog, as far as Bacau, the Can-
guinsa sandstone is intact across the axis of the anticline, and
the upper formations dip gently away to the east and west on
either side of Canguinsa River. The Bacau stage of the Vigo
shale is exposed in the river at Bacau, dipping 55° east-northeast ;
and above this exposure, in the eastern wall of the valley, the
Canguinsa and Malumbang formations are encountered dipping
at low angles to the eastward. Up and down stream from the
outcrop of Vigo shale at Bacau the relations are concealed; the
river swings to the southwest at this point, and the next ex-
posures downstream are of Canguinsa sandstone dipping gently
westward.
The existence of a minor cross-anticline, the axis of which
coincides roughly with the lower part of Canguinsa (Silonguin)
River, is suggested in the discussion of the geologic control of-
the topography. In the upper part of the gorge, which Can-
guinsa River enters after its abrupt turn to the southwest, the
Canguinsa sandstone dips to the north of west, while farther
downstream the direction of dip has swung to south of west,
indicating that the river in its course to the southwest has
passed over the axis of a small anticline trending east and west -
in the general western limb of the larger fold. In a profile view
of a cross section of the gorge, which may be obtained from
Mount Anuing, the effect of this small anticline may be detected
in the slope of the land surface to the north and south away
from the rims of the gorge. The northerly dip of the beds in the
hills along the north edge of Malumbang Plain probably re-
presents the northern limb of this cross-flexure.
It is probably due to the presence of the cross anticline at
Bacau that the Vigo shale is thrown up so as to appear again
at the surface after having been carried down by: the general
southerly plunge of the axis, far enough to escape erosion at
the same elevation farther north.
Structure in the region north of the Central anticline.—In
Sobo Creek, which drains a part of the western slope of Mount
Maclayo, strata in the upper part of the Vigo shale were ob-
served striking north 65° east and dipping 65° to the south. On
Mulanay River, above the point where the tidal influence ceases,
numerous outcrops of Vigo shale are to be seen in a majority of
which the strikes are a few degrees north of west, and the dips
are either vertical or steep both to the north and south. A
842 The Philippine Journal of Science 1913
smaller number of exposures show the usual north-northwest
strike with dips to the west or occasionally to the east.
Northeast of this region, between Guinhalinan River and the
eastern coast, the formations are found in their usual relations—
striking north-northwest and dipping to the east from 35° to
40°. On Ajus River to the northwest, likewise, the prevailing
strike conforms to the established order; but the position of the
beds indicates an overturned fold with the lower part of the Vigo
shale, which dips to the eastward at angles of from 60° to 90°,
recumbent upon the sandstones and conglomerates in its upper
portion. The overturn does not persist through the younger
formations apparently, since these are found in the range of hills
along the coast, dipping at an angle of about 45°, westward.
Inland from Catanauan and northwest of Ajus, the lime-
stone in the coastal ridge dips to the southwest at an angle of
about 45°. In the valley east of this ridge, Vigo shale is exposed,
dipping 50° to the southwest. Thus, the slight overturn at
Ajus appears to adjust itself along the strike of the formations;
the strata resume a steep southwestern inclination, northwest
of Ajus, corresponding to the lesser dip in the same direction
at Matataha and Ayoni, southeast of Ajus.
Summarizing the discussion of the structure north of the Cen-
tral anticline, the seaward dipping formations near each coast
may be interpreted as evidence of a general arch across the width
of the peninsula. The relations in the crest portion of the sug-
gested arch are complicated and obscure. It appears that fold-
ing at right angles to the general structural lines has occurred,
together with close folding and overturns along the main lines
of structure.
Malipa anticline-—The strikes and dips in the Vigo shale near
Cabongahan indicate the presence of a subordinate anticlinal
undulation in the eastern limb of the Central anticline. The
smaller fold, known as the Malipa anticline, trends north 65°
to 70° west, making an angle of about 40° with the axis of the
Central anticline. Its crest is roughly coincident with the lower
course of Vigo River. The fold is well developed in the Vigo
shale, but is only faintly reflected in the younger formations lying
in the ridge near the eastern coast. In the southern limb of the
anticline, along Malipa Creek, a thickness of 800 meters of Vigo
shale is exposed, dipping to the south-southwest at an angle of
about 55°. Above the Vigo shale, the Canguinsa sandstone ap-
pears, overlain by patches of coralline limestone.
Only a few exposures were observed which can be referred
VIII, A, 5 Pratt and Smith: Petroleum Resources 843
to the northern limb of the Malipa anticline. These are found
along Vigo River, and dip about 45° to the north-northeast.
Farther north the dips and strikes are much confused, and the
structure is not clear. The volcanic agglomerate is encountered
at the head of Tangob Creek. In this vicinity the Vigo shale dips
steeply to the east-northeast in perhaps a majority of the ex-
posures, but its relations are not uniform.
Bato anticline—Near the small village of Bato, north of
Cabongahan, the lay of the beds indicates a local anticline in the
Vigo shale, the axis of which is roughly parallel to the Central
anticline. Like the Malipa anticline this fold appears to be a
minor overturn in the general eastern limb of the Central anti-
cline. It is a sharp flexure, the strata in each limb dipping at
angles of 60° or more, but is persistent over a length of a few
hundred meters only. The stream between Bato and the ridge
to the east appears to follow the axis of this anticline. The Bacau
stage of the Vigo shale is exposed along its crest and dips away
from the stream line on either side. The upper formations
appear on top of the Vigo shale in the eastern limb, forming
the high ridge between the anticline and the eastern coast. The
dip in the uppermost beds is from 30° to 45° east-northeast.
Pusgo Bay which lies off the eastern coast at this point occupies
a syncline, and San Narciso Peninsula, east of the bay, is a mon-
ocline dipping gently westward toward this syncline. West of
the axis of the Bato anticline only Vigo shale is exposed and
the westerly dip of its beds persists for a short distance only,
beyond which the shale dips steeply to the east-northeast, mark-
ing the eastern limb of the Central anticline.
In the Florence, Colorado, oil field,'® the stream lines are some-
times marked by small sharp anticlines, which are attributed to
purely superficial phenomena, such as the expansion of rocks
through weathering and consequent thrust of surface beds into
the valleys formed by streams. It is possible that the Bato
anticline is of this type, but the fact that petroleum is found
along its crest argues that it is more than superficial in effect,
since petroleum is found usually in true anticlinal zones, else-
where in the field.
Ayoni anticline.—Inland from the villages of Ayoni and Bon-
doc on the west coast, the dip measurements and the hill forms
reveal an upward flexing of the strata along a line directed
north 35° west. This axis is about 1,200 meters and 2,000
meters from the coast at Ayoni and Bondoc, respectively. The
** Washburne, C. W., Bull. U. S. Geol. Surv. (1909), 381, 49.
344 The Philippine Journal of Science 1913
gentle anticline which is defined along it becomes evident a short
distance south of Matataha River and persists over a length of
10 kilometers to a point east of Bondoc. Sandstones, about 300
meters in thickness, are exposed in the western limb at Ayoni,
dipping from 35° to 40° west-southwest and overlain conform-
ably by limestone. The sandstones probably represent the Can-
guinsa and part of the Vigo formation, and the limestone, the
lower stage of the Malumbang series. Hast of the axis in the
west slope of the Cudiapi Range, a similar section culminating
in limestone and calcareous sandstone is revealed. The inclina-
tion of the strata in the eastern limb is generally less than 15°.
Between the northern end of the Ayoni anticline and the cross
fold at Mulanay, an area in which the strata are horizontal in-
tervenes. Mount Cancalao, left by erosion in the Matataha Val-
ley, affords a section of horizontal strata in which bluish black
shale at the base is covered by beds of sandstone, sandy micaceous
shales, and sandstone conglomerate with a total thickness of
nearly 200 meters. On the coast west of Mount Cancalao, the
strata dip seaward as they do at Ayoni, and precise measure-
ments would probably reveal a slight anticlinal fold between
the mountain and the coast.
South of the Ayoni anticline as far as Silonguin (Canguinsa)
River, the structural relations are uncertain. The identity of
the smaller fold is lost in a general slight dip to the southwest,
which probably marks the western limb of the Central anticline.
Cudiapi syncline-—The Cudiapi syncline is a shallow struc-
tural basin lying between the Central and Ayoni anticlines. The
rocks have been preserved from erosion within this zone and
form the rather flat-topped Cudiapi Range extending southeast
from the headwaters of Sibuyanin River to Silonguin River.
The Canguinsa sandstone and the Lower limestone of the Malum-
bang series are exposed over most of the surface, but remnants
of the Cudiapi sandstone occur locally.
Maglihi anticline —The Maglihi anticline—marked by Mount
Maglihi, a conspicuous peak formed by the almost vertical strata
in its crest—is an acute upward flexure in the eastern part of the
monocline which persists with a gentle eastward dip across the
southern end of the peninsula. The anticline is most clearly re-
vealed in the vicinity of Mount Maglihi, where the axis strikes
north 5° east, and the eastern limb is much steeper than the
western. South of the mountain, the axis plunges so that the
fold is barely perceptible in the strata near the southern coast.
Northward, it can be traced with some difficulty for several kilo-
meters and probably continues to Bahay where a similar fold
ee.
VIII, A, 5 Pratt and Smith: Petroleum Resources 345
is indicated. At Bahay, however, the western limb is not clearly
defined in the younger formations and the axis has changed its
direction to the north-northwest, in conformity with the general
strike in the field.
In the region of Mount Maglihi, the western limb of the fold
can be identified without difficulty. For several hundred meters
west of the axis, the Upper limestone and Cudiapi sandstone dip
from 15° to 20° to the westward, reversing the monoclinal slope
from the summit of Mount Banaba and forming the eastern limb
of a shallow syncline occupied by Malumbang Valley. The Vigo
shale, exposed at the oil seep near Banco, likewise dips to the
westward, but at a greater angle (45°). North of Banco, the
crest of the fold is less deeply eroded, and the base of the Can-
guinsa sandstone is not uncovered. On Mount Maglihi and
Mount Morabi, which are in the eastern limb close to the axis,
the Canguinsa sandstone dips generally about 55° to the east,
but locally it is vertical, or even overturned slightly to the west.
The Canguinsa sandstone is calcareous in this locality, and in
the summits of the hills just mentioned contains sandy limestone
a few meters thick (Table XI). In the Malumbang series, lying
farther from the axis in the eastern flank of the fold, the angle
of dip decreases regularly to about 30°.
The more highly inclined strata east of the anticlinal axis
are exposed in apparently greater thickness than is evident in
the western limb, and the lower part of the Canguinsa sandstone
in the eastern limb is brought into close association with the Ma-
lumbang series in the opposite limb. The relations suggest
faulting along the strike of the beds in the crest of the anticline
with an upward thrust of the eastern limb, but in the absence of
precise measurements actual movement along the suspected
fault plane cannot be established.
A commonly stated law applying to asymmetric anticlines is
that the active thrust came from the side of.gentler slope, that is,
in the case under discussion, from the west. If the force came
from the west, the eastern limb could scarcely have been thrust
up over the western. Since the evidence of the overthrust of
the eastern limb is not conclusive, and the law as to the direction
of the active forces—while not of universal application—is as-
sumed to hold true generally, the occurrence of actual displace-
ment along a fault plane in this fold must be questioned.
At Bahay the relations are similar to those in the region just
described. Bahay River, flowing north, and Milipilijuan Creek,
flowing south, have cut out a deep valley along the axis of the
flexure and parallel to the coast line. Between this valley and the
846 The Philippine Journal of Science 1913
coast is a ridge in which the strata from the Canguinsa sandstone
to the Upper limestone are found dipping from 30° to 40° east-
northeast. The top of the Vigo shale, exposed at several places
along Bahay River and Milipilijuan Creek, is the lowest horizon
reached by erosion. Most of the outcrops are in the eastern limb
of the fold and dip 55° east-northeast.
West of Bahay River, which marks the axis of the flexure, the
formations still dip to the eastward, but at very low angles. At
the mouth of Apad Creek, which flows into Bahay River from the
west, the Canguinsa sandstone dips slightly eastward. Farther
up the creek, the Cudiapi sandstone appears above the Canguinsa
and dips to the southeast from 15° to 30°. Several of the expo-
sures of Vigo shale in Milipilijuan Creek dip to the westward, and
it is probable that the Vigo shale forms a true anticline at Bahay
with dips to the east-northeast and to the west-southwest away -
from the axis. The flexure in the upper, less easily folded, strata
is anticlinal in character in that the strata are differently inclined
cn either side of its axis so as to form an arch, although the dips
are all in a single general direction (eastward). In these beds
there is only an abrupt increase in the eastward dip along a line
which becomes the axis of an anticline farther south.
There is evidence of displacement at Bahay similar to that near
Mount Maglihi. Acute folding with erosion along the crest might
account for the observed relations, but an accompanying upward
thrust of the eastern limb along a fault plane is indicated. The
objection to the theory of an overthrust of the eastern limb at
Mount Maglihi, discussed on page 345, applies with equal force
to the conditions at Bahay.
Banaba monocline.—An extensive monocline, the general north-
east dip of which is conspicuous in Mount Banaba, forms the
southern portion of the peninsula. Based on rather meager
evidence, a minor overturn in the region of Sili and Tala and a
close fold near the southwestern coast are shown in the geologic
section (Map I) as modifications of this structure.
The strike of the beds varies in different parts of the area. On
Mount Banaba it is north 30° west, near Bondoc Head it is north
50° west, and in the western part of the monoclinal area it is
north 15° west, parallel to the adjacent coast line. From Mount
Banaba to Sili the average dip is probably 15°, and in the section
between these places only the strata in the Malumbang and Can-
guinsa formations come to the surface. It it surprising, in view
of the general northeast dip, that the upper part of the Vigo shale
is not exposed in the deep valley of Amoguis River. The differ-
ence in elevation between the summit of Mount Banaba and the
eS eee ee
VIII, A, 5 Pratt and Smith: Petroleum Resources 847
floor of the valley is great enough that the entire thickness of the
strata above the Vigo shale should be included in the section ex-
posed in the eastern wall of the valley, unless the upper forma-
tions are thicker here than they were found to be farther north.
On Sili Creek, a few hundred meters south of Sili, the Bacau
stage of the Vigo shale is exposed, but only over a small area, and
west of Sili the upper formations reappear and are found in the
floor of the next valley to the westward, at an elevation as low as
that of Sili Creek. This condition suggests that the general north-
east dip of the strata is reversed to a westward dip for a short
distance west of Sili. Faulting might produce the same effect,
but there is no evidence of faulting in this vicinity. Neither were
the suggested westward dips detected at Sili proper, but north of
Sili, at Tala, dips to the west are found in the upper formations.
On the basis of this evidence, a small anticline is shown along this
line in the geologic section. It will be noted that this fold is ap-
proximately in the position which a southward continuation of
the Central anticline would occupy.
West of Tumbaga River, the Vigo shale reappears, dipping 35°
east-northeast, and the exposure extends southwest to the sea-
coast. The dip of the beds increases regularly toward the south-
west, becoming almost vertical at the eastern base of the chain of
hills along the western and southwestern coast. On top of Bon-
doc Head the Canguinsa sandstone and part of the Malumbang
series occur, lying almost horizontal. West of Bondoc Head on
the seacoast, the Vigo shale, dipping 30° to the northeast, is
encountered again. Inthe summit of the ridge near the mouth of
Bataniog Creek are sandstone and sandy conglomerate, similar
to the strata in the upper part of the Vigo shale near Matataha.
These beds dip to the east at an angle of 70° and strike about
north.
If the monoclinal structure persists to the southwestern coast,
Bondoe Head should consist of steeply inclined beds of Vigo shale.
Instead, the summit of this mountain is covered with younger
formations. At the mouth of Bataniog Creek, again, are the
sandstones and conglomerates which are found usually at the top
of the Vigo shale. If there is no reversal in the general mono-
cline, these beds are out of their usual stratigraphic position, and
the indicated thickness of the Vigo shale is at least 3,600 meters.
Both these conditions seem improbable, and a close fold recumbent
to the southwest, as shown in the geologic section, is a more
reasonable interpretation of the datain hand. The relations may
be complicated by faulting analogous to the suspected faulting in
the Maglihi anticline.
848 The Philippine Journal of Science 1913
GEOLOGIC HISTORY
The southern part of Bondoc Peninsula appears to have been
the site of shallow water deposition during the larger part of
Miocene time. Of the conditions prior to the Miocene, there is
little evidence. Quartz-veined diorite and schist, both older than
the Miocene, occur farther north on Bondoc Peninsula and prob-
ably continue into the region under discussion, lying beneath
the sedimentary strata. That rocks of this character formed a
part of the land mass from which the sedimentary beds in the
oil field were derived is proved by the presence of rounded quartz,
diorite, and schist fragments in the sandstone and cong lomo a
members of the series.
The fact that the highest beds are folded in fair Aiea with
those at the base of the stratigraphic column indicates that the
major part of the folding occurred after the close of the Miocene
and the completion of sedimentary processes in this region.
From the steeper dip in the eastern limbs of most of the anti-
clinal folds, it might be inferred that the folding stresses were
transmitted from the west. Not all the evidence obtained con-
firms this view, however, and without more data a conclusion
is hardly justified.
The interbedding in thin layers of fine-grained shale, sandy
shale, and sandstone shows that the Vigo shale formed in mod-
erately shallow water. The thickness of the series and the
regularity of the beds imply uniform conditions over the area
throughout which they are distributed. Continued deposition
of sediment in shallow water, until a succession of strata equal
in thickness to the Vigo shale is built up, would appear to
require an accompanying gradual subsidence of the sea floor.
The less clearly defined bedding planes and the increased pro-
portion of fine sediment in the Bacau stage, as compared with
the lower part of the Vigo shale, suggest that deposition became
more constant and regular and that the water became deeper
before the beds in this stage were deposited; however, shallow
water conditions must have prevailed at the close of the period
when the sandstones and fine conglomerates were laid down.
The Vigo shale may have emerged above sea level, entirely or
in part, and have been subject to erosion before the succeeding
beds were deposited. A period of volcanic activity m or ad-
jacent to the region, at about this time, is attested by the
presence of the volcanic agglomerate near the top of the Vigo
shale.
The thick massive beds of fine sediment in the Canguinsa
a ee ee ee se
ro =
VIII, A, 5 Pratt and Smith: Petroleum Resources 849
sandstone appear to have been formed as a continuous deposition
in deep or quiet water. Parts of the formation, however, are
coarse grained and were probably laid down in shallow seas
similar to those which must have prevailed during the deposition
of the Malumbang series. The growth of coral in the limestones
in the Malumbang series indicates that the water was clear at
times toward the end of sedimentation.
The Pleistocene and Recent deposits of volcanic tuff, which
are extensive in the neighboring territory of southwestern Luzon,
do not reach as far to the southeast as Bondoc Peninsula. Sub-
sequent to the Pliocene, apparently, the mass of Bondoc Pen-
insula has been above sea level, and subject to erosion which
has been very extensive and has removed great thicknesses of
strata.
OCCURRENCE OF THE PETROLEUM
The petroleum on Bondoc Peninsula appears as seepage from
the floors or sides of streams. At some places the oil rises
spontaneously and floats away on the surface of the water.
More commonly it appears only after the prospector has dis-
turbed the rocks at the bottom of the stream. Digging in the
shale of the Bacau stage where it has been freshly exposed by
stream erosion generally yields small quantities of petroleum.
The oil is invariably accompanied by inflammable gas, and in
a number of instances inflammable gas is encountered in the
absence of oil. At none of the seeps is there evidence of a large
flow of oil at the surface. To collect as much as a liter of oil
from any of the seeps involves a considerable amount of work
in turning over the rocks and stirring up the mud in the streams
along which the oil is found. The petroleum contains a large
proportion of volatile constituents, and all trace of oil is lost
soon after it appears on the surface. There is no discoloration
of the ground around the seeps, but a scum gathers on the water
and on stones or sticks in the water for a short distance down-
stream from an oil seep. The proximity of a seep is usually
manifested first by the odor of kerosene which is evolved rather
than by visible evidence of the petroleum.
In all cases where oil has been found, it occurs in or near
the Bacau stage of the Vigo shale, more or less closely below
the Canguinsa sandstone in the stratigraphic column. The seep
on Malipa Creek, near Cabongahan, is at the lowest horizon in
the Vigo shale at which oil has been encountered. Here Vigo
shale some 250 meters thick intervenes between the oil seep and
122679——4
850 The Philippine Journal of Science 1913
the base of the Canguinsa sandstone. In the lowest exposed
portions of the Vigo shale but little oil is to be observed.
The oil is associated with the shale, rather than with the
sandstone, where sandy layers are interbedded, and in several
cases it comes directly from the shale. The absence of oil in
the interbedded sandstone at the outcrop may be due in part
to the rapidity with which it volatilizes and thus escapes from
porous media.
Petroleum seeps were encountered at Banco, at Bahay, and
on Milipilijuan Creek along the Maglihi anticline; on Sili Creek,
a branch of Pagsanhan River; at Bacau on the Central anticline;
on Malipa and Tangob Creeks in the vicinity of Cabongahan;
at Bato, north of Cabongahan; and on Ajus River in the north-
eastern part of the field. Traces of oil and inflammable gas
were detected at several other places, including the outcrops of
Vigo shale dipping steeply south-southwest on the upper part
of Sobo Creek, south of Mulanay.
- PETROLEUM AT BANCO
Petroleum is found at Banco near the head of Canibo Creek
which flows to the south from the small valley in the crest of
the Maglihi anticline. The seep is at an elevation of about
200 meters. A strong odor of kerosene reveals the presence of
the oil, which on closer inspection may be seen to rise in globules
from the bottom of the small stream and to float away in films
on the surface of the water. The seepage is accelerated by
probing in the rocks and débris in the bed of the stream, and
a small quantity of petroleum can be collected by skimming the
globules and films from the water. The underlying rocks are
concealed at the immediate point of escape, but 20 meters down-
stream bedded petroliferous shale and sandstone, belonging to
the Bacau stage of the Vigo shale, are exposed. These beds dip
to the west at an angle of 45°, so that the seep is in the western
limb of the anticline. The wall of the valley rises steeply on
the west to an elevation of more than 300 meters, and is made
up of the rocks of the Canguinsa sandstone and Malumbang —
series.
About 200 meters south of the main seep, oil may be detected
in blue to black petroliferous shale on the floor of an arroyo in
the western wall of the valley. Maalat Creek, an adjacent
tributary of Canibo Creek, contains salt water, as the native
name, “Maalat,” implies.
VIII, A, 5 Pratt and Smith: Petroleum Resources 851
PETROLEUM AT BAHAY
The strongest seep in the Bondoc field is, perhaps, that at
Bahay, the drilling site of the Bahay Valley Oil Company on
Bahay River. Bahay River is about 15 meters in width at this
point, and the oil appears at numerous places over the whole
surface of the stream throughout a length of 50 meters. It
comes up spontaneously, accompanied by bubbles of inflammable
gas, and forms an extensive surface film. An unusual cloudiness
in the water is commonly attributed to the presence of the oil.
The river bed is covered by pebbles and small bowlders of lime-
stone eroded from the Lower limestone which is exposed several
hundred meters upstream, and the oil is trapped beneath the
larger rocks and escapes to the surface after the temporary
reservoirs which these afford are filled. The elevation of the
seeps above sea level is about 50 meters.
The formation is concealed within the area covered by the
seeps. Fossiliferous sandy clays, believed to represent the Can-
guinsa sandstone, were observed upstream—about 300 meters
south of the seep. The structural relations of this outcrop
could not be determined since no planes of stratification are
discernible. North of the seeps—approximately 150 meters
downstream—imperfectly bedded shale occurs, dipping to the
east-northeast at an angle of 55°. This shale is sandy, blue to
black in color, and contains carbonized impressions of leaves and
broken plant stems. From the position and dip of this shale
it appears that the seeps are probably in the eastern limb of
the anticline and from the relations elsewhere it is evident that
they are very close to the axis.
Two wells have been drilled near the seeps. The first well,
Bahay 1, is located a few meters west of the river bank opposite
the point where the seeps are most numerous. It was drilled
by hand in 1906 under the direction of Mr. E. W. McDaniel,
managing director for the Tayabas Mutual Oil Association. It
is cased with 4-inch pipe, and reached a depth of 38.7 meters.
A record of this well is not available, but the following data
appeared in the Far Eastern Review :*
The first oil sand occurred at a depth of 62 feet and continued through
six feet to a depth of 68 feet. From this strata using the mud bailer as a
pump, 46 gallons of crude oil of an excellent quality was secured in one day’s
work, * * *. Owing to the crumbling nature of the formation above
“ Toc. cit.
352 The Philippine Journal of Science 1913
and below, this oil bearing strata was cased out and the well continued to
its present depth of 127 feet and the casing extended down to 103 feet. The
second oil strata was found at a depth of 117 feet extending downward 5
feet or to a depth of 122 feet. The yield of oil at this depth was practically
the same as that of the first strata, but a satisfactory pumping test could not
be carried out with the mud bailer, there being no other appliance at hand.
It is believed that the strata, “the crumbling nature” of which
made it necessary to case out the oil from the upper horizon,
were principally shale, and probably represent the Bacau stage
of the Vigo shale. Mr. McDaniel has stated in conversation that
both the zones from which oil was obtained are sandy. Prob-
ably the shale above and below the “oil sands” was petroliferous
throughout. Occasional sandy beds have been noted in the pe-
troliferous shale, and it would be expected that where the con-
ditions were such as to prevent its escape more oil would
accumulate in the sandy beds than in the closer-grained shale.
If the wells are east of the anticlinal axis, as the relations
indicate, the strata encountered probably dip at an angle of
about 55°. Well 1, consequently, pierces beds aggregating only
22 meters in thickness, and the upper and lower sandy zones
are 0.87 meter and 1.04 meters thick, respectively.
In February, 1913, the well was pumped dry with the bailer.
About 30 liters of oil were obtained from the column of water
and oil which filled the casing to within 21 meters of the surface.
The well proved to be 35 meters deep, the original casing having
been driven to that depth recently. Apparently, the well is
caved above the lower oil horizon reported, while the upper
horizon is sealed off by the casing. It is probable that by proper
treatment this well could be made to yield daily a barrel or
so of oil.
Bahay well 2 is located 50 meters north of well 1 on the west
bank of Bahay River. If the assumed structural relations are
correct, well 2 is about 25 meters farther east of the anticlinal
axis than well 1. Well 2 was drilled with a standard rig by
Mr. O. A. Leary, and reached a depth of 91.5 meters. The casing
at the collar of the well is 10 inches in diameter. Mr. Leary has
kindly furnished the following statement which constitutes the
only information available concerning this well:
Log of Bahay oil well 2.
0 to 25 feet.
Conglomerate, yellow sand, clay and gravel with large bowlders.
25 to 100 feet.
Brown shale showing evidences of oil and gas.
VIII, A, 5 Pratt and Smith: Petrolewm Resources 353
100 to 105 feet.
Coarse gravel with-considerable quantity of oil and gas, and at this
depth pipe was roughly packed and one-half-inch connection inserted.
The gas was ignited and allowed to burn for fourteen hours without
showing any decrease in volume, the blaze being approximately 10
feet in length.
105 to 115 feet.
Very hard gray rock; experienced considerable difficulty in drilling,
owing to hardness.
115 to 170 feet.
Blue clay, showing streaks of clay lighter in color.
170 to 225 feet. ;
Brown shale heavily saturated with oil.
225 to 300 feet.
Brown shale very compact and of an elastic sticky nature. Drilling
very difficult owing to this feature.
Very little water was encountered during the entire drilling of this well.
At 20 feet a slight showing of fresh water; at 100 to 105 feet the presence
of a small quantity of salt water was noticed. The well was practically
free from water. Temperature of formation, normal.
Below the surface débris, which extends to a depth of 25 feet
(7.6 meters), this well appears to have entered the Bacau stage
of the Vigo shale and to have continued in this formation
throughout. However, it may be that the “coarse gravel” and
“hard gray rock” encountered in the well represent the con-
glomerate or gravel and the limestone exposed in Bahay River
section (Table X, page 320) above the Vigo shale. The
“evidence of oil and gas” in the “brown shale” above the “coarse
gravel” is not in accord with this possibility, however, since the
gray clayey sandstone exposed in Bahay River section above
the conglomerate certainly shows no trace of oil or gas.
If the eastward dip of 55° in the shale north of the wells
prevails at the site of well 2, the total thickness of strata pierced
is 52.2 meters, the “coarse gravel” is 0.9 meter thick, and the
“hard gray rock” is 1.9 meters thick.
PETROLEUM ON MILIPILIJUAN CREEK
Near the head of Milipilijuan Creek, which flows into Bahay
River from the north, oil is encountered seeping directly from
bluish to brownish black shale. The seep is at an elevation of
85 meters, and is approximately 1,500 meters north-northwest
of the junction of Milipilijuan Creek and Bahay River. The
shale from which the oil escapes dips northeast at an angle of
53° and contains some interbedded sandstone. Downstream’
a short distance, similar shale outcrops at several places, striking
854 The Philippine Journal of Science 1913
northwest and dipping steeply both to the northeast and south-
west. Farther downstream the Canguinsa sandstone—massive
and clayey—appears on top of the bedded shale. The oil comes,
therefore, from the usual petroliferous horizon in the Vigo shale,
immediately beneath the Canguinsa sandstone. The seepage is
sufficient to permit of the collection of a liter of oil without much
difficulty.
PETROLEUM ON SILI CREEK
A large exposure of petroliferous shale occurs on Sili Creek,
about 2 kilometers south of Tala. The outcrop is at the con-
fluence of two small streams which constitute the headwaters of
Sili Creek, and is at an elevation of 100 meters. The shale, which
probably represents the Bacau stage of the Vigo shale, is exposed
in banks about 12 meters high along either side of both branches
of the creek for a distance of 100 meters. Overlying the shale,
the Canguinsa and Malumbang formations are exposed in the
surrounding hills. The structure in this region is not clear,
but it appears that the exposure lies near the crest of a small
anticline, trending north. Faint bedding planes dipping to the
east-northeast at angles of from 30° to 40° may be discerned in
the shale. No actual seepage of petroleum was observed, but
the streams which flow across the shale are small and afford
little chance for detecting films or seepage. The odor of light
oils is very strong in the neighborhood, and traces of oil can be
obtained by macerating the shale in water.
Part of the shale outcrop at Sili is always barren of vegetation,
a condition due, in part at least, to the instability of the surface
which is constantly crumbling and sliding down into the streams.
The natives attribute the absence of the generally present cogon
to the petroleum in the shale. They maintain that the shale
has been known “to burn.” Two similar barren places occur in
the vicinity of Bondoc Head. The latter places are held by the
natives to mark the graves of asuan (spirits). The ground is
said always to be hot and to have “burned with flames” in the
past. The reports of prospectors who had heard this story from
the natives, but probably had not visited the site of the alleged
phenomena, undoubtedly gave rise to the widely circulated state-
ment that a vent, from which natural gas escaped and was con-
tinuously burning, existed near Bondoc Head.
The “graves of the asuan” are on Lomboy Creek above a vil-
lage called Dyap, in a region covered with cogon. Unlike the
exposures on Sili Creek they are not steep slopes, but are on
VIII, A, 5 Pratt and Smith: Petroleum Resources 855
fairly level ground. Each has an area of several square meters
which is barren of vegetation. The ground to a depth of a meter,
at least, below the surface is unusually warm and feels hot to
the hands. The temperature is not so high at the surface as
it is at a depth of 30 centimeters, where the ground has a moldy,
charred appearance and emits a rancid odor.
The sandy strata on which these bare spots occur are decidedly
carbonaceous, and the surface is covered with decaying vegetable
matter. It appears that a slow oxidation of the carbonaceous
material in the sandy beds and of plant remains on the surface
is in progress locally in this vicinity. The combustion may have
been started originally by the fires which burn off the surround-
ing grass periodically. While the sandstone and shale near Bon-
doc Head are strongly carbonaceous, they show little evidence
of oil or gas.
PETROLEUM AT BACAU
Petroleum at Bacau appears as films or small globules on the
surface of a pool in Canguinsa River at the foot of a steep bank
of massive, blue-black shale. The oil comes up intermittently
from several places at the bottom of the pool, in quantity about
equal to that encountered at Banco. The seeps are at an eleva-
tion of about 100 meters. The shale in the adjacent bank is
petroliferous, and when fresh pieces are raked down into the
stream they give off a film of oil. The strata dip to the east
at angles of from 50° to 60°, and apparently lie in the eastern
limb near the axis of the Central anticline. The Canguinsa
sandstone occurs in the walls of the valley on either side im-
mediately above the petroliferous shale, which is the type ex-
posure of the Bacau stage of the Vigo shale.
PETROLEUM ON MALIPA CREEK
Inflammable gas bubbles up continuously from the bottom of
Malipa Creek about 800 meters above the confluence of this
stream and Vigo River. Small films of oil are observed occa-
sionally on the surface of the water in the vicinity. The gas
seeps from the Vigo shale in the south limb of the Malipa anti-
cline. A thickness of approximately 550 meters of shale is in-
dicated by the outcrops between the horizon from which the gas
comes and the axis of the anticline, while 250 meters of shale
lie stratigraphically above the seep and below the Canguinsa
sandstone.
A sample of the gas collected and analyzed by the Bureau
of Science showed the following composition.
356 The Philippine Journal of Science 1918
TABLE XIV.—Composition of the gas from a gas seep on Malipa Creek.
Per cent by
Constituent. volume.
Hydrogen 0.7
Methane 62.3
Ethane 0.3
Carbon dioxide 2.3
Nitrogen 25.5
Oxygen 2
Carbon monoxide 2.0
It will be noted that the gas contains an unusually large per-
centage of oxygen. Some of the oxygen may be due to contam-
ination of the sample by air, although care was exercised to
prevent contamination. Not all the oxygen can he due to the ad-
mixture of air, however, because the gas does not contain the
corresponding proportion of nitrogen. It is probable, therefore,
that the oxygen is an original constituent of the gas.
Mr. E. J. Cooke, in 1906, drilled a well on the west bank of
Malipa Creek about 50 meters upstream from the gas vent. This
well is said to have reached a depth of 21 meters and to have
encountered a small quantity of oil. The top of the well is at
an elevation of 20 meters.
PETROLEUM ON TANGOB CREEK
Inflammable gas and traces of petroleum can be obtained on
the upper part of Tangob Creek by moving the stones and débris
which cover the Vigo shale in the bed of the creek. In this
vicinity Tangob Creek flows between Cambagaco Ridge on
the east and a hill of voleanic agglomerate on the west. The
outcrop of agglomerate is surrounded by Vigo shale, and the
gas and oil are encountered within a few meters of the igneous
rock. In the base of Cambagaco Ridge, Canguinsa sandstone
occurs, overlying the shale and dipping to the east-northeast
at an angle of about 20°. The lower part of the Canguinsa is
rich in fossils where Tangob Creek flows across it. The shale
at the point where the oil was observed is blue to black, and occurs
in thin beds dipping east-northeast at an angle of 65°. The
dip and strike of the shale are not constant, however, but vary
greatly in this region. The petroleum seep is about in line with
the axis of the Bato anticline, but the strata in which it occurs
are part of the confused structure in the eastern limb of the
Central anticline north of the Cabongahan.
PETROLEUM AT BATO
Petroleum has been found on the little creek just east of Bato
in the shale forming the western limb of the acute fold described
VIII, A, 5 Pratt and Smith: Petroleum Resources 357
as the Bato anticline. This locality is about 120 meters above
sea level. There is no visible seepage, but petroleum may be ob-
tained by digging into the banks of petroliferous shale along
the stream. The strata belong to the Bacau stage of the Vigo
shale.
PETROLEUM ON AJUS RIVER
At a point on Ajus River above the village of Ajus and about
4 kilometers from the mouth of the river, bubbles of inflam-
mable gas and traces of petroleum appear on the surface of the
water after a pole has been forced into the mud on the bottom.
The oil occurs in the Vigo shale which dips steeply to the east
and appears to be part of an overturned fold. The shale is
bedded and petroliferous; layers of sandstone are interbedded
in it, one of which, outcropping near the oil seep, is also slightly
petroliferous. The elevation at the oil seep is about 45 meters.
PHYSICAL AND CHEMICAL PROPERTIES OF THE PETROLEUM
The petroleum encountered in the Tayabas field has a paraffin
base, is low in specific gravity (36° to 39° Baume), and unusually
mobile. It is light brown to wine-red by transmitted light, pale
blue by reflected light. Different seeps afford petroleums which
appear to be similar in character, although anaylses are avail-
able on the oil from only one source; namely, Bahay well 1 on
Bahay River. Distillation yields a remarkably high proportion
of gasoline, and the crude oil has an odor distinctly suggestive of
light oils. George F. Richmond,'* formerly of the Bureau
of Science, made the earliest analyses of Tayabas petroleum,
and later analyses have only confirmed his results. Rich-
mond first tested a sample submitted by a commercial firm;
and later, because the percentage of light distillates was so high
as to arouse a suspicion that the sample was not authentic, he
verified his findings upon samples collected at the well by Dr.
George I. Adams, formerly of the Bureau of Science. Samples
taken from the same well during the field work for this report
were examined in the division of organic chemistry, Bureau of
Science. The following table gives Richmond’s analyses and
other analyses of Tayabas petroleum made upon samples collected
recently. For comparison, analyses of petroleums from neigh-
boring islands and of well-known petroleums from other parts
of the world are inserted.
* Loc. cit.
1913
vence
Journal of Sci
ippine
al
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359
Petroleum Resources
Pratt and Smith
VIII, A, 6
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360 The Philippine Journal of Science 1913
A number of other samples said to represent Tayabas petro-
leum have been submitted to the Bureau of Science. One sam-
ple with the characteristic appearance of the Tayabas product,
collected by Mr. E. J. Cooke, shows a specific gravity as low
as 0.805. This sample probably came from the well on Malipa
Creek.
Tayabas petroleum is of lower specific gravity than other
known Philippine oils, and the fraction distilled below 150°
C. is large enough to make the petroleum remarkable, although
by no means unprecedented among natural products. By com-
position, Tayabas petroleum is more nearly related to some of
the Sumatra oils than to those encountered in Cebu or Borneo.
The lighter and most valuable grade of Japanese petroleum,
that which is encountered in the lower productive horizons, is
similar in character to Tayabas petroleum.
In studying sample 4, from Bahay well 1, Richmond found that
30 per cent of the crude oil, 16 per cent of the gasoline fraction,
and 24 per cent of the kerosene fraction consisted of unsaturated
hydrocarbons. Upon fractional distillation, the unsaturated
hydrocarbons extracted from the crude oil began to boil at 130°
C., and 7.5 per cent remained undistilled at a temperature of
300° C. The derivatives from the fractions showed a homolo-
gous series of aromatic hydrocarbons beginning with. xylene
(C,H,,). Benzene, tuolene, nor any of the naphthalene series
were found in them.
Mr. E. R. Dovey of the Bureau of Science examined sample
8 for optical activity. His results appear in Table XVI.
TABLE XVI.—Optical properties of Tayabas petroleum. Sample No. 3.°
is «__ |Optical ro-
Specific | Refractive a °
gravity index at Wore
at 29°C. PAIN Op acted)
Degrees.
Crude petroleum _______- 0. 8323 BAGO) Capers &
Gasoline fraction --__--_-- - 7692 1. 4263 —0. 55
Kerosene fraction _-_---- . 83833 1. 4670 til
ORIGIN AND PROBABLE QUANTITY OF THE PETROLEUM
Before discussing the particular features of this field having
to do with the question of the origin of petroleum a few words
should be devoted to the subject in general.
At present there are two sharply divided schools, in one of
which the majority of geologists are to be found maintaining
VIII, A, 5 Pratt and Smith: Petroleum Resources 361
that petroleum is of organic origin. In the other school are those
who believe in the inorganic origin of petroleum, some of whom
assert that there is a close relation between volcanic activity
and the production of the natural hydrocarbons. It is only fair
to admit, that the matter is by no means settled and that there
is much which seems to support the inorganic theory.
The conditions of vuleanism under which petroleum is supposed
to originate are still obscure, and it is impossible to say what
kind of volcanic activity gives rise to petroleum. Coste,’® the
principal adherent of the volcanic theory, believes that the origin
of oil is associated with solfataric emanations. If this be so,
there are numerous localities in the Philippines where it might
be advantageous to prospect. In the Tayabas field, however,
where more oil is encountered than anywhere else in the Archi-
pelago, the phenomena of vulcanism are least abundant and
solfataric activity is unknown.
The observed facts bearing upon the question of the source of
oil in this field are:
1. The formations are practically all sedimentary. Small
isolated patches of volcanic agglomerate occur, but these are
confined to the northeastern portion of the field and aside from
the presence of this agglomerate there is no evidence of volcanic
phenomena.
2. The known oil seeps are associated with bluish to brownish
black shale and subordinate sandstone which occurs in the Bacau
stage of the Vigo shale. Where traces of oil are found below
the Bacau stage, they are always associated with beds of fine-
grained compact shale. Material of this character occurs in
other formations above the Vigo shale, but no petroleum has been
observed in the upper formations.
3. In the petroliferous shale are numerous tests of Globigerina
(Plate V) and some minute fragments of carbonaceous matter.
4. Globigerina has not been noted except in the Vigo shale.
They were found most abundantly in the Bacau stage, but occur
also at lower horizons.
5. None of the oil seeps in Tayabas appears to give off a large
quantity of petroleum. However, all trace of the oil which is
seen to be given off disappears in a remarkably short time, due
probably to the light nature of the oil. Hence, it is possible
that the quantity of oil which escapes from the seeps is larger
than it appears to be.
6. Natural sections afford opportunity for the examination
“Trans. Am. Inst. Min. Eng. (1906), 35, 288.
362 The Philippine Journal of Science 1913
of all the strata above the Vigo shale. The lower part of this
formation and the beds which underlie it are not exposed any-
where within the field, and their character is unknown. There
is a possibility also that some members of the Vigo shale above
the Bacau stage are concealed by the overlap of the uncon-
formable Canguinsa sandstone and, therefore, have escaped
examination.
7. The petroleum is of low specific gravity, and contains a
large proportion of light oils. It has been suggested that its
properties are those of a clarified, or partly refined, oil. The
lighter fractions are weakly levorotatory in their effect on po-
larized light.
Considering the field relations alone, the logical conclusion
would be that the petroleum in Tayabas is of organic origin
and is in no way connected with volcanic activity or other
inorganic processes. By some authorities,?? the property of
rotating the plane of polarized light which Tayabas petroleum
exhibits would be accepted as conclusive evidence of organic
origin.
If a definite organic source is sought, the presence of Globige-
rina and vegetable remains in the Vigo shale at once attracts
attention. Most of the oil observed occurs in the shale which
contains organic matter of this nature, and it is well known that
the decomposition, under certain conditions, of animal matter
similar to the soft parts of Globigerina does give rise to petroleum.
The decomposition of organic matter, both Globigerina and
vegetable remains, in the Bacau stage of the Vigo shale may
have yielded the petroleum which is found in these beds.
However, neither Globigerina nor the vegetable remains are
especially abundant in the petroliferous beds, and it may he
questioned whether the quantity of organic matter which was
contained in the Bacau stage was adequate to have supplied
a large quantity of petroleum, or even the quantity of petroleum
which is to be observed.
Some of the properties of the Tayabas petroleum suggest that
the oil may have migrated to its present position. Most oils
obtained directly from the rocks in which it is certain that they
have originated are high in specific gravity, and consist largely
of heavy oils, with a very small gasoline content. On the other
hand, oils which are believed to have migrated from a distant
source, to the natural reservoirs in which they have accumulated,
are of low specific gravity and are rich in volatile constituents.
7 Hngler, C., Chem. Zentralbl. (1908), 2, 376.
VIII, A, 5 Pratt and Smith: Petroleum Resources 363
The refining or fractionation of petroleum by diffusion through
porous media is well known, and the characteristic clarified or
refined appearance of Tayabas oil might be so explained. It
has been shown * experimentally that the diffusion of petroleum
through porous media exercises also a selective function by which
the unsaturated hydrocarbons are removed. The Tayabas
petroleum has a moderately high content (30 per cent) of
unsaturated hydrocarbons, the presence of which would seem to
dispute the theory that the petroleum had been subjected to the
refining effect of diffusion. However, a discussion of the origin
of the petroleum in the oil fields of Kansas ?? quotes Dr. David
T, Day in an expression of the belief that the Kansas petroleum
shows the effects of diffusion, while according to the same
authority 22 Kansas petroleums contain from 12 to 50 per
cent of unsaturated hydrocarbons. Apparently, therefore, the
presence of unsaturated hydrocarbons in the Tayabas oil is not
incompatible with the theory that the oil has been refined by
diffusion.
If the Tayabas petroleum has been refined by diffusion,
the diffusion may have been either a lateral migration through
the Bacau stage or a migration upward or downward from the
neighboring strata. -The formations exposed at the surface
above the Bacau stage show no indication of oil. If the oil was
ever present in these beds, the greater part of it must have
escaped from their truncated edges along the anticlines. The
Canguinsa sandstone is locally of such fine-grained and compact
texture that it should retain traces of petroleum just as the
shale in the Bacau stage does, if petroleum had originated in,
or moved through, it. Apparently there is little chance that
petroleum occurs in the formations above the Vigo shale.
It is possible that concealed members of the Vigo shale beneath
the overlapping Canguinsa sandstone are petroliferous, and that
petroleum from them migrates along the unconformity to the
Bacau stage, which often appears at the surface immediately
below the Canguinsa sandstone. If the petroleum were coming
to the Bacau stage along the unconformity, it would be expected
that the base of the Canguinsa sandstone would be most strongly
petroliferous. This is not the case; usually, the petroleum ap-
pears in the beds of the Bacau stage and not along the uncon-
formity. Moreover, in some places the Canguinsa sandstone
* Gilpin, J. E., and Cram, M. P., Bull. U. S. Geol. Surv. (1908), 365.
2 Univ. Geol. Surv. of Kansas (1908), 9, 191.
* Day, David T., Bull. U. S. Geol. Surv. (1908), 381, pt. 2, 22.
364 The Philippine Journal of Science 1918
has been removed by erosion so as to expose sandstone belonging
to the Vigo shale above the Bacau stage, and this sandstone
generally has not been found to be petroliferous. Thus, while
the overlap of the Canguinsa sandstone may conceal petroliferous
horizons, there is little direct evidence that these concealed hori-
zons supply the petroleum which appears in the Bacau stage
of the Vigo shale.
Similarly, there is a chance that the unexposed basal portion
of the Vigo shale or a separate underlying formation is the
source of petroleum which has moved upward through cracks
and joints in the intervening beds to the Bacau stage. However,
a relatively great thickness of strata is exposed in the limbs of
the Central anticline between the Bacau stage and the lowest
beds of the Vigo which have been uncovered by erosion, and there
is but little evidence of oil in these intervening strata. Fresh
surfaces in the occasional fine-grained beds only show traces
of oil. Petroleum passing upward to the Bacau stage from a
reservoir in the hidden lower part of the Vigo might be expected
to leave traces along the outcrops of its passage through the
intermediate rocks. From the fact that the petroliferous shale
in the Bacau stage loses all evidence of oil after a short period
of exposure, it might be argued that the relatively coarse sandy
shales and sandstones between the Bacau stage and the lowest
exposed part of the Vigo shale would retain no oil at the surface.
In the data at hand, however, there is little evidence that the
petroleum -in the Bacau stage came there by diffusion from the
base of the Vigo shale or from an underlying formation.
It appears, therefore, that while other accumulations of pe-
troleum may exist in the concealed members of the Vigo shale,
the petroleum in the Bacau stage probably originated somewhere
in that stage, although it may have migrated laterally through
the beds to the points at which it is now found.
If exploration proves that no oil exists in this field, except
that which is evident in the Bacau stage of the Vigo shale, the
possible production of petroleum will be confined to the area
over which the strata are intact below the Canguinsa sandstone.
The oil content of the petroliferous shale in the Bacau stage
is probably low. Distillation of a sample, taken from a surface
outcrop and kept in a sealed package before testing, yielded less
than 1 per cent of oil. Beneath the surface where there has
been no chance for volatilization to take place the proportion
of oil is probably greater, but must still be relatively small
because of the close-grained nature of the shale.
VIIL, A, 5 Pratt and Smith: Petroleum Resources 365
However, the petroliferous shale and interbedded sandstones
make up the larger part of at least 50 meters thickness in some
places, and probably approach this aggregate thickness on an
average. Even with the low petroleum content specified, these
beds would store up a volume of oil which assumes commercial
proportions. Distributed throughout the shale, the oil could
hardly be recovered in any quantity by ordinary methods, but
if the saturation is great enough to cause an accumulation in
the interbedded sandstones commercial exploitation should be
possible. If the lenses of sandstone in the Bacau stage which
are not exposed at the surface and consequently have not been
broken open by erosion are saturated, the usual absence of oil
in the sandstones along the outcrops of the petroliferous beds
must be attributed to the rapid volatilization of the light oil
from the surface of the porous materials.
The pore space in the interbedded sandstones is an important
factor in this connection. Much of the coarser grained sand-
stone is so poorly consolidated that the actual pore space in the
beds as they occur cannot be determined. A sample of the
harder fine-grained sandstones taken from the vicinity of the
Ajus petroleum seep contains 11 per cent of pore space. Prob-
ably the coarser sandstones are more porous.
Earlier examinations of Bondoc Peninsula have led to the
published statement by two independent observers that the sur-
face showing of oil is as favorable as those in other fields which
have become large producers after development. It may now
be added that the oil is associated with certain zones in an
extensive series of shale and sandstone, and that the geologic
structure is locally suitable for the accumulation of whatever
petroleum is present.
A definite estimate of the quantity of petroleum available
in this field, based solely on the data recorded in this report,
in advance of any exploration is not justified. It would be a
simple matter to estimate the thickness and area of the sands
in the Bacau stage which could be reached by the drill in
structurally favorable regions and to calculate the quantity of
petroleum contained in these sands on the basis of their porosity
as stated above, but the figure so obtained would have little
real significance. The present knowledge of the field, however,
does afford a basis for the belief that properly located wells
could be made to yield at least small individual productions
from the Bacau stage of the Vigo shale. From the thinness of
the sandstone beds and the alternation of sandstone and shale
122679——5
366 The Philippine Journal of Science 1913
it may be concluded that the sandstone reservoirs are of small
lateral extent and, consequently, that wells could be spaced
closely without affecting each other. This being the case, the
structurally favorable area over which the Bacau stage could
be reached by drilling is large enough to make the total possible
production of commercial importance. In addition to the pos-
sibilities of the Bacau stage there is the chance, which has been
discussed, of obtaining oil at other horizons in the Vigo shale.
As evidence which bears somewhat on the question of ob-
taining petroleum on Bondoc Peninsula, it may be worth while
to consider, briefly, the results of exploration for petroleum in
other oriental fields. The general geology of the two important
productive fields in the Orient, the Echigo field in Japan and
the Moera Enim field in Sumatra, is similar to that of Bondoc
Peninsula (compare Tables I, II, and III).
There are productive fields in Sarawak and in the eastern
part of Borneo, but in British North Borneo the attempts to
obtain petroleum have been unsuccessful. Although Borneo is
adjacent to the Philippines, very little information is available
concerning its economic geology and nothing is known of the
geology of its petroleum resources.
In Formosa (Taiwan) which is also adjacent to the Philip-
pines, only a small production, 6,200 barrels in 1908, ** is re-
corded, although many shallow wells have been drilled. One
of the few deep wells in the Byritsu Field on Formosa is said
to yield a good flow of oil, and there is a possibility that with
deeper drilling the Formosa petroleum fields will assume greater
importance.
A well drilled in 1896 on Cebu Island in the Philippines, is
said to have reached a depth of 300 meters; while it encountered
considerable petroleum, it did not yield a satisfactory flow. The
exploration was suspended before completion, because of the
outbreak of an insurrection, and it has never been resumed.
While the general geology of the two regions is similar, the local
conditions at the site of the well in Cebu are different from
those in Bondoc Peninsula. The drilling site at Toledo, Cebu,
is located on the outcrop of thé petroleum-bearing strata, and
is within a few kilometers of the basal igneous complex upon
the flank of which the beds lie, inclined at a high angle.
* Fukotome, K., Mineral Resources of Formosa (1910), 18. The Mineral
Resources of the United States for 1911 reports 8,304 barrels of oil from
Formosa in 1908 and 1,688 in 1911.
VIII, A, 5 Pratt and Smith: Petroleum Resources 367
The foregoing brief statement includes practically all that is
known concerning petroleum fields in the vicinity of the Philip-
pine Archipelago.
AREAS TO BE PROSPECTED
Drilling on Bondoc Peninsula should be directed so as to
answer three questions. It should determine (1) whether a
sufficient quantity of oil is accumulated in the Bacau stage of
the Vigo shale to afford a commercial production, (2) whether
any members of the Vigo shale concealed by the overlap of the
Canguinsa sandstone may be made to yield petroleum, and (3)
whether there is petroleum in the unexposed base of the Vigo
shale.
The same work should serve to determine points (1) and
(2), since if wells are drilled through the Canguinsa sandstone
to the Bacau stage of the Vigo shale on the limbs of the anticlines
at varying distances from the axes, as is recommended later in
this discussion, they will necessarily pass through any higher
beds in the Vigo shale which may be covered unconformably
by the Canguinsa sandstone.
If the Vigo shale is constant in the thickness which it displays
in the Matataha River sections, it would not be feasible to
explore both the Bacau stage and the basal portion of the Vigo
shale with a single well, since the depth involved—even if the
strata were horizontal—would approach 2,000 meters. It is
possible that the Vigo shale is not of uniform thickness and
that in some parts of the field a deep well might penetrate the
entire series. Even so, however, wells from 400 to 600 meters
in depth, located so as to pierce different horizons in the shale,
would probably be less expensive and more suitable for initial
exploration than a smaller number of very deep wells.
Without more data the anticlines in Bondoc Peninsula must
be considered as the most favorable zones for exploration. The
oil seeps are near the crests of anticlines generally and possibly
in all cases. Experience in other oil fields has proved the theory
of the accumulation of petroleum in anticlinal zones 7° to be of
wide application. In the South Sumatra field and the Echigo
field in Japan; which have been cited in comparison with the
Bondoc field, production is reported to have come largely from
the anticlines. In the former field only wells on the immediate
crests of anticlines have been productive.
>For a discussion of this theory consult Bull. U. S. Geol. Surv. (1907),
322, 71 et seq.
368 The Philippine Journal of Science 1913
In the local field a distinction must be made between those
anticlines in which erosion has left the possible productive
horizons intact across the arch and those in which erosion has
proceeded along the crest until the oil-bearing strata have been
cut through. Where the oil-bearing rocks are preserved across
the anticline, oil—or gas—would be expected in the crest of the
fold and wells should be located so as to explore the crest first.
Where the productive beds are cut through along the crest and
their edges exposed in the limbs of the anticline, the petroleum
may be supposed to have escaped from outcrops along the axis
and wells should be driven on the flanks of the fold in the hope
of encountering a natural reservoir which does not appear at
the surface and, consequently, has not been drained by seepage
from its outcrop.
The anticlines in Bondoc Peninsula are generally asymetric;
that is, one limb is steeper than the other. In drilling on an
anticline of this character the limb with the lesser inclination
affords better opportunity for exploration than the steeper limb.
It is probably true, also, that the gentler limb of a sharp
asymmetric anticline more generally has been found to be pro-
ductive than the steeper limb.
The Maglihi anticline is probably the most suitable territory
for the initial exploration of this field. The structure is favor-
able in that an anticlinal fold exists, although the anticline is
more acute than would generally be considered desirable, and
the petroleum-bearing strata are intact generally along its axis.
The presence of petroleum in this anticline is established by the
seeps at Banco, at Bahay, and on Milipilijuan Creek.
In the matter of the actual location of prospect wells, the
factor of comparative accessibility will demand attention. The
Maglihi anticline appears to be most favorable in structure near
Mount Morabi. It would be desirable to have several test wells
drilled through the crest and the western limb of the fold in
this vicinity. The eastern limb should also be explored, but
in it the strata dip very steeply, and the best location for the
first wells would be difficult to determine exactly. The vicinity
of Mount Morabi is relatively inaccessible as compared with
Bahay farther north along the same flexure. The valley along
the anticlinal crest near Mount Morabi is at least 250 meters
above sea level, and the distance to the coast is about 6 kilo-
meters.
At Bahay the anticline is not so clearly revealed as it is near
Mount Morabi, and the structure may be less favorable, although
the general conditions are similar. It would be feasible to
VI, A, 5 Pratt and Smith: Petroleum Resources 869
prospect the eastern limb of the anticline through the Bacau
stage of the Vigo shale by two or three wells located at varying
distances from the axis in the valley of Bahay River below the
mouth of Milipilijuan Creek. Wells in this position would also
pass through any members of the Vigo shale which may be
concealed by the overlap of the Canguinsa sandstone. Similarly,
the crest and the western limb could be explored by a line of
wells up the valley of Apad Creek.
This general site is from 40 to 50 meters above sea level and
from 4 to 5 kilometers from the coast. An old roadway, which
might be utilized, leads into the region from the beach at the
mouth of Bahay River.
Exploration of the limbs of the Maglihi anticline in the imme-
diate vicinity of the oil seep on Bahay River or that on Milipili-
juan Creek would involve more difficult transportation problems.
Moreover, while the earliest drilling in many oil fields has been
done in the vicinity of actual seeps, very often the larger produc-
tion has developed in areas where oil seeps are not prominent.
- In exploration on Bondoc Peninsula it would be unwise to ignore
the presence and distribution of the oil seeps, but it would be
equally unwise to drill only where oil is to be seen.
The Central anticline should be explored by series of wells
across its axis and both limbs adjacent to the axis in the vicinity
of Bacau and, also, farther north near Balinsog. The structure
is favorable at these places, and the presence of oil is established
by the seep at Bacau. On account of its larger size, the Central
anticline may contain larger accumulations of petroleum than
would be expected in the Maglihi anticline. Bacau and Balinsog
are each about 9 kilometers from the coast, and the intervening
country reaches an elevation of 300 meters making these regions
very inaccessible. ;
The Central anticline in the northern part of the field will
afford valuable drilling territory if petroleum is found in the
Vigo shale below the Bacau stage. On the other hand, if only
the Bacau stage proves to be productive, the northern part of
the Central anticline from which the Bacau stage has been re-
moved by erosion loses its importance. South of Bacau the
southerly plunge of the Central anticline probably carries- the
petroleum horizons down beyond the reach of the drill. Pros-
pecting in the southern part of the peninsula in line with the
Central anticline would determine this point and might prove
successful. :
The possible locations which have been discussed are all near
oil seeps and are on sharp anticlinal folds. The Ayoni anti-
370 The Philippine Journal of Science 1913
cline has no oil seep on its crest, and it is a broad gentle fold.
The fact that no petroleum escapes from it may be taken as an
unfavorable or a favorable indication, arguing either the absence
of petroleum or that the petroleum has been confined by the un-
broken strata, there having been no opportunity for it to reach
the surface here, such as is afforded by the cracked and fissured
axial portions of the sharper folds. A broad gentle anticline
is generally looked upon with more favor as a natural reservoir
for petroleum than an acute anticline. Judged by this standard,
the Ayoni anticline would be considered promising. It is readily
accessible, and there has been comparatively little erosion along
its crest. Wells on its crest and eastern limb should pierce the
upper part of the Vigo shale under favorable conditions.
On the other hand, there is an apparent transition in the
character of the Vigo shale from east to west at this latitude by
which shale grades into sandstone. It is possible that the shales
which appear to be the principal oil-bearing rocks are less ex-
tensive in the vicinity of Ayoni than elsewhere. The absence of
seepage, however, which might be taken to indicate such a change
in the character of the formations, can be accounted for readily
enough on other grounds as suggested above.
Wells should be drilled along Malipa Creek, in the southern
limb of the Malipa anticline, and also, probably, farther south
in the eastern limb of the Central anticline. The structure is
not unfavorable, and traces of oil and gas are in evidence. A
well near the axis of the Malipa anticline would reach the beds
in the lower part of the Vigo shale, and from a site farther up
the creek higher strata including the Bacau stage could be invest-
igated. This region could be reached with comparative ease by
coming up the valley of Vigo River from the coast.
The Bato anticline is not easily accessible, and the oneal
relations are not clearly enough defined to make it a favorable
site for the first drilling, although it appears to be relatively
good territory. The lower part of the western base of Camba- ~
gaco Ridge would be a favorable site for testing the beds in the
Vigo shale beneath the overlap of the Canguinsa sandstone.
Wells so located, if drilled deep enough, would also encoun-
ter the Bacau stage of the Vigo shale in fairly good structural
relations.
To reach the base of the Vigo shale and determine the value
of this zone in connection with petroleum, wells should start at
the lowest possible stratigraphic horizon. The upper valley of
Sibuyanin River in the western limb near the axis of the Central
anticline is probably the best site for such wells. The beds at
ss Pratt and Smith: Petroleum Resources 871
the surface here appear to be about 1,400 meters, stratigraphi-
cally, below the base of the Canguinsa sandstone, and the dip is
about 35°. The eastern limb just across the axis in the upper
valley of Vigo River is equally desirable as a drilling site except
for the steeper dip (from 60° to 70°) of the strata.
If oil is obtained in any of these localities, a number of places
which have not been mentioned may become desirable territory,
depending on what horizon the oil is encountered in and on other
conditions which will be revealed by the drilling. More detailed
work in the vicinities of Ajus and Sili may show that there are
favorable drilling sites at these places, and as has been suggested
the neighborhood of the volcanic agglomerate may prove valuable
as drilling territory.
It will be apparent that companies entering this field should
be prepared to drill several wells in order to prospect any local-
ity thoroughly. The failure of a single drilling should not be
accepted as establishing the absence of exploitable petroleum
resources in any particular zone or in any one anticline, and
certainly should not condemn the whole field. The drilling of
unsuccessful wells is common in producing fields, where the geo-
logy is well known and the experience gained from many com-
pleted wells is available. It would be surprising, indeed, if the
early drilling on Bondoc Peninsula did not result in a large pro-
portion of “dry” wells, even if exploration were ultimately
successful.
Skilled and experienced drillers should be secured. It is an-
ticipated that drilling on Bondoc Peninsula will be rendered
difficult by the unconsolidated, caving nature of the shale series,
and, possibly, by the necessity of sealing off water-bearing sands.
Because of the fact that these difficulties have been overcome
successfully in the California oil fields, drillers from these fields
should have experience that would be particularly valuable in the
local field.
The exact location of wells should be preceded by further and
more detailed geologic study of the region to be tested. The
relation of possible sites to the known and suspected petroliferous
zones should be carefully determined, and local variations or
irregularities in the general structural and geologic features, as
outlined in this report, should be noted before a decision is
reached as to the best drilling site. The progress of the first
drilling likewise should receive particularly close attention from
a geological standpoint since it may reveal conditions not manifest
at the surface which would alter the course of exploratory work.
872 The Philippine Journal of Science 1913
CONCLUSIONS
The existence of petroleum on Bondoc Peninsula is established
by the presence of seeps of petroleum associated with inflammable
gas at various places throughout the oil field.
All the petroleum encountered so far is similar in character
and of a good quality. It is of low specific gravity, and contains
a large proportion of light oils which would make it of relatively
high value as a commercial petroleum.
The seeps are in highly inclined strata which are probably in
all cases part of the structure of anticlinal folds. From this
association it is believed that the petroleum in this field has tended
to collect in the crests of anticlines in accordance with the gen-
eral law of petroleum accumulation.
The petroleum occurs associated with certain horizons in an
extensive series of beds of sandstone and shale (Vigo shale),
which is similar in character to the oil-bearing rocks of productive
fields. The principal seeps are found in the upper part of this
series in a zone designated as the Bacau stage, which is predom-
inantly shale, but contains subordinate beds of sandstone. In
its seepage, the petroleum is associated with the shale rather
than the sandstone and may be observed in some cases to come
directly from the shale, but this association may be due to the
ready escape of the light oil from the outcrops of the coarse-
grained beds and its retention at the surface in the fine-grained
shale only. ;
The petroleum may have originated, in part at least, in the
globigerina and other organic remains found in the strata with
which the oil is associated. There is a possibility, however, that
the oil is not indigenous to the strata in which it now occurs, but
has migrated from its source in another horizon. Beds which
are concealed so that they cannot be examined at the surface and
which, consequently, may be sources of oil occur as follows: (1)
Members of the Vigo shale above the Bacau stage, concealed by
the overlap of the Canguinsa sandstone which overlies the Vigo
shale unconformably; (2) the basal portion of the Vigo shale
which has not been uncovered by erosion; and (3) any sedimen-
tary formations which may underlie the Vigo shale.
The structure of Bondoc Peninsula includes a number of anti-
clinal folds, and the conditions along some of these anticlines
are considered favorable for the accumulation and retention of
the petroleum, whether it occurs in all or in any one of the hori-
zons at which it is suspected.
VIII, A, 5 Pratt and Smith: Petroleum Resources 373
Drilling exploration is recommended and should be conducted
along lines which have been indicated. Wells should be so located
as to explore the Bacau stage of the Vigo shale thoroughly under
favorable conditions of structure. The possible sourcés of pe-
troleum outside the Bacau stage likewise warrant exploration.
Areas considered favorable for prospecting by test wells have
been outlined.
The quantity of petroleum which might be recovered com-
mercially from this field is undetermined. Certain geologic fea-
tures which have been pointed out lead to the belief that only
wells of small individual productions will be obtained; but it is
also probable that wells of this character could be closely spaced
without mutual interference and that the territory within which
they could be located is large. A sufficient number of these wells,
drilled in groups so as to be operated from local centers, might
reasonably be expected to yield an aggregate quantity of limited
commercial proportions. There is a possibility, conditioned
largely upon the presence of oil at a horizon other than the
Bacau stage of the Vigo shale, of obtaining wells of larger
individual flow and a greater total production of petroleum.
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ILLUSTRATIONS
PLATE I
Fossils from raised coral reefs (Recent and Pleistocene). About one-half
natural size. (Photographs by Martin.)
Fig. 1. Conus flavidus Lam. Fic. 9. Crista pectinata Linn.
Figs. 2 and 3. Voluta sp. 10. Cerithium nodulosum Brug.
Fig. 4. Potamides sp. 11. Circe pectinata Linn.
5. Spondylus sp. 12. Cerithium jenkinsi K. Mart.
6. Telescopium telescopium (?)
Linn. 13. Arca cecillei Phil. (?)
7. Natica sp. 14. Strombus canarium Linn.
8. Trochus fenestratus Gmel.
PLATE II
Fossils from the Upper limestone and the Cudiapi sandstone of the Ma-
lumbang series (Pliocene and upper or middle Miocene). About one-half
natural size. (Photographs by Martin.)
Fig. 1. Pecten senatorius Gmel. Fic. 6. Cyclolites sp.
2. Cytherea sp. 7. Indet.
3. Lagenum multiforme K, 8. Turbo sp.
Mart. var. tayabum var. 9. Cardium sp.
nov. 10. Conus sp.
4, Spondylus imperialis Chem.
5. Schizaster subrhomboidalis
Herkl.
PLATE III
Fossils from the Lower limestone of the Malumbang series (upper or
middle Miocene). About one-half natural size. (Photographs by Martin.) .
Fig. 1. Indet. Fic. 4. Schizaster subrhomboidalis
2. Cypraea sp. Herkl.
3. Portion of internal cast of 5. Pyrula gigas K. Mart.
Cerithium sp. 6. Macoma sp.
PLATE IV
Fossils from the Canguinsa sandstone (middle or lower Miocene) and
from the Vigo shale (lower Miocene or Oligocene). About one-half nat-
ural size. (Photographs by Martin.)
Fig. 1. Conus loroisii Kien. Fic. 7. Indet.
2. Conus ornatissimus K. Mart. 8. Hindsia sp.
3. Pyrula bucephala Lam. (?) 9. Arca sp.
4. Tapes rimosa Phil. , 10. Cyclolites sp.
5. Corbula socialis K. Mart. 11. Strombus triangulatus K.
6. Conus djarianensis K. Mart. Mart. (?)
PLATE V
Globigerina (Rhizopoda) from the Vigo shale; a possible source of pe-
troleum. (Drawings by Moskaira.)
Fics. 1 to 3. Characteristic shapes assumed. Magnification, 20 to 25 dia-
meters.
4 and 5. Details of the structure of the shell. Magnification fig. 4,
20 to 25 diameters; fig. 5, 140 diameters.
375
ae ae
Fig. 1.
Hig. ae
Fig. 1.
The Philippine Journal of Science 1913
PLATE VI
Bahay well 2 on the property of the Bahay Valley Oil Company,
Bahay. (Photograph by Pratt.)
Looking eastward near the mouth of Cambagnaon Creek. The
hills in the distance lie on the eastern flank of the Central anti-
cline. (Photograph by Manila Mining Association.)
PLATE VII
(Photographs by Manila Mining Association)
Looking west-northwestward across Vigo River near the eastern
coast of the peninsula; the eastern slope of Mount Dagmit to
the left, and in the distance beyond the river, a part of Cam-
bagaco Ridge with characteristic slope to the eastward resulting
from the eastward dip of the strata.
The eastern wall of the upper valley of Canguinsa River south of
Balinsog Hill. é
PLATE VIII
(Photographs by Manila Mining Association)
Looking northward from near Balinsog Hill.
Looking westward from near Balinsog Hill, across the upper valley
of Canguinsa River, which marks the crest of the Central anti-
cline, to Cudiapi Range on the western limb of the Central
anticline; South Cudiapi Mountain in the middle distance.
PLATE IX
(Photographs by Pratt)
Looking east-northeastward across the valley of Malipa Creek
toward the ridge along the eastern coast, Mount Cambagaco to
the left, gap formed by Vigo River in center, and Mount Dagmit.
to the right.
South Cudiapi Mountain across the valley of Bondoc River; look-
ing northeastward from a point 2 kilometers south of Bondoc.
Mount Cancalao in the valley of Matataha River; looking westward.
PLATE X
(Photographs by Pratt)
Outcrop of Cudiapi sandstone in the eastern limb of the Central
anticline; looking northwestward from near the head of Can-
guinsa River.
Outcrop of Canguinsa sandstone in the eastern limb of the Mag-
lihi anticline on the lower part of Bahay River; looking south-
ward. :
Nearly vertical Vigo shale near the axis of the Central anticline
on the lower part of Cambagnaon Creek; looking southward.
Outcrop of volcanic agglomerate near Dumalog Creek.
MAP
Geologic reconnaissance map of a part of Bondoc Peninsula with 5 geo-
logic sections.
Fic. 1.
TEXT FIGURE
Diagrammatic section in the upper valley of Malipa Creek.
PRAT? AND SmitH: PETROLEUM RESOURCES. ]
(Pum. Journ. Scr., VIII, A, No. 5.
PLATE I.
reefs (Recent and Pleistocene).
6. Tele
Fossils from raised coral
Voluta sp. 4. Potamides sp. 5. Spondylus sp.
sp. §. Trochus fenestratus Gmel.
11. Circe pectinata Linn. 12. Cerithium jenkinsi K. M
14. Strombus canarium Linn. About one-half natural s
9. Crista pectinata Linn.
Fig. 1. Conus flavidus Lam. 2, 3.
scopium telescopium Linn. 7. Natica
10. Cerithium nodulosum Brug.
art. (?) 13. Arca cecillei Phil. (?)
ize.
PRATT AND SMITH: PETROLEUM RESOURCES. ] [PuiL. Journ. Scr., VIII, A, No.
or
PLATE Il.
Fossils from the Upper limestone and the Cudiapi sandstone of the Malumbang series (Pliocene
and upper or middle Miocene). Fig. 1. Pecten senatorius Gmel. 2. Cytherea sp. 3.
Lagenum multiforme K. Mart. var. tayabum var. nov. 4. Spondylus imperialis Chem. 5.
Schizaster subrhomboidalis Herkl. 6. Cyclolites sp. 7. Indet. §&. Turbo sp. 9. Cardium
sp. 10. Conus sp. About one-half natural size.
i
PRATT AND SMITH: PETROLEUM RESOURCES. ] [Puit. Journ. Scr., VIII, A, No. 5.
PLATE Ill.
Fossils from the Lower limestone of the Malumbang series (upper or middle Miocene). Fig. 1.
Indet. 2. Cypraea sp. 3. Portion of internal cast of Cerithium sp. 4. Schizaster subrhom-
boidalis Herkl. 5. Pyrula gigas K. Mart. 6. Macoma sp. About one-half natural size.
t
‘ =
< i
- -
>
‘ ~ .
-
,
£ sf
i =
+ : of
il 2 we 4
4 - be x
PRATT AND SMITH: PETROLEUM RESOURCES. | [Pum. Journ. Scr., VIII, A, No. 5.
PLATE IV.
Fossils from the Canguinsa sandstone (middle or lower Miocene) and from the Vigo shale
(lower Miocene or Oligocene). Fig. 1. Conus loroisii Kien. 2. Conus ornatissimus K. Mart.
3. Pyrula bucephala Lam. (?) 4. Tapes rimosa Phil. 5. Corbula socialis K. Mart. 6. Conus
djarianensis K. Mart. 7. Indet. 8. Hindsiasp. 9. Arca sp. 10. Cyclolites sp. 11. Strombus
triangulatus K. Mart. (?) About one-half natural size.
6
7
PRATT AND SMiTH: PETROLEUM RESOURCES. ] (Pui. Journ. Sct., VIII, A, No. 5.
PLATE V.
Globigerina (Rhizopoda) from the Vigo shale; a possible source of petroleum. Figs. 1-3. Charac-
teristic shapes assumed. 4, 5. Details of the structure of the shell.
PRATT AND SMITH: PETROLEUM RESOURCES. | (Pum. Journ. Scr., VIII, A, No. 5.
Fig. 1. Bahay well 2.
Fig. 2. Looking eastward near the mouth of Cambagnaon Creek.
PLATE VI.
PRATT AND SMITH: PerTROLEUM RrsouRCcEs. | (Pum. Journ. Scr., VIII, A, No. 5.
Fig. 1. Looking west-northwestward across Vigo River.
+
Fig. 2. The eastern wall of the upper valley of Canguinsa River.
PLATE VII.
PRATT AND SMITH: PETROLEUM RESOURCES. ] {Pum. Journ. Sct., VIII, A, No. 5.
Fig. 1. Looking northward from near Balinsog Hill.
Fig. 2. Looking westward from near Balinsog Hill.
PLATE VIII.
'
= ~
4 -
thee -
ov
PRATT AND SMITH: PETROLEUM RESOURCES. | {Puit. Journ. Scr., VIII, A, No.
Fig. 1. Looking east-northeastward across the valley of Malipa Creek.
Fig. 2. South Cudiapi Mountain across the valley of Bondoc River, looking northeastward.
Fig. 3. Mount Cancalao, looking westward.
PLATE IX,
PRATT AND SMITH: PETROLEUM RESOURCES. | [PuHi. Journ. Scr., VIII, A, No. 5.
Fig, 4. An outcrop of volcanic agglomerate.
PLATE X.
iPile
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Thesi
‘INDEX MAP
oilfield on Bondoc Peninsula *),
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Based on U.S. Coast and Geodetic Survey Chart al Surveys by Bureau of Lands
Topography from compass traverses and sketches by F A, Dalburg and W.E. Pratt.
<< NS
Sealevel I<
Section along Line AB i
V7 :
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Geology by Wallace F Pratt and FA, Dalburg.
seers eal (esa under general supervision of W.D. Smith.
LB LA WC) es i
i Oil Wells
Alluvyium, Recent Coral, Malumbané Series Gengemen Vigo Shale Volcanic Ag¢lomerate Oil Seeps H
and Littoral Deposits (limestone and sandstone) Sandstone
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MANILA, ‘sama ances ISLANDS—Continued > aa I
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THE PHILIPPINE ™“ie..) “use”
JOURNAL OF SCIENCE
A. CHEMICAL AND GEOLOGICAL SCIENCES
AND THE INDUSTRIES
Vou. VIII DECEMBER, 1913 No. 6
THE NIPA PALM AS A COMMERCIAL SOURCE OF SUGAR
A CONSIDERATION OF THE PRINCIPAL DIFFICULTIES ENCOUNTERED IN
COLLECTING AND PRESERVING NIPA-PALM SAP
By D. S. Pratt, L. W. THuRtow, R. R. WILLIAMS, and H. D. Gipss*
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
The nipa palm, Nipa fructicans Wurmb., covers large areas
of swamp land in various parts of the tropics. The requirements
for its growth and proper development are few, consisting of
low river land subject to periodic overflow by brackish tide
water. Large areas of this character, covered almost exclusively
with the nipa palm, exist in several provinces throughout the
Philippine Islands. At the present time the sap exuded by the
flower stalk when it is cut is utilized on a large scale as a com-
mercial source of alcohol. .
The manufacture of nipa alcohol and the distribution of the
palm in the Islands have been investigated, and preliminary
experiments by one of us? on the manufacture of sugar have
* Associate professor of Chemistry, University of the Philippines.—
EDITOR.
* Gibbs, H. D., This Journal, Sec. A (1911), 6, 99-206. At that time ex-
periments on a commercial scale seemed impossible for the reason that no
modern sugar mill existed on Luzon. This difficulty was removed by the
construction of a 10-ton mill at Muntinlupa, Rizal Province, 33 kilometers
by railroad south of Manila. A description of this mill has been published
in This Journal, Sec. A (1912), 7, 357, by Thurlow and Pratt.
123668 377
baa
soe erg!
378 The Philippine Journal of Science 1918
been carried on. These results were eminently satisfactory,
and lead directly to further study on a more extensive scale.
Many other palms, such as the coconut, buri, and sugar palms,
elaborate a sweet juice containing sucrose, and have been sug-
gested as possible commercial sources of refined sugar. ‘The
nipa offers many distinct advantages not found with other
palms. It is already extensively grown in localities that other-
wise would remain waste land, but which offer cheap water
transportation for juice from swamp to mill. The collection
of sap is greatly facilitated by the nature of the palm, since it
produces the flower stalk close to the surface of the ground
and within easy reach. With other palms, such as the coconut
and buri, the sap is gathered at a considerable elevation from
the ground that necessitates climbing and increases the cost of
collection.
The method utilized for many years in collecting the sugar-
bearing nipa sap, or tuba as it is generally called, is to cut off
the recently formed fruit at its point of attachment to the stalk.
The sap flows freely from the freshly cut surface of the stalk,
and is collected in bamboo joints called tuquils or bombones.
These vary in size and shape, depending upon the customs of
the natives working in variously located swamps. In the large
areas of Bulacan Province, the tuquils are about 50 centimeters
long, with a diameter of 10 centimeters and a capacity of from
1 to 2 liters, while those employed in other districts often exceed
a meter in length and are capable of holding several liters of
tuba. The receptacle has a small hole in the side wall near the
upper extremity through which the stalk of the palm is intro-
duced, serving to support the bombon and allow the sap to drop
into the interior. The twberos—men employed in gathering the
sap—visit the palms twice a day, and cut off a thin slice from
the end of the flower stalk to keep the wound fresh and prevent
stoppage in the flow of sap.
Jt has been shown ® that a stalk normally flows for about
three months, during which time it produces from 30 to 50 liters
of sap, the greater portion of which is secreted during the first
two months after tapping. The yield of sap may be partially
equalized by progressive tapping of new palms, but much depends
upon the season.
The number of palms per hectare varies within wide limits,
as might be expected, since many swamps have been used for
years and have received at least a moderate amount of attention,
* Gibbs, lec. cit.
wa A,6 Pratt et al.: Nipa Palm 379
while other unworked areas are overgrown and choked. The
former naturally support fewer palms of superior quality com-
prising a larger proportion of fruiting plants. A conservative
estimate for cultivated nipales, or nipa swamps, may be placed
at from 2,000 to 2,500 palms per hectare, of which 750 may be
depended upon to produce fruiting stalks and consequently be
available for sap collections. Proper attention in keeping the
swamps free from overcrowding and intelligent care in selection
would doubtless greatly increase the percentage of flowering
plants, and might raise the average individual production of
sap and its sucrose content.
THE CHARACTER OF THE SAP
The nipa sap collected in the above manner and transported
to the distilleries is of no value for the manufacture of sugar.
Many factors to be discussed later have resulted in causing more
or less complete inversion of the sucrose followed by alcoholic
and acidic fermentation. Nipa sap is very susceptible to changes
of this character, any of which are fatal to its utilization as a
source of refined sugar.
The sap as it flows from the cut surface of the flower stalk
is water white, practically neutral, and possesses a character-
istic odor. The composition varies considerably, depending
upon the age of the flower stalk—or time that has elapsed since
it was first cut—the season, the location, and the individuality
of the palm. The tendency of nipa sap to undergo inversion
within a few hours after collection, even when great care has been
employed to obtain aseptic samples, and the impracticability of
laboratory work in the swamp render it difficult to obtain as many
analyses of fresh sap as could be desired. No preservatives
have been found efficient in preventing change in the character of
the juice without introducing a relatively large amount of foreign
material. The only satisfactory method is to collect the sap
directly in clean bottles and sterilize by heat within an hour or
two after starting the collection.
The average nipa sap as it flows from the palm has approx-
imately the following composition:
Density 15°/15° 1.0670
Brix 17.0
Apparent purity 90.0
Invert sugar Trace.
Sucrose 15.0 per cent.
Nitrogen 0.049 per cent.
Ash 0.60 per cent.
Sodium chloride 0.45 per cent.
880 The Philippine Journal of Science 1913
Toward the end of the period of flow, the percentage of sucrose
and the purity decrease. Table I shows the sucrose content
of nipa sap collected in Bulacan Province on September 15, 1912.
The samples were collected in polariscope tubes hung on the
palms and polarized directly. The per cent sucrose is calculated
from the polarization, assuming an apparent purity of 90. The
error thus introduced is slight, as shown by experience.
TABLE I.—Per cent sucrose in various samples of nipa sap from 99 individual
palms. Collected in the Bulacan region, September 15, 1912.*
North of South- South of
Sample No. Sau Bate: s an Este Guagua. aa ete, Consuelo. Fe Hagonoy.
Ue os ee eee 14.3 15.9 15.7 15.6 11.6 12.2 14.8
Down aa cee oe aS 15.8 13.7 | 13.6 15.6 10.1 10.6 14.7
Siete Cee eee 15.5 14.3 14.7 17.5 13.3 11.8 15.8
Ae OL Se oe 12.8 12.9 15.0 15.6 10.9 12.5 17.3
ARR AG ee Sa Se SS 16.8 13.6 15.9 ibypal 10.2 13.1 12.9
(fees eee FE 2) eee 15.2 | 15.6 15.3 16.2 13.5 13.5 14.1
f rene nen 5 os ioe ne en 15.3 | 15.7 14.6 aby isu ty 16.2 15.5
8.2. See eae ae | 15.4 13.6 12.7 17.3 12.2 15.2 13.3
9... Seer eee 15.4 15.7 14.6 16.0 10.5 14.5 15.3
CA ee Ae aE Ne | See | 14.6 15.1 aye 10.7 17.4 14.4
BU ER, Se Se Ea a de 160) ||-2 ee see 17.4 10.8 12.5 15.2
Zee Se a es RRR Se LG: 40 3) Se 16.8 11.5 |.->s.5 23 |e
th Ae ee eee oes ee aed oe |p ae Gs) ieee ae ee 16.5 11.2) |...->.L3 4 eee
| Tae a eae eee ea va |W Mechs 1558" | eee 16.7 11.2 |) -
15 S22 se Bee eS ge Se Sie eee 14.) cate eS 3 17.8 18.9 | 2222-222 eseeeeeeee
NGOS SE SL ee Ie EES ee eS ASD) |S we- selee bs 14.7 11.5 |.22-.22) 23 BSae Sees
Viize. See Me As, ee ce Bey Oe Neate ee Re Bee 16.8 ce a eee es a | soot eae
18 Ue Ba ee coe ee ae ee ee eee elt eae ee 17.4 10.8 |. < 523] 5 eee
19 se ene he ae eed [Sree hee ee oa Me Se a (Sesto snca 17.1 11.9: |...
20 USL Soh TE eS WSeraeenas BRANT 2 [Eze Mares | 17.8 11.1). a
21 SSRs ae: a Be ered sone see 2 Bed a oe ean . dQ? ep S oe eee
20 SBE eee I NE ee |----------|---------- 12; 8) |__.. 2 2 = eee
Average _________-__ | 15.2 14.9 14.7 16.8 11.4 13.6 14.8
a8 Determinations by E. R. Dovey.
Table II shows the total sugar and volume of juice per twenty-
four hours from 20 palms with flower stalks of various lengths.
As the stalks are sliced daily when flowing, they become shorter
as the season advances. These samples represent sap flowing
near the end of an abnormal season during which lack of rain
and other climatic conditions rendered the supply of tuba very
scant and of poor quality.
VIII, A, 6 Pratt et al.: Nipa Palm 381
TABLE II.— Samples of nipa juice collected near Malolos, December 1, 1912.
Volume
No. | ete Sucrose. . Seater “ine
hours. CREE
cm. Per cent. ce. Grams.
ple ee el eid Tene aay 380 10.1 420 42.4
ise soe Fs eee Lee 60 12.4 380 47.2
Bee ee Oe Se peer | 50 11.6 500 58.0
0 ben ok Se Mark Te ea 55 9.7 730 70.8
[Tie Se, se en mee ePiee = ee NES 35 12.4 620 76.8 *
Cf eh ie 20 a a eae ON 87 12.6 630 79.4
is SUES OTN Ce eR He a 70 13.3 590 78.5
Oe Les eis See 100 12.9 940 121.1
(i we ee Se eee 65 12.0 510 61.3
Tse oe eae eles Soe eee 60 15.3 380 58.2
(1s ie eel er ok, Ye 63 13.1 460 60.8
OR erie a eee tie Ce 110 11.3 -470 53.3
Ue ee 90 14.8 510 75.4
Ay te CT ee te IN 65 14.2 320 45.5
i | aoe eae See eae ee 70 11.8 450 53.3
IG ese e ee or eee Soe 60 13.0 480 62.4
NY lea ee ee a el 70 13.1 540 70.7
1 A Rae 9s Se re ee 50 12.8 550 70.5
Tbe ies Ue SE ae 60 12.6 530 66.8
PLA EE DE here 70 11.5 740 85.0
AVCrAR@e serene sal seo eo 13.0 637 69.8
- Table III shows the percentage of sucrose and purity of nipa
juice collected near Malolos, Bulacan Province, on January 10,
1913. It is evident that the purity as well as sugar content of
the sap has decreased to a considerable extent since the analyses
given in Table I.
382 The Philippine Journal of Science 1913
TasLEe II1].—Samples collected near Malolos, January 10, 1918.
| No. Leneth | Brix. some | Purity. |
cm. | Per cent.
jE Te ei ell yee 5 10.7 7.7| 72
RN 2 eRe UTA Saale 60 1.7 9.4) 81
reels Deh eae ate 68 10.5 5:6 | 9 Si
Pieeetir REPRISES de | % 117 10.0} 85
ee ee Oe ee 90 11.7 9.4| 81
Go eel ee lee sete we 105 12.6 10.6| 83
iat BBR SNE AL se. hie 4 5 12.9 10.5] 81
|! ga Sh eet ean 75 13.1 HS 11 ST
| «iQ ina 20 SR Seine Bee 100 13.8 11.9] 86
(are iis Drew, . Wee 105 13.6 11.0] 81
eee eae a aah Sir | 45 14.3 11.5] 80
Pen: eke, beaver 30} 12.9 10.6] 82
ip eel aA ee ee 25 12.6 10.4| 83
14s es ea eg 30 18.8 11.1] 80
yO aM sy | 15 14.7 11.7| 80
16k Aone ee | 13 1.7] 82
Ee Re eeaeaa es ee En 20} 12.9 10.8 84
| Ripon 5:2 Aree es pene 60) | ete 831 B34} reo
iL naan psa : Sabie lt. | 15 16.6 13.3 | 80
20 8s ee. SE | 25 15.0 2.2) 82 |
| Sarees ae [eare 13.3! 10.9 | 81.5 |
From the above tables and other analyses * it may be definitely
stated that nipa sap as it issues from the palm is exceptionally
well adapted to the manufacture of sugar. The acids, waxes,
ete. of sugar-cane juice are absent, the sap is free from invert
sugar, contains no débris, and is colorless. If it were possible
to transport the tuba without deterioration due to inversion and
fermentation to a mill, no difficulty would be experienced in
producing white sugar.
DETERIORATION OF NIPA SAP
The inversion of sucrose and subsequent fermentation take
place very rapidly after the sap drops into the bamboo tuquils.
These are always exceedingly dirty, as no effort is made to re-
move the accumulation of slime and sediment adhering to the
interior. It could not be expected under these conditions that
a sucrose solution would long remain unchanged in a tropical
climate. However, nipa sap begins to invert within about four
hours after leaving the palm, even when collected in sterile
bottles.
Gibbs * has shown that a zymogen is present in solution in the
*This Journal, See. A (1911), 6, 99-206.
VILL, A, 6 Pratt et al.: Nipa Palm 383
sap and that atmospheric influence causes the separation of
white, flocculent invertase which rapidly attacks the sucrose
present. He recommends lining the interior of clean tuquils
with thick lime cream, and states that sap collected in recep-
tacles so treated will remain unchanged for a longer period than
ten days. We have found that sap collected early in the season
of flow may be preserved in a satisfactory manner by this means,
provided the interval between placing the tuquil in position on
the palm and removing the accumulated juice be not over twelve
hours. There is no doubt but that invertase action is effectively
stopped in alkaline solution. The principal objection to this
method of collection lies in the fact that large amounts of lime are
absolutely essential and that an even distribution of alkalinity
is uncertain. The latter difficulty is inherent in this method
of collection and preservation. The tendency of juice dropping
slowly into tuquils containing lime is to stratify. The first
juice dissolves relatively large amounts of lime, and consequently
attains a density considerably higher than the fresh inflowing
sap. These heavy layers remain at the bottom, and are gradually
covered with juice containing less and less lime until a point of
neutrality is reached. This tendency is counteracted to a greater
or less extent by the lime clinging to the sides of the tuquil, but,
if this has been carelessly applied or if the cream used was of
insufficient consistency, the desired result is seldom accomplished.
The upper portion of neutral juice is rapidly acted upon by the
invertase present, and subsequently undergoes fermentation, the
harmful results of which need not be mentioned in detail. Not
only is sucrose destroyed, but invert sugar is formed, and the sol-
uble lime salts resulting from acid fermentation render the juice
difficult to handle in boiling and greatly reduce the percentage of
available granulated sugar.
A large number of trials served to show that many of the
lime-coated tuquils contained acid-top layers of juice after twelve-
hour collections, and that this was the case in practically all
tuquils after twenty-four hours on the palm. The latter were
always covered with froth, and had developed a disagreeable
odor characteristic of fermented tuba. A simple and successful
method for obviating this difficulty will be discussed later.
OTHER NIPA: ENZYMES
We observed that many samples of nipa juice, although uni-
formly alkaline with lime, showed a gradual loss of sucrose, while
other samples could be so preserved for long periods of time
without change. Samples of juice originally containing 15 per
384 The Philippine Journal of Science 1918
cent sucrose gradually deteriorated until after two weeks they
contained only 0.5 per cent. The Brix decreased correspondingly,
while the small amounts of invert sugar originally present com-
pletely disappeared. A careful bacteriological examination by
E. L. Walker of the Bureau of Science showed these samples to
be practically sterile. The only plausible explanation of this
peculiar behavior seemed to be based upon the presence of enzyme
activity. We have found that the nipa palm actually does elabor-
ate a very active enzyme of the peroxidase type. Slices of the
plant immediately give a dark blue with tincture of guaiacum and
hydrogen peroxide and characteristic colors with all the specific
tests for this class of enzymes. The speed with which these
colors are developed indicates an activity of unusual magnitude.
The peroxidase is distributed throughout the entire palm, being
present in slight amount in the midrib of the leaf and very
strong in the immature fruit. The juice secreted by long flower
stalks producing a free flow of sap gave negative tests for the
presence of this enzyme, while tuba, from short stems approach-
ing the end of the sap flow, always gave strongly positive tests.
It is evident that the character of the juice changes as the season
of flow advances, probably due to the varying requirements of
the maturing fruit. A careful series of experiments proved
* beyond doubt that some enzyme capable of destroying both su-
crose and invert sugar is present in the nipa palm. It is active
in neutral or alkaline solution, but is killed by inorganic acids
or heat. Solutions of pure sucrose, both neutral and alkaline
with lime, were treated with thin slices of palm tissue containing
the enzyme. These solutions were polarized, and the Brix was
determined at regular intervals. The sucrose content and den-
sity decreased regularly, both in the neutral and alkaline solu-
tions. Tables IV and V show the rate at which sucrose was
destroyed in two representative experiments.
TABLE I1V.—Enzyme destruction of sucrose in neutral solution.
phate Sucrose. |
Time Brix.
3 De-
Present. smapcik
Hrs. | Percent.) Percent.
0 14, 40 0 14.5
12 14.15 OT eee
24 13. 90 3.47 14.4
86 18. 70 AUSG: ee eee eee
48 13. 40 6.94 14.2
60 13.20 es eee ere
72 13.00 9. 72 14.0
VIII, A, 6 Pratt et al.: Nipa Palm 885
TABLE V.—Enzyme destruction of sucrose in alkaline solution.
Sucrose. | Alka-
aS eee eb nity,
Time. Brix.
D cao pe
e- aO per
Present. stroyed.| 100 cc.
Hrs. | Percent.| Per cent.
0 12 "0 0. 637 13.9
12 HOSS |p LGR! | ee See) ee
24 10.6 5.36) 0.484 13.3
36 10.4 TeTAn Deere o {ee fe
48 10.2 8.98 0.409 13.2 |
60} 10.1 rit aeons na [bees
72 9.9 11.61 | 0.397 13.1
Both of the above solutions gave strongly positive tests for
peroxidase at the end of seventy-two hours. The decreasing
alkalinity indicates the formation of acid-decomposition products
that combine with the lime and reduce the Brix, partially at
least, by actual precipitation of calcium salts. The action of
carbon dioxide was excluded in all cases. Solutions, similar
in every respect except that they contained no enzyme, under-
went no change in composition during this time.
Dextrose and levulose in neutral solution are destroyed by this
enzyme at approximately the same rate as in the case of sucrose.
Table VI includes data showing the oxidation in neutral solution
of nearly 10 per cent of the original dextrose within seventy-two
hours.
TABLE VI.—Enzyme destruction of dextrose in neutral solution.
; | i
Dextrose.
Time. |
| i Present.
|
De-
stroyed.
‘Hrs. | Per cent.| Per cent.
11.4 0
11.1 2.6
11.0 8.5
10.9 4.5
10.8 6.3
; 0
12
24
36
48
60 10.6 7.0
72 10.3 9.7
The destruction of invert sugar proceeds rapidly in solutions
containing lime with the formation of many decomposition prod-
ucts and a reduction in alkalinity and Brix. The additional
effect caused by enzyme action is relatively small in these cases.
386 The Philippine Journal of Science 1913
TABLE VII.—Destruction of dextrose in lime solution without enzyme.
Dextrose. Alka-
[oe eee ed Re YS
Time. gram Brix.
De-
Present. stroyed.}| 100 cc.
Hrs. | Per cent.| Per cent.
0 8.0 0.0 0. 280 9.7
12 5.0 CERO |e fee ee eae
24 3.2 60.0 0.215 9.3
36 PRN TB20 Wis 2 Be ees oe
48 1.6 80.0 0. 182 9.2
60 1.3 B40) 22-53 ee
72 0.9 | 88.9 0.145 9.1
TABLE VIII.—Destruction of levulose in lime solution without enzyme.
Levulose. | Alka- |
linity,
Time. gram Brix.
De- CaO per
Present. stroyed.| 100cc.
Hrs. | Per cent.| Per cent.
0 6.7 0 0.302 10.0
12 5.3 7At ee ih ee ee eee meee
24 4.3 35.8 0. 201 9.9
| 36 3.8 50.0 | er ae AE eS Se
48 2.8 58.2 | 0.151 9.7
60 2.4 64, Ol oe = 52. Sale obs eee
12 2.0 70.1 0. 106 9.5
Tables IV and V serve to bring out clearly the remarkable
activity of the enzyme present in nipa, and explain why
certain samples of juice, uniformly alkaline with lime, gradually
decreased in sugar content. Experiments also showed that nipa
sap containing palm tissue suffered an even more rapid loss of
sucrose by enzyme action than did the sugar solutions prepared
in the laboratory. This was to be expected, as the juice contains
a variety of constituents that might well activate the enzyme.
The presence of this active enzyme in the nipa palm has a very
important bearing on the commercial production of sugar. A
loss of from 5 to 10 per cent of the total sugar due to this cause
might be a deciding factor between success and failure, and such
a contingency must be guarded against in any commercial under-
taking. It would be less important if all juice could be collected
from long stalks, flowing freely, and secreting a sap compara-
tively free from enzyme. However, this is impossible under
the conditions that prevail in practice. The contents of many
VIII, A, 6 Pratt et al.: Nipa Palm 387
tuquils must be combined for transportation to the mill, and a
few rich in enzyme might thus contaminate a large collection.
Laboratory experiments with tissues of nipa palm showed that
the presence of a small amount of sulphite was sufficient effec-
tively to destroy the enzyme. The results of these experiments
led us td believe that the addition of sulphite, in small amount,
to the lime cream before placing it in the tuquils would result
in better preservation of the tuba. The actual results obtained
by this means exceeded our expectations, and appear to solve
the question of preserving nipa juice. A long series of further
studies in the swamps demonstrated that sap collected from very
short stems producing only a few hundred cubic centimeters of
juice in twenty-four hours could be collected and preserved for
over ten days when sulphite had been added to the lime cream in
the tuquil. Sap flowing from palms of this type always gave a
strong positive test for peroxidase.
EXPERIMENTS IN BULACAN PROVINCE
A number of samples were collected on January 25, 1913, in
Hagonoy, Bulacan Province, at the extreme end of the season
when the flower stalks were short and had nearly ceased flow-
ing. Small samples were first collected in clean glass bottles and
analyzed to show the composition of the fresh sap and its rate of
flow. Tuquils were then cleaned, lined with lime cream, and
placed on the palms. The collections were made twenty-four
hours later and analyzed at once. All these tuquils showed acid
layers of juice at the top and much frothing due to fermentation.
Tuquils were then lined with lime cream containing a small
amount of sodium bisulphite and placed on the same palms.
These samples were also collected after twenty-four hours and
analyzed. A much smaller percentage showed acid tuba and
foaming, and the juice was nearly colorless in every case. None
of the first series collected with lime alone contained sucrose
after further standing for one day, while those in which sulphite
had also been used showed no further change. The latter were
then combined to form a composite sample, that was transported
to Manila and carbonated to faint alkalinity. The precipitate
of carbonate was removed, leaving a bright juice of slightly
yellow color and high purity. Tables IX, X, and XI show the
results of these analyses.
888 The Philippine Journal of Science 1913
TABLE 1X.—Analyses of fresh juice.
No. SEU Sige in Bric polarize | Sucrose. | Purity.
|
em. ce. pet A Per cent.
60 60 12.2 45.0 1.2] *918
80 55 11.3 40.7 10.1 89.3
90 100 GU BY Ne) MEER 9.5 84.1
90 110 13.7 48.8 12.0 87.6
go | 90 11.8 42.7 10.6 89.8
75 45 14.4 51.4 12.6 87.5
80 40 15.5 | 57.4 14.0 90.3
15 70 10.6 33.7 8.4 719.2
60 60 12.5 42.1 10.4 83.2
50 15 (ig alle ee ee
100 60 Tey 46.5 11.3 82.5
90 100 11.6 33.6 ah8: 71.5
95 80 13.4 47.3 Te 87.3
95 25 13.2 | 44.4 11.0 83.3
90 45 12.5 41.0 10.1} 80.8
110 120 12.5 | 42.0 10.4 83.2
80 40 12.3 43.0 | 10.6) 86.2
Pare rea ren Pe tg 5 CP Ream Ie ee 10.7| 84.8
a Fermented
TABLE X.—Analyses of 24-hour collections with lime.
Composition of uncarbonated samples.
No. ‘ Brix. | r clam. Sucrose. | Purity.
VAS Per cent.
10.0 20.6 5.1 51.0
9.3 15.0) O10) | eee
9.2| 18.7 47 | 6L1
11.3 13.7 3.4 30.1
9.2 15.6 3.9 42.4
12.1 24.6 6.1 50.4
10.1 9.0 728) 22.7
9.4 = 2 070) 2a
11.8 23.0 5.7 48.3
9.3 = ih) OS Oe eee ees
12.2 BES 3.0 Peal
9.8 lad) ORO" |e == SEs
12.2 16.0 4.0 $2.8
10.6 16.5 4.1 38.7
6.9 — 5.0 0.0
9.8 20.8 5.2
11.0 26.0 6.5
en ails Le eae ae 3.2
VILL, A, 6 Pratt et al.: Nipa Palm 389
TABLE XI.—Analyses of 24-hour collections with lime and sulphite.
Composition of uncarbonated samples.
| No. Brix. pitenies Sucrose.| Purity.
V.° ‘| Per cent.
ge ee ae See 12.0 40.1 9.9 82.5
aes Se eee = See 8.7 27.7 7.0 80.4
Saks eae Be eg eee 11.0 34.1 8.5 Toe
Beh aye eee nS 13.0 45.6 11.3 86.9
Ce ee a eee 11.7 34,5 8.6 73.5
(Wie CUR. Be ea aie ae eas i139 38.1 9.5 79.8
( Bt see ane eee ea 14.7 50.2 12.3) 83.7
Beas a ee ae | 10.7 31.2 7.8 12.9
Nae ety at Ngee a 12.6 39.6 9.8 17.8
11) se eat A a A ee 12.2 30.8 7.6 62.3
3) eee Oa a eee 13.1 40.9 10.1 yueal
BAL Sapa A, See iy a ne 10.9 30.8 GY 70.6
1S Se ee Oh a ee 12.0 40.1 9.9 82.5
gS ee el epee eee a 36.7 91 17.8
preeS ee eee 12.5 39.6 9.8 78.4
OBE soe eo ot Ed Sh ee as 11.8 38.9 9.6 82.7
Uo eee vt oe eae ala ae 39.6 9.8 83.7
Avera pe lssesnene anak sree aon eens 9.3 18.8 |
ee eee
The composite sample resulting from the juices tabulated in
Table XI showed a rise in purity of 4 after carbonation. In-
creasing the average of Table XI by this amount gives a purity
of 82.8, or only 2 lower than the corresponding average of Table
IX, for original juice from the same palms. The sugar content
and Brix are decidedly lower, due to dilution caused by the lime
and sulphite cream. The behavior of sample 10 is especially
noteworthy. The juice flowing from this palm gave a strong
reaction for peroxidase, and could not be collected in a sterile
bottle for analysis without spoiling. With lime and sulphite the
sample appeared to have undergone no deterioration, although
the purity of the sample was very low. It is probable that the
original juice of this palm was of no value, but the results
obtained in an extreme case are significant.
EXPERIMENTS IN OTHER SWAMPS
Experiments on a large scale were carried out in one swamp
further to test the efficiency of lime cream and sulphite as a
preservative. Unfortunately, these tests were made during the
month of February when the nipa in this district produces a
small second crop of flower stalks. Consequently, few short
stems were encountered, and a large excess of thick lime cream
without sulphite appeared to be sufficient for preserving the
juice. Little or no peroxidase was found in the sap from these
plants. The data obtained are found in Table XII.
1918
The Philippine Journal of Science
390
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392 The Philippine Journal of Science 1913
The data in Table XII were obtained from 10 sets of nipa palms
representing about 200 plants. The composition of the juice
as it issues from the palm is tabulated under “original juice.”
Samples of this juice after analyses were preserved by the
addition of 10 per cent by volume of lime cream containing
0.5 per cent sodium bisulphite and having a density of 36°
Brix. These samples were thoroughly mixed to insure uniform
distribution of alkalinity, and were preserved in clean bottles.
The composition after varying intervals of time is recorded
under the heading ‘“‘bottled juice.”
Juice was also collected from the same palms in tuquils coated
with lime cream containing sulphite as above. The contents
of these tuquils were poured into bottles at the time of collec-
tion, and analyzed after varying intervals. The data so obtained
are recorded under the heading ‘“‘tuquil juice.” The sap collected
in tuquils from the first 3 sets especially showed acidity in the
upper layers. A lime cream of 46° Brix was used in the remain-
ing 7 sets, as this consistency adheres better to the sides of the
vessels and lessens stratification.
The samples of juice collected in bottles and subsequently
treated with lime and sulphite clearly show that once the juice
is uniformly mixed with this preservative no further deteriora-
tion of importance will take place. The use of sulphite in the
lime cream has the further advantage of adding nothing to the
cost of manufacture. The sulphite may be added to the lime
at the mill by making the lime cream of proper consistency and
running into it the requisite amount of sulphur dioxide. This
will obviate the necessity of bleaching when the juice is worked
up. The amount of sulphur dioxide best suited to the purpose
will have to be determined by experiment in actual practice.
THE MODIFIED BAMBOO TUQUIL
We have carried out a series of experiments using a modifica-
tion of the bamboo tuquil for gathering nipa juice that gives an
even distribution of alkalinity throughout the entire collection.
The lime and sulphite cream was placed in the bottom of tuquils,
no care being necessary to have a layer clinging to the sides.
The juice was then allowed to drop into small funnel tubes
reaching to the bottom of the tuquils and terminating in bevel
ends to allow free exit of the juice. This resulted in carrying
the entire collection of sap to the bottom of the tuquils, where it
immediately became alkaline, and future change was perma-
nently prevented. There is no possibility when funnels are used
for the formation of dense layers of juice containing a large
VIII, A, 6 Pratt et al.: Nipa Palm 393
excess of lime which prevent fresh juice from reaching the
preserving cream. A uniform circulation is accomplished in a
simple manner, and the beneficial results are evident.
A further confirmatory test of the lime and sulphite pregerva-
tive using funnels was made by a competent independent in-
vestigator on March 10, 1913. The palms for this test were
in Bulacan Province, had very short flower stalks, and had prac-
tically ceased to flow. The juice gave a strong positive test for
peroxidase, and could not be preserved with lime alone. Very
few palms were flowing any juice at this time, and the long dis-
tances between available trees made it impractical to study more
than those recorded in Table XIII. The figures refer to the juice
carbonated in Manila two days after collection.
TABLE XIII—Analyses of tuba collected in Bulacan.
] 3
Volume
Volume fs D
No. of of of lime | Polariza- Brix. Shnowate. | evel,
sample. | ._- cream tion.
; see used.
ce. cc. vac Per cent.
1) 150 80 54.8 15.5 13.4 86.5
2 185 40 64.0 18.7 15.5 82.9
8 240 40 44.0 13.4 13.4 81.3
4
230 40 48.0 16.3 11.7 70.5
5 250 40 49.0 19.6 11.8 60.3
Samples 4 and 5 contained no sulphite when tested before car-
bonation. No attempt had been made to clean the tuquils used
in collecting this juice, and it is probable that the greater part of
the sulphite was destroyed by the accumulation of organic slime.
The above results are of great interest as showing what may
be accomplished under the most adverse conditions.
Various other experiments show that all tuquils in which fun-
nels had been used with lime and sulphite cream gave juice alka-
line throughout, with a purity about 5 units higher than corre-
sponding collections from the same palms following the old
method. Moreover, all tuquils in which funnels were not used
contained top layers of acid juice with twenty-hour collections.
The use of the funnel method would involve no great difficulty
when applied to the collection of nipa juice on a commercial
scale, and has much to recommend it. The bowls for the funnels
could be turned out of wood at slight expense, and the stems
made from branches of spineless bamboo. The amount of lime
actually necessary for preserving tuba is very small, probably
not exceeding 1 per cent. A large excess is absolutely neces-
sary when the ordinary tuquil is used, although the greater part
128668——2
394 The Philippine Journal of Science 1913
must remain undissolved and be wasted. Moreover, the cream
must be thick enough to adhere to the sides of the tuquil, and
such a cream is difficult to handle in the swamp. Native work-
men are prone to be careless, and unless supervised might slight
the application of lime or use excessive amounts.
The tubero could measure a thin lime cream by means of a long-
handled bamboo cup, and pour it into the tuquils when funnels
were employed. No time would: be lost in attempting to coat
the interior, as the reason for this precaution would no longer
exist. The time necessary for adjusting funnels to catch the
dripping juice would not be greater than that spent in apply-
ing lime for the old method. A marked decrease in operating
expense would result, due to the reduction in the amount of lime
used, the great saving of carbon dioxide when the juice is car-
bonated at the mill, and the small consequent burden on the filter
presses. This takes no account of the certainty of obtaining
high purity juice under all conditions and the complete absence
in this juice of the very objectionable calcium acetate resulting
whenever acid fermentation takes place. The presence of neu-
tral lime salts in solution after carbonation necessitates treat-
ment with soda ash for their removal, and is coincident with
decreased purity. The amount of these salts affords a valuable
index of the efficiency of preservation. Reference to Table XII
shows that a properly preserved juice need not contain more
than about 0.03 gram of CaO per 100 Brix, a negligible amount.
TRANSPORTATION OF SAP
The character of nipa swamps is such that all transportation
must be carried on by water. The native tuberos use bancas
(canoes hewn out of a single large log), and penetrate all parts
of the swamps in these light-draught boats. In some places it
has been necessary to construct artificial waterways, but a nat-
ural network of small tide-water streams greatly reduces this
expense. The sap at present collected for the alcohol industry is
carried from the palm to the distillery in large earthen jars called
tinajas, or is occasionally emptied directly into the bancas.
Neither method recommends itself when the sap is destined for
a sugar mill. The ordinary 5-gallon kerosene tins are much
lighter and easier to carry from palm to palm than the tinajas,
and will probably be the most satisfactory means for the pur-
pose. One tubero can readily carry 2 of these cans, represent-
ing the collection of juice from 30 or more tuquils. The filled
cans may then be placed in bancas and carried to the mill.
VIII, A, 6 Pratt et al.: Nipa Palm 395
THE MILL
Nipa juice, properly preserved with lime and sulphite, offers
no difficulties in the mill. A tank should be provided at the
water’s edge into which the tubero may pour his cargo of juice
for analysis and credit.
The subsequent treatment need differ in no respect from cus-
tomary sugar practice. The juice breaks readily when carbon-
ated to the proper alkalinity and heated to 100°. The sediment
settles promptly, leaving a bright juice requiring no further
treatment. The filter cake from the sediment is firm, and may
be reduced by washing and steaming to a total sucrose content
not exceeding 0.2 per cent.
COST OF NIPA JUICE
The price paid by the distilleries for collecting nipa juice in
the ordinary manner is about 8 centavos (4 cents United States
currency) per tinaja containing from 30 to 36 liters according
to locality. This represents about one-half the total cost of pro-
duction. Swamps are also frequently worked on equal shares.
The nipa-land owners, therefore, expect a return of about 2.50
pesos per 1,000 liters of sap produced. This forms a profitable
basis for the manufacture of alcohol and consequently for sugar.
The extra labor incident to liming the tuquils will increase
the cost of collecting juice to a slight extent. Where labor may
be obtained for 1 peso (50 cents United States currency) per day,
we estimate the cost of collection at 30 centavos per 100 liters.
EXTRACTION OF SUGAR
White sugar can be made from nipa juice at a manufacturing
cost far less than that of either cane or beet sugar. During mill
experiments with large quantities of low-grade juice, we have
extracted sugar until the final molasses had an apparent purity
of only 50. Since this extraction is at least 10 per cent greater
than the beet-sugar practice, it represents a further source of
profit. Table XIV shows the percentage of available granulated
sugar on total solids for purities of from 80 to 90. These figures
_ are very conservative, and no doubt could be exceeded in a well-
controlled mill.
396 The Philippine Journal of Science 1913
TABLE XIV.—Available granulated sugar in nipa juice.
Avail- | Avail-
Purity. able Purity. able
sugar. sugar.
Per cent. Per cent.
80 | 60 86 72
81 62 87 14
82 64 88 16
83 66 89 78
84 68 | 90 80
85 70 |
For example, 1,000 liters of juice with a purity of 83.1, Brix
of 16.8, and sucrose content of 14 per cent would amount to
1,069 kilograms of juice with 179.6 kilograms of dry substance.
From the above table of extraction, 66 per cent, or 118.5 kilo-
grams, of granulated sugar could be obtained from this juice
without making any allowance for loss. This represents an ex-
traction of 11.1 per cent. The filter press and unknown loss
should not exceed 0.5 per cent, leaving 10.6 per cent, or 113
kilograms of sugar per 1,000 liters of juice.
SUMMARY
Yield of nipa sap.—Nipa palms produce about 40 liters of sap
per tree during an average season. A conservative estimate of
producing palms may be placed at 750 per hectare, yielding
30,000 liters of juice. The nipa district in the Provinces of
Bulacan and Pampanga alone is estimated to contain 18,000
hectares, and many other large areas in various islands are
available for sugar manufacture.
Season of flow.—The average season during which sap is avail-
able in sufficient quantities to supply a sugar mill covers
approximately six months. The daily collections reach a
maximum during the second month, and gradually diminish
after the third or fourth month.
Quality of sap.—The average nipa sap as it flows from the
palm during the season contains about 15 per cent sucrose, and
has an apparent purity of not less than 85. Invert sugar is
present only in traces. About 0.5 per cent of sodium chloride
slightly reduces the purity without lowering the extraction of
sugar, as it is classed among the nonmelassigenic salts. Waxes,
acids, pectins, and other foreign material are practically absent.
The sap contains active enzymes of the invertase and peroxidase
types, the latter being present only during the final period of
VIII, A, 6 Pratt et al.: Nipa Palm 397
secretion. This peroxidase is capable of oxidizing sucrose and
invert sugar in either neutral or alkaline solution.
Collection and preservation of sap.—Nipa sap may be collected
without appreciable deterioration in bamboo joints or tuquils
containing lime cream and sulphite. The latter may be added
to the lime at the mill by passing the requisite amount of sulphur
dioxide into a lime cream of proper consistency. The presence of
this additional preservative in the lime cream will destroy the en-
zymes present and prevent deterioration of the sap. It also
avoids the necessity of further bleaching. The use of small fun-
nels for conveying the inflowing juice to the bottom of the tuquils
avoids stratification and results in more perfect preservation.
The additional expense attendant upon their use is slight, and
more than counterbalanced by the resulting advantages.
Cost of collection—Nipa sap can be collected and delivered to
a mill on a commercial scale with negligible loss of sucrose and
decrease in purity for approximately 3 pesos (1.50 dollars United
States currency) per 1,000 liters.
Extraction of sugar.—Approximately 115 kilograms of com-
mercial white sugar polarizing at from 99° to 99°.5 can be re-
covered from 1,000 liters of sap possessing average composition.
No important modification of methods now used in sugar practice
will be necessary. Furthermore, no expense corresponding to
the grinding of cane or the extraction of beets need be included
in the cost of manufacture. The lack of fuel caused by absence
of bagasse may be largely overcome by utilizing the cheap and
plentiful wood of mangrove swamps.
Cost of manufacture.—Manufacturing sugar from nipa sap
will be less expensive than from cane or sugar beet. It is be-
lieved that data presented in this paper will form a sufficient
basis for calculating costs and profits.
Area of swamp necessary for a 10-ton mill About 9,000 liters
of nipa sap will be required to produce 1 metric ton of 96° sugar;
therefore, a 10-ton mill running at full capacity will necessitate
90,000 liters of sap daily. One hectare of nipa swamp yielding
30,000 liters of juice per season should produce from 200 to 250
liters per day during the months of maximum flow. Therefore,
about 450 hectares of good producing swamp would supply such’
a mill operating at full capacity during the height of the season.
Many distilleries at the present time are receiving a larger vol-
* The former estimate (Gibbs, loc. cit., 142) was based upon 2,000 plants
per hectare; that is, on the assumption that all plants fruit each year,
which is not the case.
898 The Philippine Journal of Science 1913
ume of juice per day than is required in this estimate. Some of
the factors concerning the yield of sap per hectare and the cost
of production cannot be accurately determined, but we have in-
vestigated this phase of the problem as thoroughly as possible,
and have allowed ample margins of safety in every case. A mill
designed to manufacture sugar from nipa juice will also be avail-
able during that portion of the year when no sap is flowing for
refining Philippine sugars in which there is a reasonable profit.
Every indication is for the establishment of a successful in-
dustry, and the unfavorable criticism of H. C. Prinsen Geerligs®
seems unwarranted.
The Bureau of Science will gladly furnish samples of nipa
sugar to any one interested.
Notre.—A further study of the various enzymes present in the nipa palm
is in progress to determine, if possible, the exact nature and action of the
one responsible for the destruction of sugar.
* Rep. Eighth Int. Cong. Applied Chem. (1912), 27, 60.
ee
eS es
=~ —-. —™.
i Ee ta a
ee ee ee ee ee eee
-
;
;
|
THE ABSORPTION SPECTRA OF VARIOUS PHTHALIDES AND
RELATED COMPOUNDS
By Davip S. PRATT
(From the Laboratory of Organic Chemistry, Bureau of Science,
Manila, P. I.)
Fifteen text figures
Phthalic acid is the parent substance from which a large num-
ber of condensation products are obtained that have long oc-
cupied a prominent position in chemical discussions. The
marked change of color exhibited by the phthaleins upon salt
formation has given these compounds a prominent position
in all theories regarding constitution and color. The rapid pro-
gress in spectroscopic investigation and the ever increasing vol-
ume of data available concerning the relation between molecular
structure and optical activity has resulted in broadening our
conceptions of color changes and modifying our ideas of the
underlying causes. Before the absorption spectra of complex
substances such as the phthaleins can be rationally interpreted,
it is essential to have considerable data relative to similarly con-
stituted compounds possessing simple structures not subject to
molecular rearrangement in the quinoid-benzenoid sense. Many
of the phthalids are suitable for the purpose, and therefore form
the basis of this investigation. Since many simple phthalids
of definite, fixed structure dissolve in concentrated sulphuric
acid with the production of color, this solvent was included for
comparison with absolute alcohol.
DESCRIPTION OF THE ABSORPTION SPECTRA
PHTHALIC ACID
COOH
CoH on
Phthalic acid in ordinary solvents has been studied by many
observers and its absorption spectrum been found to show a
band heading at + 3700. The solution in sulphuric acid
exhibits a very different spectrum. Here two well-marked bands
make their appearance (fig. 1).
That nearer the red heads at 4 = 3300, and the second in
the benzene region shows at : = 3800. Both bands exhibit
399
400 The Philippine Journal of Science 1918
more persistence than that given by the alcohol solution, and
appear at lower concentration. Both solutions show a purple
Oscillation frequency.
38000 32 34 36 38 4000 42 44
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
ces
Te
Fic. 1. Curve 1. Phthalic acid in alcohol. Curve 2. Phthalic acid in sulphuric acid.
fluorescence under the iron-nickel arc, that noticed with alcohol
being rather faint compared to the decided color emitted by
the sulphuric acid solution.
ae eee ee SS | ee UC Oe
VIII, A, 6 Pratt: Phthalides and Related Compounds 401
PHTHALIC ANHYDRIDE
C=0
CoH »o
c&o
The absorption spectrum of phthalic anhydride was studied
in glacial acetic acid solution to avoid any possibility of dis-
rupting the lactone ring. It shows a small band heading at
= 3440, very similar in outline and persistence to that given
by phthalic acid, but less refrangible (fig. 2). This solution is
not fluorescent to a noticeable degree.
The anhydride in sulphuric acid fluoresces purple under the
are, and gives an absorption spectrum identical with that of
phthalic acid in the same solvent.
MALEIC ANHYDRIDE
HC —-0=0
i »o
HC—C=0O Q
The anhydride was prepared from malic acid according to
directions given by van der Riet': and recrystallized from ether
and from chloroform until pure. The solution in glacial acetic
acid shows a band of very slight persistence heading at about
1 _ 3400 (fig. 8).
Xr
The solution in sulphuric acid shows even less selective ab-
sorption, with a step-off at about s — 3500 to 3900.
PHTHALIDE
Phthalide was made both by reducing phthalyl chloride? and
from phthalimide.? Both products were purified by repeated
boiling with bone black and recrystallization from water. This
was necessary to remove traces of resinous impurities that give
*Ann. d. Chem. (Liebig) (1894), 280, 216.
? Ber. d. deutsch. chem. Ges. (1877), 10, pt. 2, 1445.
* Graebe, Ann. d. Chem. (Liebig) (1888), 247, 291.
402 The Philippine Journal of Science 1918
color with alkali. The absorption spectrum of pure phthalide
in alcohol shows a well-marked band heading at = 3680. The
Oscillation frequency.
2000 32 34 36). 38 4000 42 44
Akay an
Vt ANIA
CEERI
si lca
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 2. Curve i. Phthalic anhydride in glacial acetic acid. Curve 2. Phthalic
anhydride in sulphuric acid.
spectrum is not altered by the addition of one equivalent of
sodium ethoxide. The solution in sulphuric acid shows faint
—
vuLa,é Pratt: Phthalides and Related Compounds 4038
Oscillation frequency.
3000 32 I4 36 38 4000
ea
ae oo
oe
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 8. Curve i. Maleic anhydride in glacial acetic acid. Curve 2. Maleic anhydride
in sulphuric acid.
404 The Philippine Journal of Science 198
purple fluorescence, with two bands, one heading at . = 3400
and a more persistent band at : = 4000 (fig. 4).
The two preparations of phthalide showed no differences, and
were evidently identical.
Oscillation frequency.
32 3Ft 36 38 4000 42 44
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 4. Curve 1. Phthalide in alcohol. Curve 2. Phthalide in sulphuric acid.
PHTHALIMIDE
Phthalimide in alcohol shows a well-marked absorption band
heading at = 3460 and incipient benzene bands (fig. 5).
SS Oe
q vir,a,6 Pratt: Phthalides and Related Compounds 405
The addition of alkali causes a broadening of the band and a
reduction in persistence, until, in the presence of 5 equivalents
Oscillation frequency.
28 3000 32 38 4000
is
aa ana
ee
3.8
: 3.6
34
3.2
ro
PRE
ee |
MAO <a
adene
ai
3.0
28
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 5. Curve 1. Phthalimide in alcohol. Curve 2. Phthalimide in sulphuric acid.
Curve 8. Phthalimide in alcohol + 5 equivalents of sodium ethoxide.
of sodium ethoxide, the general absorption closely approaches
the visible region of the spectrum. The band is broad and
shallow, but shows no change in the position of its head.
406 The Philippine Journal of Science 1913
The sulphuric acid solution fluoresces green, and also gives a
single band that heads nearer the red at : = 3120, and shows
remarkable persistence.
PHTHALIMIDENE
C=H2
CH NH
C=O
Phthalimidene was prepared from phthalimide‘ and purified
similarly to the preceding compound. The alcohol solution gives
two absorption bands, a very narrow one heading at q = 3600
and a broader one slightly more refrangible at .= 3720. The
spectrum is not altered by the addition of one equivalent of so-
dium ethoxide (fig. 6).
The sulphuric acid solution also gives two bands, a shallow one
at = 3520 and a well-marked one at i= 4040.
NITROSOPHTHALIMIDENE
C=H,
CoH NNO
C=O
Nitrosophthalimidene, prepared from phthalimide by the ac-
tion of nitrous acid,* was obtained in long yellow needles after
recrystallization from dilute alcohol. The absorption spectrum
in alcohol is complicated and contains three bands. The color
band heading at + = 2320 is very well marked and of consider-
able persistence. A shallow band shows at 2 = 2940, and the
third heads at + = 3820 (fig. 7).
The addition of one equivalent of sodium ethoxide produces a
decided change in color, and shifts the bands to = 2160, 2940,
and 3480. The intermediate band now appears at much greater
dilution, and is more persistent.
“Graebe, loc. cit.
VIII, A, 6 Pratt: Phthalides and Related Compounds 407
Oscillation frequency.
Be eer 265 8 £000 22 et
aa oh |
Soee.t\! /\)
> Sa
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 6. Curve 1. Phthalimidene in alcohol. Curve 2. Phthalimidene in
sulphuric acid.
408 The Philippine Journal of Science 1913
Oscillation frequency.
2090 22 rr 26 28 3000 32 34 36 38 $000 42
Logarithms of relative thickness in millimeters of 1/10,000 molar solution,
hy
&
Fic. 7. Curve i. Nitrosophthalimidene in alcohol. Curve 2. Nitrosophthalimidene
in alcohol + 1 equivalent of sodium ethoxide.
BENZYLIDENE PHTHALIDE
C=CH:C,;H;s
CHC De
C=O
Benzylidene phthalide was prepared from phthalic anhydride
and phenylacetic acid® and recrystallized from alcohol. The al-
cohol solution shows a faint blue fluorescence with the arc, and
gives two absorption bands heading at = 2960 and 3430 that
are separated by a very shallow transmitted portion (fig. 8).
* Ber. d. deutsch. chem. Ges. (1885), 18, pt. 2, 3470.
yi vuna,eé Pratt: Phthalides and Related Compounds 409
The solution in sulphuric acid is yellow, and possesses a beauti-
ful steel blue fluorescence, remarkably vivid under the influence
of the arc. Two well-marked bands at 2 = 2700 and 3660 were
observed in the absorption spectrum. ;
Oscillation frequency.
24 26 28 3000 32 34 36 38 4600 42
' Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 8. Curve 1. Benzylidene phthalide in alcohol. Curve 2. Benzylidene phthalide
in sulphuric acid.
CYANBENZYLIDENE PHTHALIDE
C=C(CN)CeH;s
Ce a yo
C=O
Cyanbenzylidene phthalide, prepared from benzyl cyanide and
phthalic anhydride,* was recrystallized from alcohol, glacial acetic
acid, and methyl alcohol after repeated boiling with bone black.
The very faintly colored yellow needles dissolve without apprecia-
* Ibid. (1885), 18, pt. 1, 1264.
123668——3 :
410 The Philippine Journal of Science 1918
ble color in alcohol. This solution shows a peculiar absorption
spectrum containing a small band heading at : = 2960 and two
step-offs (fig. 9).
The sulphuric acid solution is canary yellow to orange, and
shows a greenish fluorescence with the arc. It gives a well-
marked band at : = 2800 and a small band at = = 3820.
Oscillation frequency.
24 26 28 3000 32 34 I6 38 4000 42
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 9. Curve 1. Cyanbenzylidene phthalide in alcohol. Curve 2. Cyanbenzylidene
phthalide in sulphuric acid.
PHTHALYLACETIC ACID
Vinge
CeH O
6 NG A
C=O
Phthalylacetic acid, made from phthalic anhydride and acetic
anhydride,’ was repeatedly recrystallized from glacial acetic acid
"[bid. (1893), 26, pt. 1, 952.
VIII, A, 6 Pratt: Phthalides and Related Compounds All
after boiling with bone black until finally obtained as colorless
_plates. It melted at from 260° to 265° uncorrected, thus cor-
responding with the determination of Roser.’ The solution in
Oscillation frequency.
28 3000 32 34 36 38 4000 42
an
melee
Ree ehh
es ae
Sea
Been
Bee
BAL |
BISNIS
fee | |
Fic. 10. Curve i. Phthalylacetic acid in glacial acetic acid. Curve 2. Phthalylacetic
acid in sulphuric acid.
2.8
2.6
2.4
ee
2.0
48
6
1.4
Logarithms.of relative thickness in millimeters of 1/10,000 molar solution.
72
glacial acetic acid is colorless, and shows two bands heading at
1 = 3200 and 3660 (fig. 10).
The sulphuric acid solution is light yellow, with faint purple
fluorescence under the arc, and is characterized by a well-marked
band at Ol eat twa amall hands’ at = — 3750 and 4080.
* Ibid. (1884), 17, pt. 2, 2619.
412 The Philippine Journal of Science 1913
DIPHTHALYL
C=O
and So
hte
i
cat 0
C=6
Oscillation frequency.
2426 28 3000 32 34 36 38 4000 42 44
o
S
Ss
>=
S
n
8
E 20
: ee
PE 18 =
be = ST, OP oe
zs = 16
ae
an ee”: CP too hd Mae
2
% 12
2 10
g/L SPP | la
4
Fic. 11. Curve 1. Diphthalyl in glacial acetic acid. Curve 2. Diphthalyl in sulphuric
acid.
Diphthalyl was made by reducing phthalic anhydride in
glacial acetic acid solution with zine dust.° It-was recrystal-
lized from glacial acetic acid after boiling with bone black until
colorless. The glacial acetic acid solution is colorless, and shows
a band at += 2880 accompanied by a shallow band at about
1 _ 3900 (fig. 11).
x
The sulphuric acid solution is light yellow with bluish
*Tbid. (1884), 17, pt. 2, 2178.
VIII, A, 6 Pratt: Phthalides and Related Compounds ' 413
green fluorescence under the arc, and shows a strong band at
= 2700. Two smaller bands show in the benzene region at
= 3840 and 4170.
| > |e
PHTHALANIL
C=O
CoC os CeHs
Oscillation frequency. a
26 3000 8? 6.34) > 36. «38
So ae
Bee
Beek
See
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
Fic. 12. Curve 1. Phthalanil in alcohol. Curve 2. Phthalanil in sulphuric acid.
Phthalanil was prepared from aniline and phthalic anhydride
by distillation’? and recrystallized from alcohol and from glacial
acetic acid until pure. The colorless alcohol solution gives a
single band at : = 3440 (fig. 12).
The canary yellow sulphuric acid solution also causes a single
band that is nearer the red at 4 = 3120.
* Laurent und Gerhardt, Jahresber. d. Chem. (1847-48) , 605.
414 The Philippine Journal of Science 1913
PHTHALOPHENONE
C=(CeHs)2
CoH yo
C—O
Phthalophenone, from phthalyl chloride and benzene, was
purified .by repeated crystallization from alcohol. The colorless
alcohol solution shows a well-marked band at +3600 (fig. 18).
The solution in sulphuric acid is orange with a very strong
Oscillation frequency.
2000 22 24 26 28 __ 3000 ___32 34 36 38 4000 _42
Fanngee
PCO
J aa
ee |
Logarithms of relative thickness in millimeters of 1/10,000 molar
solution,
Fic. 13. Curve 1. Phthalophenone in alcohol. Curve 2. Phthalophenone in sulphuric
acid.
color band heading at} =2220, a shallow band at about =3320,
and a third in the benzene region at > —3920.
PHTHALOPHENONE ANILIDE
C=(CeHs)2
CoH SN: CsHs
Cc=0
Phthalophenone anilide was prepared from phthalophenone
VIIL, A, 6 The Philippine Journal of Science 415
and aniline.** It was recrystallized from alcohol and glacial
acetic acid until colorless, and melted at 188° uncorrected. The
1 _3800 (fig. 14).
colorless alcohol solution shows a small band at =
Oscillation frequency.
22 24 26 28 3000 32 34 36 38 4000 42
eA ee
ee eee
ALA Eo
Bees
pe bars
pt
pare
pees
Pees.
es
Eee
silts
Logarithms of relative thickness in millimeters of 1/10,000 molar solution.
nN
Fic. 14. Curve 1. Phthalophenone anilide in alcohol. Curve 2. Phthalophenone
anilide in sulphurie acid.
The sulphuric acid solution is yellow, with faint greenish blue
fluorescence under the are. A strong color band at t 2220 and
a small band at * 3800 characterize the spectrum.
™ Fischer und Hepp, Ber. d. deutsch. chem. Ges. (1894), 27, pt. 3, 2793.
-
416 The Philippine Journal of Science 1918
PHTHALOXIME
C=NOH
Yellow phthaloxime ” was prepared from phthalic anhydride
and hydroxylamine. It has been shown to give an absorption
Oscillation frequency.
26 28 SOOT TS 34 36
hye
3.0
2.6
2.6
Logarithms of relative thickness in millimeters of 1/10,000 molar solution,
Fic. 15. Curve i. Yellow phthaloxime in alcohol. Curve 2. Yellow phthaloxime in
sulphuric acid.
spectrum in alcohol solution containing a band att =3400 and a
small band at 13740."
The sulphuric acid solution is faintly yellow, and shows a
well-marked band att =3200 and a small band at + —3740 (fig.
LES
2 Orndorff and Pratt, Am. Chem. Journ. (1912), 47, 89.
** Pratt and Gibbs, This Journal, Sec. A (1913), 8, 165.
VIII, A, 6 Pratt: Phthalides and Related Compounds ALT
DISCUSSION OF RESULTS
The substitution of two saturated groups in the ortho position
has been shown “ to modify the absorption spectrum of benzene
by causing several of the narrow bands to coalesce into a well-
marked band of considerable persistence. When one or both of
the substituting groups contain unsaturated centers possessing
residual affinity, the position of the resulting band is modified.
Thus ortho xylene shows a broad band heading at =—3700, while
ortho chloraniline gives a similar band at 4 —3450.
Phthalic acid must be considered as containing two ortho
groups possessing little residual affinity. The position of the
absorption band corresponds to that of ortho xylene, but the
persistence and type are decidedly different. The band cannot,
therefore, be attributed to the disubstituted benzene ring alone,
but results from the mutual influence of the two carboxyl groups
and the ring. The activity of carboxyl is undoubtedly inherent
in the doubly bound oxygen with its latent valencies, but the
resulting effect is much less than that produced by a true carbonyl
grouping. The hydroxyl exerts a counterinfluence that has
been demonstrated in many instances and accounted for in a
variety of ways. Smedley’® and others suggest that the carboxyl
group may represent a canceling of residual affinities between
=CO and —OH, which may be indicated by a structure such
—C=O .
as ee Although this graphic representation serves to
account for some of the facts in a more or less satisfactory man-
ner, it has not as yet received sufficient confirmation for general
acceptance. The extra double bond between the oxygen atoms
introduces a condition not possible in phthalic anhydride, but
the absorption spectrum of this compound indicates no such
radical difference in structure. Some such internal compensa-
tion is probably taking place, but thus far an insufficient variety
of groups causing an analogous result has been studied to permit
any definite conclusions being drawn. o0-cyanbenzoic, o-chlor-
benzoic,” and o-sulphobenzoic * acids give absorption spectra
of the same type as phthalic acid.
*“ Baly and Ewbank, Journ. Chem. Soc. London (1905), 87, 1355.
* Baly and Ewbank, loc. cit.
*® Journ. Chem. Soc. London (1909), 95, 281.
* Scheiber, Ber. d. deutsch. chem. Ges. (1912), 45, 2403.
* Scheiber und Knothe, Jbid. (1912), 45, 2252.
418 The Philippine Journal of Science 1913
It was at first thought that an equilibrium might exist between
the partial valencies of the two doubly bound carbonyl groups
of phthalic acid and that the resulting influence of this conju-
gation on the benzene ring, although modified and lessened by
hydroxyl, might still be of sufficient magnitude to result in a
characteristic band. In this event, the elimination of hydroxyl
upon anhydride formation should increase the activity of the
carbonyl groups and cause phthalic anhydride to produce a band
emphasizing this condition. Reference to figs. 1 and 2 shows
that the result of removing hydroxy] is to shift the band toward
the longer wave lengths without altering the persistence and
general type. It is not reasonable to suppose that the equi-
librium of the carboxyl] groups is the same as that of the lactone
ring when these compounds are dissolved in solvents such as
alcohol or acetic acid. The fact that the absorption spectra
show such great similarity indicates a closer relationship between
the benzene ring and the band than between the side chain and
the band.
In all of these compounds there exists conjugation between
the benzene ring and the substituting groups, and this condition
is primarily responsible in every case for the characteristic
modification of the benzene spectrum.
This type of conjugation existing between a side chain and
a benzene ring was briefly discussed by Thiele ° in his original
paper on partial valency, and his structural formula for phthalic
acid appears to be in accord with the absorption spectrum of
this compound. However, the peculiar equilibrium of valencies
depends upon two doubly bound oxygen atoms in the carboxyl
groups, as indicated in the formula:
OH
WK
(allema ate
NO
oH
This represents the benzene ring modified by the action of
two partial valencies acting with side-chain influences. A similar
effect could be ascribed to the lactone ring in phthalic anhydride,
and the absorption spectra of these and analogous compounds
thus explained. When one double bond is destroyed by substi-
tuting two atoms or groups for a carbonyl oxygen, the equilibrium
of the resulting molecule could no longer be similarly repre-
*% Ann. d. Chem. (Liebig) (1899), 306, 130.
Et Oa. me |
———
via,s Pratt: Phthalides and Related Compounds 419
sented. Nevertheless, phthalide gives an absorption spectrum
closely resembling that of phthalic acid. This serves to em-
phasize the fact that absorption spectra are caused by types of
force equilibria, each giving characteristic manifestations, but
which are often incapable of rational expression by the struc-
tural formulas employed at present. Phthalids belong to the
same type as phthalic acid and its anhydride, and the change
from acid to anhydride involves no fundamental alteration in
the arrangement of forces within the molecule. This lends
support to the equilibrium between phenolphthalein as a lactone
and its acid as advanced by Kober and Marshall.?°
Maleic anhydride possesses a structure corresponding to the
side ring of phthalic anhydride during that benzene phase when
the double bond occurs between the corresponding carbon atoms.
OT a HC—C7
acer | No
heritage ae 4
Wants HC—Cy
Phthalic anhydride. Maleic anhydride.
Maleic anhydride, however, shows very little selective absorp-
tion, and gives no well-defined band, but rather a rapid extension
of transmitted light occurring at high concentration. The effect
of introducing this group into the benzene ring corresponds very
well with what might be expected. The equilibrium within a
compound of two well-defined tendencies, one capable of pro-
ducing a step-off at about + =3400, the other giving well-marked
banded absorption between + = 3724 and ‘ = 4200, might well
result in selective absorption as shown by phthalic anhydride.
The character of the resulting absorption would represent an
equilibrium between the ortho disubstituted benzenes with
saturated groups as in o-xylene and the anhydride influence
shown in maleic anhydride.
The band is shifted toward the red by the latter influence,
and phthalic anhydride, therefore, gives a less refrangible band
than o-xylene. The effect is less marked in phthalic acid be-
cause the influence of the side chain is reduced by hydroxyl
groups that cancel a large part of its residual affinity and leave
the band nearer the normal benzene region. The opposite effect
» Rep. Eighth Int. Cong. Applied Chem. (1912), 6, 157.
420 The Philippine Journal of Science 1918
is to be noted when the activity of the lactone ring is increased
by the introduction of unsaturated centers. Reference to the
curves obtained with substituted phthalids of this class clearly
shows that in every case an absorption band was found less
refrangible than that given by phthalic acid.
One of the carbonyl groups of phthalic anhydride may be re-
placed by two atoms of hydrogen giving phthalide. This re-
moves one of the double bonds, and would entirely destroy the
absorption band if it were due solely to conjugation between
the two carbonyl groups. This is not the case, as phthalide
shows well-marked selective absorption (fig. 4), and, moreover,
the band retains its characteristic type. It heads between that
of phthalic acid and its anhydride, thus showing greater activity
than the former and less than the latter. The effect of destroying
one of the double bonds joined to the lactone ring does not
appear ever to result in eliminating the absorption band, but
merely modifies its position or persistence. If conjugation be-
tween latent valencies is taking place, it must be between the
anhydride oxygen and the remaining carbonyl group. This is
rendered improbable by the great similarity between the spectra
of phthalic acid and its anhydride. Moreover, other acids con-
stituted similarly to phthalic acid, such as phthalylhydroxamic
and anilidophthalamic acids in which no anhydride oxygen is
present, have been shown to cause a similar absorption band.”
The manner in which these latent valencies of a carbonyl
group are called into play by near-by atoms or radicals deter-
mines the position of the resulting band, its persistence, and the
concentration at which it appears. In the case of phthalic an-
hydride the two carbonyl groups are in the £6 position, and
conjugation of the a diketone type represented by:
‘C=O: c—@
| or [toes
‘C=O: ‘C=O
does not appear to be the deciding factor. A very marked
difference between the absorption spectra of camphorquinone and
methylene camphor ”? shows the effect of disturbing such a con-
dition, although the double bond is not removed. The substi-
tution of methylene with little residual affinity for the active
oxygen atom greatly reduces the activity of the entire molecule.
The substitution of two hydrogen atoms for the oxygen of
= Pratt and Gibbs, This Journal, Sec. A (1913), 8, 165.
* Lowry and Southgate, Journ. Chem. Soc. London (1910), 97, 915.
VIII, A, 6 Pratt: Phthalides and Related Compounds 4?1
phthalic anhydride giving phthalide effects no analogous change,
but merely lessens the activity to a slight degree. The opinion
seems justified that some interaction does take place between
the two carbonyl groups of the lactone ring, but that it is
subordinate to other influences which may be attributed to
internal activity of the carbonyl group.
The solutions in concentrated sulphuric acid present very
marked contrasts to those where alcohol or glacial acetic acid
is employed as solvent. In many cases an entirely new band
makes its appearance, and the existing spectrum is further al-
tered by a shift of the original band. Alcohol possesses a low
degree of residual affinity, while sulphuric acid shows this prop-
erty in a marked degree. The effect of the latter solvent is to in-
crease the energy of the solute, thus causing the absorption band
to shift toward the longer wave lengths. The only exception
noted was with maleic anhydride, in which case the sulphuric
acid solution showed less-marked selective absorption than the
acetic acid. Here the increased activity was manifested by the
band appearing at much lower concentration than in glacial
acetic acid solution.
The spectra of phthalic acid and anhydride in sulphuric acid
are especially interesting. Both substances give the same curve
with two well-marked bands. It was thought possible that the
small amount of acid used might be dehydrated and consequently
be entirely converted into phthalic anhydride. This is not the
case, aS was clearly shown by adding a hundredth molar sul-
phuric acid solution drop by drop to ice-cold absolute alcohol,
thus giving a thousandth molar concentration. This solution
was photographed at once, and the resulting curve coincided with
phthalic acid and not with the anhydride. If the latter com-
pound had resulted from dehydration by the concentrated sul-
phuric acid, it would not have been hydrolyzed by cold alcohol
and its presence could have been detected on the photographic
plate. The cancelling effect of hydroxyl in phthalic acid has
been prevented by the high residual affinity of the solvent.
It is also significant that in sulphuric acid solutions a band
frequently makes its appearance in the benzene region. In the
case of phthalic anhydride the original band is shifted from
2 = 8440 to 3300 and a benzene band at ; = 3800 is produced.
The two opposing influences previously merged and resulting in
a single band representative of the equilibrium thus produced
have now been resolved by increasing the energy of the lactone
4922 The Philippine Journal of Science 1913
ring until the period between them has reached a point where
separation takes place. The band due to a disubstituted benzene
ring appears in its characteristic position, while the original
absorption shifts in the opposite direction toward the red. The
results of this new condition within the molecule are frequently
evident to the eye either by the production of color or through
fluorescence.
A similar effect may be produced by increasing the residual
affinity of the side chain through the actual substitution of
active groups. ‘Thus benzylidene phthalide (fig. 8), cyanbenzyl-
idene phthalide (fig. 9), phthalylacetic acid (fig. 10), and di-
phthalyl (fig. 11) all contain such unsaturated centers, and give
absorption spectra characterized by two bands even in alcohol
solution. The action of sulphuric acid on these compounds is
less marked, but entirely analogous. The less refrangible band
is shifted toward the red, while the second approaches the shorter
wave lengths characteristic of disubstituted benzene absorption.
Phthalophenone in alcohol shows a single band (fig. 13) similar
to the simple phthalide from which it is derived. The effect of
replacing two hydrogen atoms by two phenyl groups does not
greatly alter the equilibrium. A slight shift of the band toward
the red and a decrease in its persistence mark the change. The
solution in sulphuric acid, however, is decidedly altered. As
before, the single original band is divided, the result being a less
refrangible band accompanied by disubstituted benzene absorp-
tion. A very strong band of great width and persistence also
appears at = 2220 in the color region. Oxydipheny! phthalide
and phenolphthalein have been shown to give a similar band in
this solvent,?? but the authors do not comment on the spectra.
The change from a colorless solution to a colored one, or an
alteration in the existing color in compounds of the type studied
in this paper, cannot be explained logically by the quinoid theory.
In many cases such a change in structure is impossible. It is not
probable that phthalophenone assumes a true quinoid form when
dissolved in concentrated sulphuric acid. A more reasonable
explanation may be found in assuming a conjugation between
latent valencies of the unsaturated phenyl and carbonyl groups -
similar to that suggested for the alkali salts of phthaloxime.*
In this case, the increased energy is supplied by the solvent
* Meyer und Fischer, Ber. d. deutsch. chem. Ges. (1913), 46, 80.
“Pratt and Gibbs, This Journal, Sec. A (19138), 8, 165.
VIII, A, 6 Pratt: Phthalides and Related Compounds 423
instead of by introducing a metallic atom into the ring. The
resulting equilibrium may be represented by the formula:
Ph
ae a
Lap Nees
CHK 0 eS
Ss = on ou
A similar structure may be applied to the phthaleins dissolved
in sulphuric acid without invoking quinoid rearrangement.
Evidently the condition is unstable, and depends entirely upon
the free affinity of the solvent to supply energy for its main-
tenance. The addition of water destroys this free affinity of the
acid, and consequently restores the molecule to its normal color-
less configuration.
It is also possible to supply the necessary energy to accomplish
this change in equilibrium by introducing more active centers
in the molecule as in the case previously considered. Meyer and
Fischer ?° have studied the absorption spectra of fluoran and di-
thiofluoran in alcohol and glacial acetic acid. The former com-
pound gave a curve closely resembling those here shown of the
phthalide type as might be expected from its analogous structure,
while the latter compound is deep red and gave selective ab-
sorption analogous to phthalophenone in sulphuric acid. These
authors dismiss the question of the marked difference in color
by attributing it to the stronger chromophoric action of the
thionyl groups substituted for carbonyl. This increased chro-
mophoric development may be further amplified by considering
that the greater free affinity of the sulphur atoms increases
the activity of the lactone ring and causes conjugation with
the C,H, residue. The result is then very similar to that
postulated for phthalophenone in sulphuric acid solution, and
may be represented by an analogous structural formula.
I have recently succeeded in preparing a thiophthaloxime
that further strengthens this view, as it is a brilliant red and
gives deeply colored salts. This interesting compound is now
being investigated, and will be described further in a subsequent
paper. Other similar colored thio compounds might be men-
tioned, for example, dithiodipheny] phthalide.
* Loc. cit.
424 The Philippine Journal of Science 1913
Nitrosophthalimidene also typifies a condition of high activity ©
in the side chain, and its absorption spectrum in alcohol contains
three bands, one of which is in the color region (fig. 7). The
introduction of the unsaturated nitroso group replacing the imido
hydrogen has augmented the residual activity of the molecule and
has also provided the condition necessary for conjugation. The
complete structural formula corresponding to the absorption
spectrum may be represented as:
CsEsCom SNEM@ ss a) GH gy SNES
HK » eee LY A, i
No So__. H(M)
containing a six-membered conjugated ring. The equilibrium is
shifted to the right by alkalies with salt formation.
The absorption spectra of the compounds studied in which
nitrogen has replaced an atom of oxygen in the side chain are
especially interesting, but still more difficult to explain. Phthal-
imide (fig. 5) and phthalanil (fig. 12) give very similar absorp-
tion in ordinary solvents. The bands are shifted toward the
longer wave lengths about equal distances in sulphuric acid solu-
tion, but the persistence of the band of the former compound is
very greatly increased while that of the latter is only slightly
greater. The appearance of a benzene absorption band is not
evident in either compound in sulphuric acid. Phthalimidine
‘(fig. 6) more closely resembles the phthalic acid type, although
even here sulphuric acid does not result in the production of a
new absorption band.
Phthalophenone anilide (fig. 14) shows much less pronounced
selective absorption than phthalophencne. The sulphuric acid
solution of the former still gives a color band heading at the
same place as that of the latter, but it appears at very much
greater concentration and is only about half as persistent.
The absorption spectrum of phthaloxime is not greatly altered
by using sulphuric acid as a solvent, and no new bands are
produced.
In every case the introduction of nitrogen in place of oxygen
has decreased the effect caused by sulphuric acid. This may be
explained readily if the theory regarding the action of sulphuric
acid on the phthalids be accepted. The natural affinity between
vi,a,¢ Pratt: Phthalides and Related Compounds 425
oxygen and sulphur makes it possible for sulphuric acid to sup-
ply considerable energy to the side chain of compounds such as
phthalic anhydride and the phthalids. No such affinity exists
between the latent valencies of nitrogen and sulphur, as was
pointed out by Thiele *° in explaining the addition of sulphurous
acid to quinone diimide where the acid residue attaches itself,
not to the nitrogen, but to the carbon. The condition of all these
compounds in concentrated sulphuric acid is different from true
chemical combination only in degree. The attraction between
the acid and the molecule is insufficient to produce a stable ad-
dition product capable of isolation, but the first phase of such
combination is nevertheless reached. The tendency is most
marked in the molecules here considered that still retain either
the two original carbonyl groups or equivalent doubly bound
atoms possessing attraction for the latent valency of sulphur,
and least in those such as phthaloxime where not only has one
carbonyl oxygen been removed, but has been replaced by a
nitrogen atom. The action of sulphuric acid becomes almost neg-
ligible in this case, and the absorption spectra in acid or alcohol
are very similar.
Phthalanil retains the carbonyl groups in addition to having
nitrogen in the lactone ring, and consequently shows a marked
shift in the position of its absorption band by sulphuric acid.
No new band is developed in the benzene region, however, as
the amount of energy supplied by the acid is not sufficient, in the
presence of the opposing nitrogen, to separate the two influences
into their components.
When one carbonyl oxygen of phthalanil is replaced by two
phenyl groups, the effect is further reduced. The band in the
ultra-violet is not shifted by sulphuric acid in this case, and so
little energy is supplied to the molecule that only slight conjuga-
tion takes place between the remaining carbonyl] and the phenyl
groups. The color band must head at the same place as it is
caused by the same mutual influence, but it now appears at log.
3.3 instead of log. 1.5 and is greatly reduced in persistence.
SUMMARY
1. The absorption spectra of various derivatives of phthalic
acid representing the phthalide and lactone type have been
studied in ordinary solvents and in concentrated sulphuric acid.
* Ann. d. Chem. (Liebig) (1899), 306, 130.
128668——4
426 The Philippine Journal of Sctence 1918
2. A theory based upon the latent valency of this acid has been
advanced to account for the remarkable changes it produces in
these spectra.
3. This theory includes the color of phthalids and phthaleins
dissolved in sulphuric acid and of the thio derivatives of this type
of compounds.
4. The counterinfiuence of substituting nitrogen in the side
chain is discussed in relation to its effect on absorption spectra.
Fie. 1.
. Curve
. Curve
. Curve
1
2
1
2
1
Dy
. Curve 1.
2
1
2
3
. Curve 1
2
Curve
Curve
Curve
Curve
Curve
Curve
Curve
Curve
. Curve 1.
Curve 2.
ILLUSTRATIONS
TEXT FIGURES
. Phthalic acid in alcohol.
. Phthalic acid in sulphuric acid.
. Phthalic anhydride in glacial acetic acid.
. Phthalic anhydride in sulphuric acid.
. Maleic anhydride in glacial acetic acid.
. Maleic anhydride in sulphuric acid.
Phthalide in alcohol.
. Phthalide in sulphuric acid.
. Phthalimide in alcohol.
. Phthalimide in sulphuric acid.
. Phthalimide in alcohol + 5 equivalents of sodium ethoxide.
. Phthalimidene in alcohol.
. Phthalimidene in sulphuric acid.
Nitrosophthalimidene in alcohol.
Nitrosophthalimidene in alcohol + 1 equivalent of sodium
ethoxide.
. Curve 1.
Curve 2.
. Curve 1.
Curve 2.
. Curve 1.
Curve 2.
. Curve 1.
Curve 2.
. Curve 1.
Curve 2.
. Curve 1.
Curve 2.
. Curve 1.
Curve 2.
. Curve 1.
Curve 2.
Benzylidene phthalide in alcohol.
Benzylidene phthalide in sulphuric acid.
Cyanbenzylidene phthalide in alcohol.
Cyanbenzylidene phthalide in sulphuric acid.
Phthalylacetic acid in glacial acetic acid.
Phthalylacetic acid in sulphuric acid.
Diphthalyl in glacial acetic acid.
Diphthalyl in sulphuric acid.
Phthalanil in alcohol.
Phthalanil in sulphuric acid.
Phthalophenone in alcohol.
Phthalophenone in sulphuric acid.
Phthalophenone anilide in alcohol.
Phthalophenone anilide in sulphuric acid.
Yellow phthaloxime in alcohol.
Yellow phthaloxime in sulphuric acid.
427
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ANALYSIS AND COMPOSITION OF RED LEAD
By Aucustus P. WEsT*
_ (From the Laboratory of General, Inorganic, and Physical Chemistry,
Bureau of Science, Manila, P. 1.)
When lead is heated to a temperature of low redness, the
monoxide (PbO) is obtained. When the temperature is carefully
regulated and kept below the melting point of the monoxide, the
product obtained is a yellowish powder known as massicot. If
the monoxide is melted during the preparation, the product is a
reddish solid known as litharge. The commercial monoxide of
lead is a yellow to reddish yellow solid, the color and specific
gravity of which vary with the conditions of formation. When
lead monoxide is heated in the air at a temperature of from about
300° to 550°, oxygen is gradually absorbed and a red product
is obtained known as minium or red lead. At temperatures
above 550°, red lead is decomposed to lead monoxide.
Various methods have been proposed for estimating the purity
of red lead, but they are all more or less unsatisfactory. Al-
though red lead has been investigated extensively, the exact com-
position is still an unsettled question. The object of this paper
is to describe a method which has been found satisfactory for
determining the purity and composition of red lead.
Commercial red lead is usually regarded as a mixture of
minium (Pb,O,), uncombined lead monoxide (PbO), and small
amounts of impurities (such as red clay, barium sulphate, iron
oxide, and sand).
Analyses of 16 samples by F. Lux? showed the impurities to
vary from 1.4 to 13.5 and the uncombined lead monoxide from
2.3 to 42.5 per cent.
D. Woodman ? in 21 analyses found the uncombined lead mon-
oxide to vary from 8 to 59 per cent.
Woodman’s method for determining the purity of red lead
consists simply in leaching out the free litharge with lead acetate
solution and in determining the red lead by difference.
When minium is treated with dilute nitric acid, it decomposes
according to the equation
Pb;0. + 4HNO; > PbO: + 2Pb (NOs): + 2H:O
+ Assistant professor of chemistry, University of the Philippines.
* Zettschr. f. anal. Chem. (1880), 19, 155.
* Journ. Am. Chem. Soc. (1897), 19, 339.
429
430 The Philippine Journal of Science 1918
Some of the most accurate methods for estimating the purity
of red lead are based on the direct estimation, either volumetri-
cally or gravimetrically, of the lead dioxide thus formed.
The method of Lux, for instance, consists in merely determin-
ing the amount of black lead dioxide (PbO,) and calculating the
percentage of minium (Pb,O,).
Probably one of the best general methods which has been sug-
gested for determining the purity of red lead is that outlined by
Baucher.* :
This consists in determining insoluble impurities, lead dioxide
(PbO,), and free litharge (PbO), and calculating by difference
the combined lead monoxide. In this method the free litharge
is determined by leaching with a solution of lead acetate, and
consequently the results obtained are not especially accurate.
That these various methods do not give very accurate results is
brought out in the following analytical data, in which the per-
centage of red lead was determined by treating the sample with
nitric acid, filtering off the insoluble lead dioxide, drying, weigh-
ing, and calculating as minium.
Sample A.
Per cent.
Insoluble matter none
Red lead (Pb:0,) 77.44 (equivalent to
27.02 per cent
PbO;)
Free litharge (PbO) 18.54
Not accounted for 3.99
100.00
77.44 per cent Pb:O, is equivalent to 70.47 per cent Pb
18.54 per cent PbO is equivalent to 17.21 per cent Pb
Total Pb calculated 87.68 per cent
Pb by direct determination 91.37 per cent
Pb not accounted for : 3.69 per cent
The figures show a wide discrepancy between the total lead
as calculated and the actual lead content. Soluble lead salts
were shown to be absent by leaching the sample with hot water
and attempting to precipitate the lead as sulphate. Since the
above results were obtained in closely agreeing duplicate deter-
minations, it would seem that the error of 3.66 per cent in the
calculated total lead content was due to errors in method both
in analysis and calculation. Probably the actual percentage of
* Petit Monit. Pharm., 47, 2651.
vi,a,6 West: Analysis and Composition of Red Lead 431
red lead in the sample is not to be directly computed from the
percentage of lead dioxide.
In 1850, Mulder * showed that in red lead the percentage of
oxygen above that required in lead monoxide varies from 1.16
to 2.67 per cent. Several samples of red lead agreed in com-
position with the formula Pb,O,. In Table I is given the oxygen
content of various oxides of lead.
TABLE I.—Oxygen content of various lead oxides.
Oxygen |
greater
than oxy-
gen con-
tent o:
PbO.
Compound. Oxygen.
Per cent. | Per cent.
According to Mulder’s results, it appears that some samples
of red lead consist of mixtures of different oxides of lead.
In 1851, Mulder’s results were confirmed by Jacquelain,*? who
examined a number of samples of red lead and noticed that the
oxygen content varied considerably.
In 1889, Lowe’ pointed out that both the oxides Pb,O, and
Pb,O, may be present in red lead, but that the commercial arti-
cle containing free extractable PbO probably consists of a
mixture of Pb,O, and PbO.
Whether one or both of the oxides Pb,O, and Pb,O, are present
in a sample of pure red lead, can be determined in the following
manner: By leaching with a solution of lead nitrate, any free
PbO can be eliminated, leaving only pure red lead. Now minium
when heated above 500° gives lead monoxide and a loss of 2.34
per cent of oxygen. If the compound Pb,O, behave in a similar
manner, it would be decomposed according to the equation Pb,O,
— 4 PbO + O and the oxygen loss would be 1.76 per cent. Know-
ing the oxygen loss of a mixture of the oxides Pb,O, and Pb,O,,
we can calculate the amount of each present in the mixture.
However, since the figures representing the loss of oxygen are
rather small, the experimental error involved in determining
* Journ. f. prakt. Chem. (1850), 50, 438.
' *Tbid. (1851), 53, 161.
7 Dingler’s polytech. Journ. (1889), 271, 472.
432 The Philippine Journal of Science 1918
such a factor would make it a somewhat undesirable method. A
more practical method will be described later.
Minium is regarded as composed of lead dioxide combined with
two molecules of lead monoxide, PhO, . 2PbO, and a compound of
the formula Pb,O, would consist of one molecule of lead dioxide
combined with three molecules of lead monoxide, PbO, .3PbO;
in other words, both compounds may be considered as composed
of PbO, plus combined PbO.
If red lead consist of a mixture of various oxides such as
PbO, . 2PbO, PbO, . 3PbO, and free PbO, we can easily determine
the various constituents in the mixture as follows:
Decompose the complex oxides with dilute nitric acid. Sep-
arate and weigh the resultant black lead dioxide, and calculate
the lead monoxide from the lead present in the filtrate. The
latter result gives the free plus combined lead monoxide. In
a separate sample determine free lead monoxide by leaching
with a suitable solvent, and compute the lead monoxide by
difference. This method of separation is clearly shown in the
following diagram:
Commercial red lead,
precipitated by dilute HNOs.
Total PbO determined as Pb.
PbO dissolved with Pb (NOs) 2 solution.
The percentage of lead dioxide plus the percentage of combined
monoxide gives the percentage of red lead.
Knowing the percentage of combined lead monoxide, we can
calculate the actual amount of each of the oxides Pb,O, and
Pb,O, in the following manner:
Suppose an analysis of a mixture of the oxides Pb,O, and
Pb,O,; shows 70.25 per cent combined PbO. Since
Pb.O; contains 73.68 per cent combined PbO and
Pb;O, contains 65.11 per cent combined PbO,
the percentage of each constituent in the sample may be cal-
culated as follows:
Per cent Pb;O.+per cent Pb.O;<=100
(0.6511 x per cent Pb,O.) + (0.7368 X per cent Pb.O;) =70.25,
which by computation shows 40 per cent Pb,O, and 60 per cent
Pb,O,, respectively.
a
vil,a,¢é West: Analysis and Composition of Red Lead 433
Table II shows the combined lead monoxide content cor-
responding to each of a series of mixtures of the oxides Pb,O,
and Pb,O,, ranging from pure Pb,O, to pure Pb,0O,.
TABLE II.—Mixtures of lead oxides and the corresponding combined PbO
content of each mixture.
| Mixture. || Mixture. | Mixture. || Mixture.
Mixture. |
Com- oeeecd eee Goris] om s fe gents ae ee Gore
a | bined jj = 1» | bined ||. = 1» | bined || = | bined || = i» | bined
Qo; 2 | Pho. |} 9 | QO | Pho. || O | O | Pho. Q,} QO | Pbo. || O | O | PbO.
Bile sles Eh pMool ule Ska |
P. ct. |P. ct. P. cent. 'P. ct.|P. ct.| P. cent.||P. ct. P. ct.| P. cent.||P. ct.|P. ct.| P. cent.||P. ct.'P. ct.| P. cent.|
100 0} 65.11 80 | 20] 66.82 |} 60} 40} 68.54 || 40] 60} 70.25 |} 20] 80] 71.97
99 1| 65.19 79 | 21) 66.91 | 59 | 41) 68.62 || 39} 61] 170.34 19} 81 | 72.05 }
98 2| 65.28 || 78| 22] 66.99 || 58] 42] 68.71]; 88| 62)| 70.42 | 18| 82) 72.14
97 3] 65.36 || 77 | 23] 67.08 || 67| 43] 68.79 || 37| 68] 70.61 |] 17] 83! 72.22 |
96 4| 65.45 16 | 24/ 67.17 | 66 | 44) 68.88 36 | 64} 70.59 16 | 84) 72.31
95 5 | 65.64 75! 25] 67.25 65 | 45) 68.97 35 | 65} 70.68 15 | 85 | 72.39
94 6| 65.62 74) 26 67.34 || 54 | 46 69.05 34] 66| 70.76 || 14} 86| 72.48
98 7| 65.71 || 73 | 27) 67.42 | 53] 47} 69.14 || 38] 67 70.85 || 18] 87 | 72.56
92 8} 65.79 | 72 | 28! 67.61 52 | 48) 69.22 32 | 68} 70,94 | 12} 88 | 72.65 |
91 9 | 65.88 71} 29) 67.59 51 | 49! 69.81 81} 69) 71.02 11 | 89 | 72.74
90} 10) 65.97 70 | 30]! 67.68 50; 50] 69.39 80} 70; 71.11 10 | 90 | 72.82
89 | 11) 66.05 69 | 31] 67.77 49| 51/ 69.48 29] 71 71.19 OE 2397
88; 12)| 66.14 68 | 82) 67.85 48} 52] 69.57 28) 72; 71.28 8 | 92] 72.99
87 | 18] 66.22 67 | 83] 67.94 47| 53} 69.65 2h tool) who ST 7| 93 | 73.08
86} 14) 66.31 66 | 34) 68.02 46 54) 69.74 26; 74| 71.45 6 | 94] 73.16
85 | 15! 66.39 65] 35; 68.11 || 45] 55; 69.82 25; 75| 71.541) 5 95 | 78.25
84} 16) 66.48 64| 36] 68.19 44! 56] 69.91 24/ 76] 171.62 4)| 96 | 73.35
83 | 17 | 66.57 63 | 87)| 68.28 43 | 57} 69.99 7S 0A VB AC Nf 3 | 97) 73.42
82; 18) 66.65}; 62| 38]| 68.37 | 42] 68} 70.08 || 22] 78) 171.79 2) 98} 73.51
81; 19) 66.74 |} 61} 39] 68.45 || 41] 59) 70.17/| 21] 79| 71.88 1| 99 | 73.59
Sane be: segatts goes bases ssahaars) iments eal 0 | 100 | 73.68
In estimating the purity of samples of red lead, the following
method is satisfactory. By determining the amount of combined
PbO and referring to Table II, one may ascertain the amount of
each of the oxides Pb,O, and Pb,O,. The calculated total lead
content of the sample checks with the percentage of total lead as
obtained by direct determination.
METHOD OF ANALYSIS
a. Insoluble matter—Baucher’s method ® gives very good re-
sults for this determination, and may be carried out satisfactorily
in the following manner:
A 2-gram sample is treated with 100 cubic centimeters of 10
per cent nitric acid solution; after a few minutes’ boiling, the
red lead is completely decomposed, leaving only the black lead
* Petit Monit. Pharm., 47, 26651.
434 The Philippine Journal of Science 1918
dioxide. Fifteen cubic centimeters of a cane-sugar solution,
prepared by dissolving 1 part of cane sugar in 3 parts of
water, are slowly added. On boiling a short time, the lead
dioxide is reduced to lead monoxide and dissolves in the nitric
acid. The liquid is filtered through a Gooch crucible, and the
insoluble residue is weighed. In red lead of good quality there
is usually less than 1 per cent of insoluble matter.
b. Free litharge——The free lead monoxide is best determined
by the method of Lowe.® This method gives excellent results
when carried out in the following manner: A 0.5-gram sample
is treated with 100 cubic centimeters of 10 per cent lead nitrate
solution. The mixture is digested on a water bath about one
hour, after which it is boiled ten minutes, diluted to twice its
volume with hot water to dissolve basic salts, and filtered through
a Gooch crucible. The residue is then weighed.
c. (PbO, + insoluble matter) and (PbO free + PbO com-
bined) —A 0.5-gram sample is treated with 100 cubic centimeters
of 10 per cent nitric acid. After heating on a water bath about
one-half hour, all the red lead is decomposed to the black lead
dioxide; the liquid is then filtered through a Gooch crucible, and
the residue of lead dioxide and insoluble matter is weighed. The
percentage of insoluble matter having already been ascertained,
the difference gives the percentage of lead dioxide.
To the filtrate add 20 cubic centimeters of sulphuric acid (1
part concentrated H,SO, to 5 parts H,O), evaporate until white
fumes are evolved, cool, and add carefully 40 cubic centimeters
of water. Now add 100 cubic centimeters of 75 per cent alcohol,
stir, and, after the precipitate has settled, filter through a Gooch
crucible, dry at 100°, and weigh. If there is considerable in-
soluble matter present, the precipitated lead sulphate is probably
contaminated with foreign matter. In this case more accurate
results are obtained by dissolving the lead sulphate in ammonium
acetate and reprecipitating.
From the weight of lead sulphate obtained, the percentage of
(PbO free + PbO combined) is calculated. Having previously
determined the percentage of free lead monoxide, the percentage
of combined lead monoxide is obtained by difference.
The percentage of lead dioxide plus the percentage of combined
lead monoxide gives the percentage of red lead present in the
original sample. Having obtained the percentage of combined
° Dingler’s polytech. Journ. (1889), 271, 472.
viu,a,6 West: Analysis and Composition of Red Lead 435
lead monoxide, the amount of each of the oxides Pb,O, and Pb,O,
which compose the total red lead present in the sample is ascer-
tained by reference to Table II. |
d. Total lead.—This determination serves simply as a check
on the other determinations.
_ Treat a 0.2-gram sample with 30 cubic centimeters of 10 per -
cent nitric acid, boil until all red lead is completely changed to
the black dioxide, cool, and add 20 cubic centimeters of sulphuric
acid (1 part H,SO, to 5 parts H,O). Boil a few minutes. The
soluble lead nitrate is changed to lead sulphate. Now add 2
cubic centimeters of concentrated hydrochloric acid, and the lead
peroxide is changed to lead chloride.
Evaporate to white fumes, cool, add 10 cubic centimeters of
water, and again evaporate to fumes. The lead chloride is con-
verted to lead sulphate. The lead is now determined as sulphate
as in the determination of free plus combined lead monoxide.
In the presence of insoluble matter more accurate results are, of
course, obtained by dissolving the lead sulphate in ammonium
acetate and reprecipitating.
As red lead is only very slightly hygroscopic, moisture de-
terminations are seldom necessary. Occasionally, adulterated,
artificially colored samples are encountered. In such cases,
the adulteration is best detected by leaching with suitable
solvents.?°
In the case of rapid work, when only approximately accurate
results are desired, it is not necessary to make a complete anal-
ysis. In the absence of insoluble matter, the free lead monoxide
may be determined by leaching with lead nitrate solution. One
hundred per cent—per cent free PbO=per cent red lead. In
the presence of insoluble matter
100 per cent— (per cent free PbO+per cent insoluble matter)
=per cent red lead.
This method of analysis gives very satisfactory results when
applied to high-grade samples which contain only red lead, free
litharge, and no insoluble matter.
As previously pointed out, the analysis of red lead sample A
gave unsatisfactory results when the percentage of red lead was
calculated from the PbO, content. My method of analysis and
“ Technical methods of testing miscellaneous supplies. Bull. U. S. Dept.
Agr., Bur. Chem. (1908), No. 109, 20.
436 The Philippine Journal of Science 1918
calculation when applied to the same sample gave the following
results:
Sample A.
Per eent.
Insoluble matter none
Lead dioxide (PbO:) 27.02
Combined lead monoxide (PbO) 54.52
Free lead monoxide (PbO) 18.54
: 100.08
Lead dioxide (PbO:) 27.02
Combined lead monoxide (PbO) 54.52
Red lead 81.54
1 gram of original sample contains ee eran of sel lead d
Combined PbO in red lead proper = 66.86 per cent.
From Table II, 66.86 per cent combined PbO corresponds to
a mixture of (80 per cent Pb,O,+20 per cent Pb,O,).
81.54 x 0.80 = 65.23 per cent Pb;O, in original sample.
81.54 x 0.20 = 16.31 per cent Pb,O; in original sample.
According to this method of calculating results, the analysis
of sample A would be:
Per cent.
Insoluble matter none
PbO (litharge) 18.54
Pb,O. (minium) 65.23
Red lead :
ed les {pb,0. 16.31
100.08
When the lead content is computed from these data and
checked by a total lead determination, the following.results are
obtained :
Per cent.
Total Pb by direct determination 91.37
Total Pb by direct calculation 91.21
Difference 0.16
By this method of calculation the total lead determination
serves as a check on the entire analysis and the agreement
between the calculated and determined total lead content of the
sample is very close.
In Table III are given the data for a number of samples of
red lead which have been investigated in accordance with this
method of analysis and calculation.
vur,4,6 West: Analysis and Composition of Red Lead 437
TABLE III.—Analyses and composition of red lead.
Sample. A. B. Cc. D. E. F. G. H.
j-
Insoluble matter -___-_-..-_----------- none} 0.51] none! none | none} 0,08] none | none
VOW SET) 12) 0 RE Spe Nee OER as pe ee | 18.64 | 23.76 | 27.74 | 6.66 | 29.22 | 41.36 | 21.54] 5.36
Red lead |
PED Olg ae tosses on af ok eee ae 27.02 | 24.53 | 24.76 | 31.28 | 23.18 | 19.80 | 26.80 | 81.96
Gompined epO)..2- 55-0. s220e 64.52 | 50.92 | 47.82 | 62.02 | 46.74 | 38.46 | 52.18 | 62.52
Red lead as obtained from Table I:
Pb30,4 =-------------------------| 65. 23 55.08 | 66.05 | 78.37 | 55.94 | 51.85 | 65.92 | 83.14
Ey Opec Sy. ia 8 | 16.81 | 20.37 | 6.53 | 14,98 | 13.98 | 6.41 | 12.56 | 11.34
Total Pb determined ___________- | 91.37 | 89.90 | 91.20 | 90.65 | 90.86 | 91.11 | 91.13 | 90.88
Total Pb calculated__________--_- 91.21 | 90.55 | 91.58 | 90.74 | 90.58 | 91.23 | 91.20 | 90.68
Total (insoluble matter + free
PbO + Pb3gO,4 + Pb4O>5) -----| 100.08 | 99.72 |100.32 | 99.96 | 99.14 | 99.70 |100.02 | 99.84
As shown by the figures, there is a close agreement between
the calculated total lead content and that obtained by direct
determination.
As shown by the data presented in Table III, the method of
analysis and calculation gives very accurate results.
Although many investigations on red lead have been carried
out, its exact composition is still in doubt. The formula is
usually written Pb,O,. Several investigators regarded it as a
mixture of Pb,O, and Pb,O,. Lowe considered it a mixture of
Pb,O, and PbO. Milbauer* calculated his results on the sup-
position that it is only Pb,O,,.
According to the results, it would appear that red lead as or-
dinarily prepared consists’ of a mixture of the oxides Pb,O,,
Pb,O,, and PbO, and the exact composition of any particular
sample depends upon the conditions of manufacture which estab-
lish the equilibrium of the various component oxides.
“Chem. Zeitg. (1909), 33, 513.
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EDITORIAL
COPRA SPOILAGE ON A LARGE SCALE
One plate
The Swedish freight steamship Nippon, with a large cargo
composed chiefly of dried coconut meat, or copra, was driven
upon Scarborough Reef during a severe typhoon in May, 1913.
The reef lies off the west coast of Luzon, and is practically
submerged even during periods of low tide. The unfortunate
vessel was firmly held by the coral, and the copra in the various
holds was thus alternately submerged and exposed to a greater
or less extent by the fluctuations of the tides.
The conditions thus presented unique opportunities to study
the spoilage of copra on a very large scale. The salvage crew
boarded the Nippon several days after the disaster, and found the
hatches tightly closed. It was necessary to lighten the vessel
before attempting to drag it into deep water. During an attempt
to investigate the holds preparatory to discharging the copra,
one member of the crew was fatally overcome by noxious gases
and several others were rescued with difficulty. This dangerous
condition persisted even after the holds had been open several
days, and greatly interfered with the work of salvage. Every
one who stayed below for a short time was affected with gid-
diness and marked palpitation of the heart, followed by uncon-
sciousness unless immediate relief was sought in the open air.
The eyes became seriously inflamed, and contact with water in
the holds resulted in burns and sores.
The condition appeared so remarkable that an investigation
by the Bureau of Science to explain the causes of the trouble was
decided upon; and I was detailed to undertake the work. It was
desirable to ascertain the nature of the poisonous gas and the
caustic products present in the bilge water, not only in their
bearing on the health of the workmen employed on the Nippon,
but also as throwing light on the very important problem of copra
deterioration.
Pumps had been installed on the Nippon before this investiga-
tion was started, and were regularly operated during the day.
The sea water that penetrated during the night through the
439
440 The Philippine Journal of Science 1918
various leaks was thus partially removed. In spite of the daily
circulation established, it was possible to obtain samples of bilge
water containing sufficient decomposition products for partial
identification. It was found that bacterial action was taking
place throughout the mass of copra, with the production of a
large amount of hydrogen sulphide. Distinct tests for this gas
were obtained in the open air at a distance of about 150 meters
from the scene of the wreck, and vessels stationed near to render
assistance were completely blackened within a short time. The
hydrogen-sulphide-producing organism was found to be a motile
rod. It appeared to act on the cellular tissue and cause an ex-
traordinary selective destruction of the copra. One of the crew
volunteered to obtain a sample of bilge water early in the morning
before pumping was started. Accordingly, I left a bottle with
him the preceding evening, with directions to fill it and im-
mediately wire on the rubber stopper. This sample was car-
ried to Manila for experimental purposes, and opened some days
later in the laboratory. It consisted entirely of coconut oil,
of slightly dark color and disagreeable odor. No water was
gathered with the oil, indicating that the amount of free oil in
the hold at that time must have been’ considerable, but owing
to the darkness its presence had not been noted. Unfortunately,
the sample bottle was made of opaque blue glass, with the result
that I had no intimation of its true contents until after my return
to Manila. Moreover, the floating débris of discharged copra
had already rendered the adjacent surface of the ocean oily and
effectively masked the effect of free oil which must have been
pumped out early in the morning. The bacterial action had
broken down the cellular tissue of the copra and liberated the
oil. This oil contained 60 per cent free oleic acid.
The water passing through the copra was decidedly acid, a
specimen taken late in the afternoon containing 0.5 per cent
calculated as sulphuric acid. The acidity must have been much
greater before the pumps were installed, and accounted for the
caustic action of the water. Sulphurous and sulphuric acids were
identified in the water, accompanied by various organic acids with
indol and skatol resulting from decomposition. The action of this
poisonous water was very severe, causing intense smarting where
it came in contact with the skin, accompanied by very pronounced
swelling of the testicles. These evil effects were mitigated by
frequent bathing in salt water, and a shower was maintained on
the deck for this purpose. This acid water was being pumped
continually into the open sea, and the decaying copra was dis-
VIII, A, 6 Editorial 441
charged as rapidly as possible. The relatively large amount of
free acidity thus produced may be judged from its effect on a
bronze propeller shaft used on one of the ship’s small launches.
The portion exposed to the water Was reduced to about one-half
its original diameter (Plate I). It should be remembered that
this was corroded, not in a protected bay or harbor, but in the
open sea.
It is very probable that the many instances of deterioration
known to take place during the shipment of copra are repeti-
tions of the above conditions on a small scale. Sea captains
have frequently informed me that it was always considered un-
wise to remain long in holds filled with copra. This finds its
explanation in the slow production of toxic hydrogen sulphide.
The rate of bacterial action depends upon the care used in pre-
paring the copra and the degree of moisture present. With
carefully dried copra, the deterioration due to hydrogen-sulphide-
producing and other organism will be at a minimum, although
it is doubtful if it can be entirely avoided until more satis-
factory and sterilizing methods of preparation are generally
employed.
DAVID S. PRATT.
123668——5
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ILLUSTRATION
PLATE I
(Photographs by Cortes)
Fic. 1. Bronze propeller shaft, showing corrosive action of acid from de
caying copra.
2. Side view of cross section of the shaft shown in fig. 1. (The ends
were protected by the bearing and propeller, respectively.)
443
Beer wh
a,
OER sk ocine aca BAR
ioe chee Pere wes Panay gatead >.
ea
PRATT: CopRA SPOILAGE. ] j (Puiv. Journ. Sci., VIII, A, No. 6.
Fig. 1. Bronze propeller shaft, showing corrosive action of acid from decaying copra.
Fig. 2. Side view of cross section of the shaft shown in fig. 1.
(The ends were protected by the bearing and propeller, respectively. )
PLATE I.
INDEX
{New names are printed in heavy-faced type; numbers in italics indicate synonyms or
references of minor importance.]
A
Absorption spectra and constitution of the
two phthaloximes, 165.
Absorption spectra of phenol, o-cresol,
o-hydroxybenzyl alcohol, salicylic acid and
its methyl ester, methyl ether of salicylic
acid and its methyl ester, benzyl alcohol,
benzyl acetate, benzyl methyl ether, benzyl
chloride, and methyl benzoate, 33.
Absorption spectra of phenoquinone, 2,
§-dianilinoquinone, 2, 5-dianilinoquinoneanil,
and 2, 5-dianilinoquinonedianil (azophenine),
51.
Absorption spectra of various phthalides and
related compounds, 399.
Acetates, and benzoates, absorption spectra of
the phthaloximes, their methyl ethers, 177.
/Bquipecten, 275.
mioalternans, 275.
northamptoni Micht., 275.
Affinity constants of benzoic acid and methyl
ether of salicylic acid, 33.
Affinity constants of methyl salicylate, 1.
AGCAOILI, FRANCISCO, The composition of
various milks and their adaptability for
infant feeding, 141.
Alectryonia Fischer, 280.
folium Linn., 254, 280.
Area Lamarck, 278, 834.
cecillei Phil. (?), $24.
nodosa K. Mart. (7), 254, 278, $27.
Arcids, 254, 278.
Arthropoda, 298.
Astartide, 254, 279.
Astralium stellare Gmel., $25.
Astreacez, 255, 290.
Azophenine, absorption spectra of, 51.
Azor Gray, 270.
coarctatus Gm., 254, 270.
, B
Balanus sp., 827.
Benzoates, absorption spectra of the phthal-
oximes, their methyl ethers, acetates, and,
177.
Benzyl acetate, absorption spectra of, 33.
alcohol, absorption spectra of, 33.
chloride, absorption spectra of, 33.
methyl ether, absorption spectra of, 33.
Benzylidene phthalide, 408.
Bondoc Peninsula, Tayabas Province, P. I., the
geology and petroleum resources of the
southern part of, 301.
Buccinide, 258, 258.
Buccinum ventriosum, 258.
Bursa Bolten, 266.
ampulla Linn., 326.
(Ranella) subgranosa Beck., 254, 266.
Cc
Callianassa Leach, 298.
dijki K. Mart., 255, 293.
Carboxyl, the mutual influence of hydroxyl
and, and some related groups in the ortho
position, 33.
Cardiide, 254, 277.
Cardita Bruguiére, 279.
boettgeri K. Mart., 254, 279.
Cardium Linnzeus, 277, 326.
elongatum Brug., 254, 277.
fiavum Linn. (?), 254, 277.
Caryophyllia Stokes, 287.
(?) laoagana Smith, 255, 287.
Casside, 254, 268.
Cassidaria Lamarck, 268.
echinophora Linn. (?), 254, 268.
Cassis Lamarck, 263.
nodulosa Gmel., 254, 263.
pila Reeve, 254, 268.
Cement, a bonus system for the purchase of
Portland, 107.
Cenosphzra Ehrenburg, 281.
affinis Hinde, 254, 282.
Cerithiide, 254, 267.
Cerithium Adanson, 268.
herklotsi K. Mart., 326.
jenkinsi K. Mart., 324.
nodulosum_Brug., 269, $24.
sp., 827.
vicentinum Bay, 269.
(Campanile) sp., 254, 269.
(Potamides) palustris Linn.,
269.
Chenendopora Lamouroux, 289.
(?) major Smith, 255, 290.
Chione Gray, 272.
(Venus) chlorotica Phil., 254, 278.
pulcherrima K. Mart.,
273.
254,
254,
445
446
Chlamys Bolten, 275.
( 4quipecten)
275.
Clementia Gray, 271.
papyracea Gray, 254, 272.
sp., 254, 271, 826.
Coelenterata, 285.
Conductivity measurements of benzoic acid and
methyl ether of salicylic acid, 33.
Conductivity measurements of methyl salicyl-
ate, 1.
Conidz, 258, 255.
Conus Linnzeus, 255.
achetinus Chem., 256.
acutangulus Chem. (?), 255.
arenatus Brug., 256.
djarianensis K. Mart., 258, 256.
flavidus Lamarck, 324.
hardi (7?), 255.
hochstetteri K. Mart., 334.
imperialis Reeve, 256.
insculptus Kien., 255.
loroisii Kien., 255, $384.
odengensis K. Mart., 258, 256.
ornatissimus K. Mart., $30.
palembuanensis K. Mart., 255.
parvulus K. Mart., 255, 257.
sinensis Sow., 255.
SD., 258, 256, 325, 326.
striatellus Jenk., 384.
sulcatus Hwass var.
Smith, 258, 256.
vimineus Reeve, 255.
Copra spoilage on a large scale, 439.
Corallinacez, 254, 281.
Corbula socialis K. Mart., 330.
Crista pectinata Linn., 324.
Cucullaea Lamarck, 278.
holoserica Reeve (7), 254, 279.
Cultellus Schumacher, 270.
maximus Gm., 254, 271.
-Cyanbenzylidene phthalide, 409.
Cycloclypeus communis K. Mart., $30.
Cycloseris Edwards et Haime, 288.
decipiens K. Mart. (7), 255, 288.
Cycloseries sp., 826.
Cypraea erosa Linn., 830.
sp., 327.
Cytherea, 272, $25.
(7?) sp. indet., 254,
philippinensis
D
DEL ROSARIO, J. I., see Pratt, D. S., 59.
Dentalium Linnezus, 292.
tumidum Smith, 255, 292.
Dianilinoquinoneanil, 2, 5-, absorption spectra
of, 51.
Dianilinoquinonedianil (azophenine), 2, 5-, ab-
sorption spectra of, 51.
Dictyomitra Zittel, 282.
tenuis Hinde, 254, 282.
Diphthalyl, 412.
Doliidz, 254, 264.
Dolium Lamarck, 264.
costatum Menke, 254, 264.
hochstetteri, 264.
Index
Dosinia Scopoli, 273.
boettgeri K. Mart., 254, 273.
Sp., 325, 826, 330.
DOVEY, E. R., The composition of carabao’s
milk, 151.
E
Echinodermata, 291.
Echinoidea, 291.
EDDINGFIELD, F. T., Alteration and enrich-
ment in calcite-quartz-manganese gold de-
posits in the Philippine Islands, 125; Gogo,
Entada scandens Bentham, and its effect on
gold and gold solutions, 185; Ore deposits of
the Philippine Islands, 81.
EDITORIAL. Copra spoilage on a large scale,
439.
| Entada scandens Bentham, and its effect on
gold and gold solutions, gogo, 135.
Eye strain, the optical efficiency of tinted
glasses in relieving, 193.
FE
Flabellum Lesson, 287.
australe Moseley (7), 255, 287.
Foraminifera, 283.
Fossil invertebrate fauna of the Philippine
Islands, contributions to the stratigraphy
and, 235.
Fruits: Philippine,
characteristics, 59.
Fuside, 253, 257.
Fusus Lamarck, 257.
glomus Gené, 257.
SD., 826, 834.
tjidamarensis K. Mart., 257.
verbeeki K. Mart., 257.
(Turbinella), 257.
their composition and
G
GALAJIKIAN, A. S., see Gress, H. D., 1.
Geology and petroleum resources of the south-
ern part of Bondoc Peninsula, Tayabas Proy-
ince, P. I., the, 301.
GIBBS, H. D., and PRATT, D. S., The mutual
influence of hydroxyl and carboxyl and some
related groups in the ortho position. A
study of the absorption spectra of phenol,
o-cresol, o-hydroxybenzyl alcohol, salicylic
acid and its methyl ester, methyl ether of
salicylic acid and its methyl ester, benzyl
alcohol, benzyl acetate, benzyl methyl ether,
benzyl chloride, and methyl benzoate, 33; see
Pratt, D. S., 51, 165, 377.
GIBBS, H. D., WILLIAMS, R. R., and GA-
LAJIKIAN, A. S., Methyl salicylate IV.
The saponification of methyl salicylate, me-
thyl benzoate, and the methyl ether of
methyl salicylate, 1.
Globigerina, 334, 861, 362.
Gogo, Entada scandens Bentham, and its effect
on gold and gold solutions, 135.
Gold and gold solutions, gogo, Entada scandens
Bentham, and its effect on, 135.
Index
Gold deposits in the Philippine Islands, altera-
tion and enrichment in calcite-quartz-man-
ganese, 125.
Gasteropoda, 255.
H
Hindsia Adams, 258.
dijki K. Mart., 258, 258.
sp., 330.
tambacana, 258.
Hydroid zoéphytes (7), 291.
Hydroxyl, the mutual influence of, and car-
boxyl and some related groups in the ortho
position, 33.
if
Infant feeding, the composition of various
milks and their adaptability for, 141.
L
Lagenum multiforme K. Mart. var. tayabum
Smith, 325.
Lamellibranchiata, 270.
Lead, analysis and composition of red, 429.
Lepidocyclina Giimbel, 283.
) formosa Schlumb. (7?) 254, 285.
inermis Douvillé, 234.
inflata Provale, 284.
insule-natalis Jones et Chap.,
254, 284,
cf. marginata Mich., 234.
richthofeni Smith, 284, $30.
smithi Douvillé, 284.
verbeeki Newt. et Holl., 284.
Lithistidz, 255, 289.
Lithophylliacez, 254, 285.
Lithothamnium Philippi, 281.
ramosissimum
281, 327.
Lophoserinz, 255, 288.
Lucina Bruguiére, 276.
(Codakia) sp., 254, 277.
Lucinide, 254.
Reuss., 254,
M
Macrocallista Meek, 272.
ventricola K. Mart. (7), 254, 272.
Madrepora Linnzus, 290.
duncani Reuss (?), 255, 290.
Madreporide, 255, 290.
Maleie anhydride, 401.
Melania Lamarck, 265.
denticulata, 265.
laterita Lea, 254, 265.
Sp., 325, 326.
woodwardi K. Mart., 254, 265.
Melaniidee, 254, 265.
Melongena Schumacher, 264.
Meretrix subpellucida, 272.
Methyl benzoate, absorption spectra of, 33.
Methyl benzoate, saponification of, 1.
Methyl ether of salicylic acid and its methyl
ester, absorption spectra of, 33.
Methyl ethers, acetates, and benzoates, absorp-
tion spectra of the phthaloximes, their, 177.
447
Methyl methyl salicylate, saponification of, 1.
Methyl salicylate IV. The saponification of
methyl salicylate, methyl benzoate, and the
methyl ether of methyl salicylate, 1.
Milk, the composition of carabao’s, 151.
Milks, the composition of various, and their
adaptability for infant feeding, 141.
Mitra javana K. Mart., 330.
Sp., 326, 334.
Modiolus Lamarck, 271.
SDp., 254, 271.
Montlivaultia Lamouroux, 285.
bulacana Smith, 254, 285.
cortada Smith, 254, 286.
robusta Smith, 254, 286.
Mytilidz, 254, 271.
N
Nassa Martini, 261.
caniculata Lam., 254, 261.
dertonensis Bell, 261.
siquijorensis A. Adams, 254, 261, 262.
Sp., 826.
verbeeki K. Mart., 254, 261, 262.
Nassidz, 254, 261.
Natica Lamarck, 265.
globosa Chem., 254, 265, 206.
mamilla Linn., 330.
marochiensis Gmel., 254, 265, 266.
rostalina Jenk. (?), 254, 265, 266.
SD., 824, $34.
(Lunatia) sp., 254, 266. _
Naticidz, 254, 265.
Natural gas, 356.
Nipa palm as a commercial source of sugar,
377; character of the sap, 379; cost of nipa
juice, 395; deterioration of nipa sap, 382;
experiments in Bulacan Province, 387; ex-
periments in other swamps, 389; extraction
of sugar, 395; other nipa enzymes, 383;
the mill, 895; the modified bamboo tuquil,
392 ; transportation of sap, 394.
Nummulinide, 254, 283.
0)
O-cresol, absorption spectra of, 33.
O-hydroxybenzyl alcohol, absorption spectra
of, 33.
Odontocyathus Moseley, 288.
coloradus Smith, 255, 288.
coronatus Moseley, 288. as
Oil, see Petroleum, 301.
Olivia sp., 325, 326.
Operculina d’Orbigny, 283.
costata d’Orb., 254, 283, 826.
Optical efficiency of tinted glasses in relieving
eye strain, 193.
Orbitolites Lamarck, 283.
complanata Lam. (?), 254, 2838.
Ore deposits of the Philippine Islands, 81.
Ostrea Linnzus, 280.
orientalis Chem. (7), 326.
sp., 254, 280.
Ostreidse, 254, 280.
448
P
Pachyseris Edwards et Haime, 289.
cristata K. Mart. (7), 265, 289.
Paleontology, 253.
Parallelodontidz, 254, 278.
Pattalophyllia d’Ach., 286.
(2?) bonita Smith, 254, 286.
eyclolitoides, 287.
Sp., 826, 330.
Pecten Klein, 278.
fricatum Ry., 274, 880.
leopardus K. Mart., 327.
leopardus Ry., 274.
leopardus (7?) Reeve, $25.
pallium Linn., 254, 274.
reticulatus Rv., 274.
senatorius Gmel. 254, 274, 275, 825, 826,
830.
solaris Rv., 274.
subareuatus Bitg., 274.
suleatus Miill., 254, 274.
SD., $26, $30.
Pectinidz, 254, 2738.
Petroleum resources of the southern part of
Bondoc Peninsula, Tayabas Province, P. L.,
the geology and, 301.
Phenol, absorption spectra of, 83.
Phenoquinone, absorption spectra of, 51.
Philippine petroleum resources, 301.
Phthalanil, 413.
Phthalhydroxamie acid, the absorption spectra
of, 186.
Phthalic acid, 399.
anhydride, 401.
Phthalide, 401.
Phthalides and related compounds, the absorp-
tion spectra of various, 399.
Phthalimide, 404.
Phthalimidene, 406.
Phthalopfenone, 414.
anilide, 414.
Phthaloxime, 416.
Phthaloximes, the two: A study of their
absorption spectra and constitution, 165.
Phthalylacetic acid, 410.
Phthalylphenylhydrazine, 188.
Platypoda, 293.
Pleurotoma carinata Gray, 260, $26.
coronifera K. Mart., 260.
filavidula Lam., 380.
gendinganensis K. Mart., 260.
neglecta K. Mart., 260.
sp., §26.
suturalis Gray (7), 880.
tjemoroénsis K. Mart., 826.
Pleurotomide, 254, 260.
Plicatula Lamarck, 276.
imbricata Menke, 254, 276.
Polynices (Natica) mamilla Lam., 254, 266.
Portland cement, a bonus system for the
purchase of, 107.
Index
Potamides Brongniart, 269.
babylonicus (?) K. Mart., 269.
herklotsi K. Mart., 269.
noetlingi K. Mart., 269.
palustris, 269.
sp., 824.
PRATT, DAVID S. (Editorial) Copra spoil-
age on a large scale, 489; The absorption
spectra of various phthalides and related
compounds, 399; The optical efficiency of
tinted glasses in relieving eye strain, 193;
see Gipss, H. D., 33.
PRATT, D. S., and DEL ROSARIO, J. L,
Philippine fruits: Their composition and
characteristics, 59.
PRATT, D. S., and GIBBS, H. D., The absorp-
tion spectra of phenoquinone, 2,5-dianilino-
quinone, 2,5-dianilinoquinoneanil, and 2,5-
dianilinoquinonedianil (azophenine), 51; The
two phthaloximes: A study of their absorp-
tion spectra and constitution, 165.
PRATT, D. S., THURLOW, L. W., WIL-
LIAMS, R. R., and GIBBS, H. D. The nipa
palm as a commercial source of sugar. A
consideration of the principal difficulties en-
countered in collecting and preserving nipa-
palm sap, 377.
PRATT, WALLACE E., and SMITH,
WARREN D. The geology and petroleum
resources of the southern part of Bondoc
Peninsula, Tayabas Province, P. I., 301.
Prionastraea Edwards et Haime, 290.
(?) vasta Klz., 255, 291.
Psammosolen coarctatus Gm., 270.
Ptychocyathus (7), 289.
(?) incognitus Smith, 255, 289.
Pyrazisinus haitiensis Dall, 269.
Pyrula Lamarck, 264.
gigas K. Mart., $27.
SD., 834.
(Melongena) sp., 254, 264.
R
Radiolaria, 254, 281.
Ranella elegans Beck., 267.
, gyrina Linn., 267.
nobilis Reeve, 267.
raninoides K. Mart., 267.
sp., 880.
spinosa Lam., 267.
Red lead, analysis and composition of, 429.
REIBLING, W. C., A bonus system for the
purchase of Portland cement, 107.
Rhizopoda, 281.
Rimella Agassiz, 262.
javana K. Mart., 254, 262.
spinifera, 262.
Ss
SADDERA MAS6, MIGUEL, and SMITH,
WARREN D., The relation of seismic dis-
turbances in the Philippines to the geologic
structure, 199.
Index
Salicylic acid and its methyl ester, absorption
spectra of, 83.
Saponification in nonhomogeneous solutions, 1.
Scaphopoda, 292. .
Schizaster Agassiz, 291.
sp., 327. ei
subrhomboidalis Herkl., 255, 291, 825,
$26.
Seismic disturbances in the Philippines, the
relation of, to the geologic structure, 199;
discussion of important earthquakes, 224;
distribution of seismic disturbances, 216;
practical considerations, 231; summary of
the physiography of the Philippine Islands,
206; types of seismic disturbances, 212.
Septarea arenaria Lam., 330.
arenaria Linn., 292.
SMITH, WARREN D. Contributions to the
stratigraphy and fossil invertebrate fauna
of the Philippine Islands, 235; see PRamtt,
WALLACE E., 301; see SADDERA Masé6, Mi-
GUEL, 199.
Solenidz, 254, 270.
Solenoconche, 255, 292.
Solubility of methyl benzoate and methyl
methyl salicylate in water, 1.
Spatangide, 255, 291.
Spectra of various phthalides and related com-
pounds, the absorption, 399.
Spondylidex, 254, 275.
Spondylus Linnzeus, 275.
ducalis Chem. (7), 254, 276.
imperialis Chem., 326.
SD., 254, 276, 824.
Spongiz, 2389.
Stratigraphy and fossil invertebrate fauna of
the Philippine Islands, contributions to the,
235.
Strombide, 254, 262.
Strombus canarium Linn., 324, 830.
labiosus Gray, 825.
Sugar, the nipa palm as a commercial source
of, 377.
Sugar-cane experiments, 159.
T
Tagelus caribbeus Lam., 270.
(Solen) coarctatus Gm., 270.
Tapes rimosa Phil., 334.
Tayabas Province, P. I., the geology and
petroleum resources of the southern part of
Bondoc Peninsula, 301.
Telescopium telescopium Linn., 824.
TEMPONGKO, CLODOALDO,
experiments, 159.
Thalassinidz, 255, 293.
Thallophyta, 281.
Sugar-cane
449
THURLOW, L. W., see Pratt, D.'S., 377.
Tinted glasses, the optical efficiency of, in
relieving eye strain, 193.
Tridacna Bruguiére, 279.
gigas Lam., 254, 280.
Tridacnidz, 254, 279.
Tritonide, 254, 266.
Tritonidea Swainson, 258.
(Pollia) ventriosa K. Mart., 268, 258.
Trochocyathus nummiformis Duncan, 286.
Trochus fenestratus Gmel., 324.
sp., 826.
Turbinella ilocana Smith, 258, 257.
(Fusus) tjidamarensis K. Mart.,
258, 257.
Turbinolide, 287.
Turbo borneénsis (7) Bttg., 826.
sp., 825, 326.
Turricula Adams, 259.
batavianna K. Mart., 258, 259.
jonkeri K. Mart., 258, 259.
Turris Humph., 260.
(2?) agusana Smith, 254, 261.
(Pleurotoma) andaénsis Smith, 254, 260.
ecarinata Gray var. wood-
wardi, 254, 260.
flavidula Lam. var. sonde
K. Mart., 254, 260.
Turritella Lamarck, 267.
bantanensis, 267.
cingulifera Sow., 254, 267.
terebra Lam., 254, 267.
Turritellidse, 254, 267.
U
Undaria, 289.
V
Veneride, 254, 272.
Venus, 272.
Vermetus Adanson, 292.
giganteus K. Mart., 255, 292.
Vermitide, 255, 292.
Vicarya Jenkins, 267.
eallosa Jenk. var. semperi Smith, 254,
268.
verneuili D’Arch., 268.
Voluta Linnzus, 259.
sp., 258, 259, 824.
Volutide, 2538, 259.
Ww
WEST, AUGUSTUS P. Analysis and com-
position of red lead, 429.
WILLIAMS, R. R., see Gipps, H. D., 1; see
PrATT, D. S., 377.
x
XKenophora dunkeri K. Mart. (72), 825, $26.
sp., 826.
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