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Por wie yO PUL rete arb any wee re atic ery ok dala von e inter een ey nal RR GON ak ea Heiss Ky Ree Panay Rian *“ ean) et twee 41% Weyer we yan tele rok vals oth. al at 2 : vues > ¥ Lae we Oh, Sika pdiaienre vitae WE har aril ari eel UN iat eT ue mia Nahas ole: Wider 25 vue san _ Pike py bt Bh 4 Sah se vivavmey pa a va ore iis i reali an eee » Rey te rt tt cma ™ Ci i 46: lof he kg LA ae nse ae he * a ero Soe Kaniree a wena ae ae oS eee Derren uo merit 7 wa Seed: Cea te orks anes Raves MA pw ndleeeiyet isee Reade wipes fas Aw ; soe pops cs opti ee is {st -“ + 0 tes iprisetoney ears eet nites Pra " eee Baas * oo been tet Sieet ya faye Wes 0 he - Cee her rt se Sen h-oe4 sah wile No be. Note nee, Renn nee trees Soret: ests Arar ite r me mites pate Soa ee oti, ig AA, CDSS DO a i , hy P a) " ‘ H's ’ il " . ; ui, ; j . a) i 4 ’ | { ba fh 4a be: » | aM ei 2 / i tah alte MI mt 7 , 1 . SS eee Hit) ‘¢ 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 H. C. BRILL, Pu. D.; J. R. WRIGHT, Pu. D.; G. W. HEISE, M. S. J. C. WITT, PH. D.; T. DAR JUAN, A. B.; A. H. WELLS, A. B. R. C. MCGREGOR, A. B.; H. E. KUPFRER, A. B. VOLUME XII 1917 WITH 11 PLATES AND 12 Text FIGURES MANILA BUREAU OF PRINTING 1917 151034 CONTENTS No. 1, January, 1917 Briut, HARVEY C. The fermentation of Philippine cacao...................... HEISE, GEORGE W. The interaction of chloride of lime with the normal constituents of natural waters and sewage....................... Five text figures. BRILL, Harvey C. A chemical investigation of the seeds of Pangium elena Ob EL VOMOCAr pus: AlCa lee eee nccennpncenqneneecenencdnesceqecesnecanaenceacaze RI SAI Se a ae a ne er Rn uahae aw ommbenediisetvSttenret ities - No. 2, March, 1917 Cox, ALVIN J. The study of copra and other coconut products............ BRILL, HARVEY C.; PARKER, HARRISON O.; and YATES, Harry S. Rieu SSemmET ETT Cham COCONINO oes arses te ee Pe cee sean ae Pe ees reach uSceesucessatn PARKER, HARRISON O., and Britt, HARvEY C. Methods for the production of pure coconut oil.........................- Sy Sete i te CE NE oe BRILL, HARVEY C., and PARKER, HARRISON O. The rancidity of APEIIEPSTET MME CO COM Ga tOUle cree. CO ee re Ree cates nar ceeceane aoe menseccsderucsenncta No. 3, May, 1917 WELLS, A. H. Destructive distillation of Philippine woods................ BRILL, HARVEY C., and ALINCASTRE, CECILIO. The possible maximum vitamine content of some Philippine vegetables..........22.0..- Witt, J. C., and Reyes, F. D. The effect of calcium sulphate on PEMMOM Gre ens 2 bon ct-- a. Re eee et ace See ea eau eee mer nin Ret et Sere accent Loe cutets WRIGHT, J. R., and HEISE, GEoRGE W. The radioactivity of Philip- TE TNAVE. TESTIS carts accepts eae ae ne Be ca a toe eet ne eae ea One plate and 2 text figures. No. 4, July, 1917 e _ Britt, H. C., and WELLS, A. H. The physiological active constituents of certain Philippine medicinal plants: II Four plates. BRILL, HArveEy C. The antineuritic properties of the infusorial earth extract of the hydrolyzed extract of rice polishings................ BRILL, HARVEY C., and WILLIAMS, RoBERT R. The use of chaul- moogra oil as a specific for leprosy No. 5, September, 1917 BROWN, WILLIAM H., and ARGUELLES, ANGEL S. The composition and moisture content of the soils in the types of vegetation at different elevations on Mount Maquiling Three plates and 1 text figure. AGuiLAR, R. H. A comparison of linseed oil and lumbang oils as [DOB ENGI SG (Gp Rae ee aie ae SOLVE en ee pn One plate and 1 text figure. HEISE, GEORGE W. The crater lake of Taal Volcano One plate and 1 text figure. 111 127 133 145 167 199 207 221 iv Contents No. 6, November, 1917 BrILL, HARVEY C., and THuRLOW, Leavitr W. Alcohol from discard molasses: in) the Philippine Wslands:2=. 2). ee HEISE, GEORGE W. The radioactivity of the waters of the mountain- ous region of northern Luzon One plate and 2 text figures. HEISE, GEORGE W. The constancy in the radioactivity of certain Philippine waters Page. 267 293 309 313 THE PHILIPPINE i JOURNAL OF SCIENCE A. CHEMICAL AND GEOLOGICAL SCIENCES AND THE INDUSTRIES VoL. XII JANUARY, 1917 No. 1 THE FERMENTATION OF PHILIPPINE CACAO * By Harvey C. BRILL (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) In an article by me? the statement was made that “‘the necessity for fermenting or sweating cacao is now generally acknowl- edged.” This assertion “challenges trouble,” declares the editor of Tropical Life,? since “no two experts seem agreed on this matter.”” However, the consensus of opinion appears to be with the above statement.‘ Booth and Knapp, of Messrs. Cadbury Bros. Ltd., state: In general, we believe that if the planter only allows ripe pods to be gathered, ferments for a reasonable period, cures with care, and keeps the beans dry they will have the right appearance, and that he will be producing the best that the types of trees on his plantation will produce. * * * We understand that wnfermented cacao finds purchasers, but fermented cacao, always obtains the higher price; unfermented beans are more difficult to shell, and they produce an inferior cocoa. Partially fermented beans suffer from the same defects. W. H. Johnson, F. L. S., director of agriculture, Southern Provinces, Nigeria, says: Fermentation is more generally practiced than hitherto, but the period of fermenting and curing is too restricted. S. H. Davies, of Messrs. Rowntree & Co., while insisting that the fermentation is due to the action of wild yeasts in the beginning and that the later action is due to true yeasts, believes * Received for publication November 17, 1916. * The enzymes of cacao, This Journal, Sec. A (1915), 10, 123. * Smith, Harold Hamel, Trop. Life (1916), 12, 5. * Booth, H. P., and Knapp, A. W., Proc. Third Internat. Cong. Trop. Agr. (1914), 225 et seq. 146844 2 The Philippine Journal of Science 1917 that fermentation alone brings out the best flavor. Bainbridge and Davies * have shown that this flavor is due to the presence of an essential oil, which they believe is formed during the process of fermentation. The only discordant voice raised at this Congress was that of Professor Perrot, of the Ecole Supérieure de Pharmacie, Paris, who reported an experiment in which he submitted 200 kilograms of cacao, sterilized at the Ivory Coast, to one of the French chocolate concerns. When roasted, this cacao became fragrant and in no respect was inferior to the products obtained by fermentation in the same region. He states that the pulp was removed by means of potassium carbonate solution and that the color was a fine violet. These two properties, the tenacity of the pulp and the violet color of the ribs, are characteristic of the unfermented cacao and are reasons for fermenting, since both are undesirable. Knapp,°® in discussing the Perrot method, states that the beans had a compact, cheesy interior, that they dried more slowly than the fermented beans, and that the process would be more costly than the present methods and would require skilled labor. He concludes with a plea for the encouragement of the use of the best-known methods of fermenting by the planters. In his book on cacao, van Hall? says of fermentation: All based on the same principle and have the same effect. This effect is the development of an essential oil, which gives the cocoa its peculiar aroma; the conversion of part of the bitter-tasting compound, so as to lessen the bitter taste; and, finally, the liberation of the theobromine, the substance which gives cocoa its peculiar tonic and stimulating properties. These prominent authorities agree, with the exception of Professor Perrot, that the fermentation of cacao produces an improved product even though the changes taking place are not completely understood. To obtain various data that might throw some light on this process, the experiments recorded in this paper were performed. However, before this phase of the work is taken up, several other points will be discussed. Recently I have had an inquiry from the Hershey Chocolate Company in which a method for the improvement of the color in poorly fermented cacao was requested. * Bainbridge, J. S., and Davies, S. H., Journ. Chem. Soc. London (1912), 101, 2209. ‘Knapp, A. W., Trop. Life (1915), 9, 227. "Van Hall, C. J. J., Cacao. Macmillan & Co., London (1914), 201. XII, A, 1 Brill: Fermentation of Philippine Cacao 3 In my article dealing with the enzymes of cacao the state- ment was made that no glucoside-splitting enzyme was found in the forastero cacao examined at that time. Since this article appeared, I have made an investigation of the enzymes of the criollo variety and found that an emulsinlike enzyme which splits amygdalin, setting free hydrocyanic acid, exists in the latter. This same enzyme occurs in the forastero type, though not in as great activity. The enzymes found in the criollo and in the forastero types are identical in character, but in general they exist in somewhat larger quantities or more active forms in the former than in the latter. None was found that was peculiar to either type, and for this reason the results of the investigation of the enzymes of criollo are not recorded. The main difference is one of intensity of activity. The list stands as summarized for the forastero type in the preceding paper with the addition of an emulsinlike enzyme that exists in the unfermented seeds in some- what greater activity than in the fermented product. The cor- rected list for the fermenting bean is casease, protease, oxidase, raffinase, diastase, invertase, and emulsinlike enzymes. The Philippine Bureau of Agriculture, through its inspectors, has made a census of the various districts of the Islands for the purpose of obtaining information regarding the quantity of cacao produced and the methods of handling it. In only a few provinces was there more than enough raised for local consump- tion, but in most of them the presence of trees was n: ted, thus demonstrating that cacao will grow in many places in the Philippines. No conscious effort is made to ferment the beans, and the methods of preparation are very crude. These methods consist in drying the beans, without preliminary treatment, in the sun from three to six days, rubbing between the hands with ashes or rice husks to remove the pulp previous to placing in the sun, or mixing with rice hulls and sand and treading with the feet and washing to remove the pulp and then drying in the sun. While the quantity grown at present is small, the fact that the regions in which cacao can be grown are wide- spread throughout the Archipelago is encouraging. The ex- perience of other cacao-growing countries lends hope to the belief that the Philippine Islands may become important as a cacao-growing country. Tables showing the production in other countries, as recorded by van Hall,’ follow: "Ibid., 499. 4 The Philippine Journal of Science 1917 TABLE I.—Production of cacao by countries, in tons of 1,000 kilograms. | Increase or de-| “Y€F= | Country. 1908 | 1909 | 1910 | 1911 | 1912 | crease of 1912 | 305 Aechmea) i Pr ae for 5 | age over 1908. | years. | Tons. \P. cent. Tons. |\P. cont Gold Coast----- 12, 946 | 20,584 | 23,112 | 40,357 | 39,500 | 26,554 | 205.1 | 27,292 | 14,346 | 110.9 Ecuador 32,119 | 31,564 | 36,305 | 38,804 | 35,500 | 3,381 10.5 | 34,858 | 2,739 8.5 | San Thome ----| 28,728 | 30,261 | 36,665 | $5,000 | 35,500 | 6,772 23.5 | 33,231 | 4,503 | 15.7 Brazilises esas 32,956 | 33,818 | 29,158 | 34,994 | 30,000 |—2,956 | —9.0 | 32,177 | —779 | —2.3 Trinidad__-_---- 21,370 | 23,390 | 26,281 | 21,220 | 18,900 |—2,470 | —11.1 | 22,224 854 3.9 San Domingo--| 19,005 | 14,818 | 16,628 | 19, 828 | 20,900 | 1,895 9.1 | 18,285 | —770 | —4.0 Venezuela-.-_-- 16,303 | 16,848 | 17,251 | 17,381 | 12,500 |—3, 803 | —28.3 | 16,057 | —246 | —1.5 Grenada------- 5,159 | 5,441 | 5,846| 5,948 | 5, 500 341 6.6 | 5,579 420 8.1 Cy | eee eS 1,388 | 2,276 | 2,978 | 4,471, 38,500! 2,112; 152.2! 2,928; 1,535 | 110.6 German colo- | | MGS esse eee 2, 738 3,823 | 4,073 | 4,404! 5,400] 2,662 97.2 | 4,165} 1,427] 52.1 | Ceylon--.-_------ 2, 836 | 3,570 | 4,069 | 38,064} 3,500 664 23.4 | 3,408 572 | 20.2 | Fernando Po --) 3,001} 2,726] 2,349' 3,000} 2,300! —701 | —23.3 2,675 326} 10.8 | Jamaica --.----- 2,694 | 3,216 | 1,743 2,783 | 3,400 | 706 26.2 | 2,767 73 2.7 RWI secies Be 2,378 | 2,460] 2,579 | 2,460 | 2,000 | —8378} —15.5]| 2,375 | Se a a! | Surinam- ------ 1,699} 1,897; 2,043; 1,565) 1,000 | —699 | —41.1] 1,641 —68 | —3.4 ES hip eee 2,709 | 2,122} 1,851 } 1,485 | 2,000; —709 | —26.2} 2,033 | —676 _—24.9 French colo- | | | Mickieeeca==— 1,421} 1,372} 1,575; 1,364] 1,500 79 5.5 | 1,446 26) | 138 Cuba ase 827 | 1,940 | 1,412] 1,251 | 2,000) 1,173 | 141.8] 1,485 | 658 79.6 | St. Lucia ------ | 615; 553! 748/ 940} 900] 285] 46.3! 750} 185/ 21.9 Belgian Congo-_ 612 769 | 902 681 800 188 30.9 153 | 141) 23.0 Dominica-..--- 488 985 573 | 576 600 j12 23.0 | 644 | 156 | 32.0 Columbia ------ 621 | 730 297 400 400 | —221 —35.6 490 —131 |—2L 1 Costa Rica-_-_--- 340 235 184 343 400 60 17.6 | 300 | —40 |- 11.8 Other coun- | | | triesiss- 2.52 | 800 | 1,000} 1,000; 1,500; 1,600 700 87.5 | 1, 160 | 360, 45.0 | sa he | Be a ee ee | ee te Total! soos 193, 753 |206, 337 |219, 562 |243, 819 |230, 000 | 35, 747 | 17.9 |218, 868 | 25,567 | 11.6 | For the purpose of comparison and information the consump- tion of various countries is added. TABLE Ii.—Consumption of cacao by countries, in tons of 1,000 kilograms. Country. | 1908 | 1909 | 1910 | 1911 | 1912 42,615 | 53,379) 50,315 | 58,965 57,000 34,352 | 40,725 | 43,941 | 50,855 | 55, 100 20,445 | 23,254] 25,068 | 27,340 26,900 21,052 | 24,264; 24,082] 25,396 28, 100 15,821} 19,387) 19,187 | 23,586! 24,900 5,821 | 6,684 9, 089 9,852 | 10,300 6, 580 5,980 | 5,517 6, 379 | 5, 300 18,455 | 21,165 | 23,967) 27,665 | 32, 400 padunouoAd er0~ | Z°L8 | 8°68 | LST 88 |0°so | o‘ar | OST Pal 09 “poopy | N-7 wey? 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FAN a a re > > | Biel <5) & | 52 |f22 E58) 28 | Se an eee he |ex ej) 8.) a “10]09 | “t0pO 3 7135 = Re REG i Ae Gs | | B8/8s| & |es| ws) Ses] ge | $815 Bell S hg a enei| Reverie ec. lees R oo Stow!) sums aa Biot mee Gatierel Pele euy Nor me eee {COs | Gear lea Saale cea eget o0P SS EAS ODS ak ae eerie 9-4 OOF 1 fee le 9 Ops a| Fay 5 ae F- 00F Geers oe Ope "anit Soa eaees cae ae 00P auou |-oreqyser0g |--~~-~~------ n-a 082 hoe [ae opm--"---==o"" BWA oF rg ase 2 ODE ais ao een 3 I-L-0 oor ae em Opa ar 00 Cle ellie be) a= teed P S-d.L-9-9 eg ae eee 2 ener 00r Wye Iesi = OD Raa ere aa 4 dL-9-9 (HP y= Sa fae ae a B £-9- oF eet Neer = ODS sealer ae 1-9 00F Eee tae Le) ei | Sire Gk ea 9-9 Ci aime ot Fa op eee 9-9 00F | j Aime (i Ya ete Lee t-9 oo¥ a | es Ope Si age ey 2-0 00 = jeuou |-~- offopag |=-== === === n-o ‘sun \'sfing) | B | = = et < | ¥ | i) Te al ze (8s 8 ao | 5 §5 | ‘Ajewe, ‘ajduresg 2 Zo 1o as ‘ | *suneqg onona fo uoynzuaumsaf fo spoyjzew pun sajdwns fo uoydriosaq— A] TIAV I, Cacao ippine al Fermentation of Ph Brill XI, A, 1 ‘sUBeq paT[eYys ‘AIP ay} JUBaUL SI sqiu Ag y Sg pcs tela ye J\L-L- 88 poo os yon “FI-L-J Ueyy pedojeaap sso, yeymMoulog “sey Fee ae eae Ppedojasep A[ySIy ON “are pecnsee ag to Se 4-9-0} aBpIaNIg CaO A SS eee age ae 4-9-9 09 aBl!WS “p- 9F O-J UBYI JOpo ez¥joD049 peounoucad oso ¥28 0°SL 8°9L 8°18 b'r8 6°98 0°08 8°88 §°88 £°96 T Ls 0-Ss £68 9 °9& €°88 8°18 €s1 SOT 9L OFT Lot §L 981 TST v's L¥9 LT9 o°L9 9°ss 0°LS 81g o'99 9°9F €°G¢ £°8P 8 GF g°9P 08h 2'8P o-sy 98T Ty 66 TLT 98T 98 TL Ost OOP OOF S08 OOF 00F 008 ggg ooY ONO (=) r= be ww *L- 01048810, | 0} Q-q ABBA “L-O --- o7forag | 03 Q-9 eBvr0ay aac Op 8 Val d . os el a IN Poa t cas Ops} 8 O-La = Oise |ieeemmrnn Ci Om Bae ODsceallbercsaae aor ASO n 8 The Philippine Journal of Science 1917 This cacao was fermented by placing the wet beans in beakers, at the top and bottom of which were layers of cotton to retain the juices given off when the beans underwent fermentation and to prevent the too rapid escape of the moisture from the beaker. Twice daily the beans were removed from the beakers and care- fully stirred in order that they might ferment uniformly and that they might come in contact with the air. They were kept in an incubator at a temperature of 37.5° C. This was neces- sary, since the small bulk of seeds allowed the heat from the fermentation to escape so rapidly that, if left in the open air, the fermentation would have been very incomplete. Under these conditions the highest temperature reached by any of the samples was 45° C. The criollo fermented much more rapidly than the forastero. Active fermentation was practically complete at the end of four days, and a considerably finer product re- sulted, judging by the odor, color, and other organoleptic prop- erties. More difficulty was experienced in fermenting forastero. The fermentation proceeded considerably more slowly, and the temperature did not rise high enough to kill the germ of the seeds in all cases; consequently there was a tendency to sprout. In larger masses of the beans the temperature would undoubt- edly rise higher and the germ wouid be destroyed, but the above tendency illustrates the difference in the speed of fermentation of the two types under the conditions of the experiment. (a) Samples C-—6-y and F-6-—7 were sterilized by heating in hot water until the germ was killed and the activity of the enzymes destroyed. When the samples had become cool, yeast was added, and they were incubated. (6) The treatment of samples C-6-TD and F-6-TD was identical in all respects with that of samples C-6-y and F-6-7, except that taka-diastase was added instead of yeast. (c) Sample C—6-y-S had yeast added, but it was not sterilized. (d) Sample C-6-TD-S had taka-diastase added, but it was not sterilized. (e) Samples C-7-C and F-7-C had chloroform placed on the sterile cotton covering to prevent the introduction of yeast and of bacteria. From time to time additional amounts of chloro- form were added to take the place of the volatilized portion. (f) Samples C-7-T and F-7-T had toluene added instead of chloroform. The subsequent treatment was identical with that of samples C-7-C and F-7-C. (g) Samples C-7—A and F-7—A had alcohol added instead of chloroform or toluene. The subsequent treatment was identical with that indicated in paragraphs ‘“e” and “f.” mie A, 1 Brill: Fermentation of Philippine Cacao 9 Table V carries some further analytical data in regard to these samples of cacao. All these results are calculated on the basis of the water-free product in order that they may be directly comparable with each other and with the results listed in Table VI. All results were obtained from the shelled seeds. TABLE V.—Analytical data of Philippine cacao. [Numbers give percentages. ] ] ! Fes ne el ed | EE | g | | | 8 | | 8 | | a Se 3 3 . (28 Sample No. = | es) | E | E ic} Sac g] 4° Sr iee las 2 |B 8 Bul a 3 o & 2 $ i | Ago Bis 3 3 5 & = 3 =) | FE ste =e | 8 | 2 Soleo eee ee uel eB | sel re ee Biel |S labafels | a | 2.8 is (See 48.13 | 0.71, 12.18 | 0.73 | 2.08 | 3.62 | 4.88 | 14. 83 ! 16.25 | 5.05 | 2.39 | 4.06 = 52.27 | 1.27 | 12.81 | 0.63 | 0.85 | 5.14 | 4.31 | 14.18 | 12.88 | 5.57 | 2.16 | 3.39 aa Se - e 52.06 | 1.11 | 12.25 | 0.46 | 0.11 | 5.52 | 4.27 | 14.69 | 13.13 | 5.10 | 2.43 | 3.35 (Ch. ee 51.00 | 0.90 | 12.06 | 0.45 | 0.00 | 5.41 | 4.04 | 15.71 | 11.88 | 4.63 | 2.30 | 3.26 Gree ee 55.34 | 1.10 | 11.44 | 0.10 | 0.00 | 5.85 | 4.04 | 16.43 | 12.25 | 4.92 | 2.45 3.13 Cs ie 538.13 | 0.84 | 12.19 | 0.36 | 0.00 | 5.91 | 3.65 | 15.36 | 11.25 | 4.70 | 1.80 | 2.72 Ja. 56.69 | 0.84 | 11.38 | 0.27 | 0.00 | 4.58 | 2.88 | 11.12 | 11.08 | 2.95 | 1.63 | 2.77 (CHtHil ) pe 58.62 | 0.75 | 13.06 | 0.49 | 0.27 | 4.81 | 3.18 | 11.14 12.75 | 2.98 | 1.46 | 2.35 GRISUaS Sees 50.79 | 0.70 | 12.69 | 0.15 | 0.00 4.62 | 3.55 | 18.48 | 11.38 | 4.10 | 2.55 | 3.51 C-GIED-S - 252) 50.11 | 0.80 | 18.43 | 0.15 | 0.45 | 4.26 | 4.11 | 17.91 | 12.83 | 4.60 | 2.60 | 3.30 Cees 50.08 | 1.06 | 12.94 0.39 | 0.56 | 3.96 | 2.96 | 14.26 | 11.58 | 5.12 |} 2.12 | 2.70 oa) ae 46.12 | 1.10 | 18.19 | 0.77 | 0. 22 | 5.17 | 3.27 | 14.86 | 18.50 | 5.22 | 2.58 | 2.52 CHoi 45.64 | 1.20 | 12.75 | 0.92 | 0.10 | 5.36 | 3.59 | 14.63 13.88 | 4.90 | 2.32 | 3.82 ic) 2S Se 43.67 | 0.70 | 12.88 | 0.91 | 1.71 | 2.33 | 6.20 | 14.78 | 17.13 | 4.93 | 2.42 | 4.17 pee | 49.92 | 0.80 | 13.50 | 0.13 | 1.83 | 5.00 | 5.81 | 14.61 | 15.00 | 4.77 | 2.33 | 3.67 a | 49.93 | 1.05 | 13.00 | 0.02 | 1.38 | 5.18 | 4.83 | 18.94 | 15.00 | 4.98 | 2.42 | 3.74 ifS5 Lr 51.09 0.85 | 18.18 | 0.25 | 0.22 | 5.42 | 4.31 | 14.76 | 18.07 | 4.55 | 2.23 | 3.02 DST ae ene 52.21 | 0.88 | 18.91 | 0.21 | 0.45 | 5.49 | 4.20 | 14.21 | 14.18 | 4.68 | 2.20 | 2. 82 se eee oe 53.55 | 1.02 | 13.00 | 0.10 | 0.27 | 5.92 | 3.69 | 14.75 | 12.18 | 4.77 | 2.57 | 2.99 Da Tat epee eee 50.30 | 0.75 | 13.88 | 0.24 | 0.00 | 4.52 | 3.07 | 10.65 | 11.07 | 2.55 | 1.16 | 2.16 IPSS DE ee 55.99 | 1.00 | 13.88 | 0.05 | 0.40 | 5.07 | 3.385 | 10.71 | 8.85 | 8.25 | 1.38 | 2.03 net Lee ae 46.29 | 1.08 | 18.50 | 0.33 | 0.64 | 4.15 | 5.09 | 14.89 | 14.85 | 5.27 | 2.12 | 2.51 Uh S/ Gt e e 48.36 | 0.80 | 138.75 | 0.44 | 0.30 | 4.18 | 3.55 | 14.88 | 12.03 | 5.00 | 2.24 | 2.91 Daya \ es 41.67 | 0.85 | 18.69 | 0.87 | 0.61 | 4.56 | 3.55 | 14.44 | 12.50 | 4.98 | 2.22 ! 2.78 Average of C-U to C-7, inclu- BRveme eens 51.99 | 0.97 | 12.15 | 0.46 | 0.51 | 5.24 | 4.19 | 14.69 | 12.96 | 4.99 | 2.22 | 3.32 Average of F-U to F-7, inclu- 4.89 | 4.76 | 14.51 | 14.41 | 4.78 | 2.36 | 3.40 ® For general methods of analysis, see Parry, E. J., Foods and Drugs. Scott, Greenwood & Son, London (1911), 1, 20. For purposes of comparison some figures taken from a paper by Ridenour ® are entered in Table VI. I have recalculated these to the dry weight of the cacao in order that they may be directly comparable with the results of Table V. ° Ridenour, William E., Am. Journ. Pharm. (1895), 67, 207. 1917 Journal of Science ippine al The Ph 10 818 98°% 99°F 887 ory IL€ SLOT | 06k TPT | O27L 996 196 TOSE | OO°@E | 98BL | 9E°BT | OOS | LL CT 96S Tas 98°8 63°L 0&°9 ie) LIF &P 108 6L'T &FT Lga'é 86 °0 Ts 0 Sh T ve" 9L°9 Ae 6h" 9L°% 120 9F 0 SPT ue ¥6°% SIT OLT S6° Po ET STL SLOT | 86°L ShSE | G3°CL | SPST | 86°L 880 46°0 20°T 6L° 66 T 60°T 18° LIT 90 °0S 66 1S LOO | @h'6E | SLT | LLY | GL 6h | SL TS = “O10}8EI | “O][OIIO -oy ourddr ourddr | ‘ese | ‘uinur | ‘uinur | “oqAvo a) I “00 “UG AOF |-1!Ud 1OF) AOA W | -LUNAL | “XBW | -BABAL |-[Byoe HM! -sequyl, OSBIOAY jODVIDAY *{OadIp 19}}BU BATVORAYXT v 98°% 62 OL va VT 98 °S 19°9 89° 16 T TOL 6L° LS“9F 99° | 96's |e | 6F's 19"e— | 99°. | ses | 6e'6 oa2t | s6‘rr | o6'et | 09°FT 1s's | ss |go'9 | er'9 80° | L9°T | 2e'9 | 9P°9 19°T |9L°9 | ¥8° 9° vez |r | up'T | o8'T seIr | 2L"0r | onan | 94°6 oz | 16" 06° 22'T zy'6s | 00'9r | 19°9p | FO'LF | -emeg | SUV | ahr, | eaBe [‘seBezuco1ed aa1B sraquinny] 12° TZ P1 L0°LT Il'y 18° Le° €&T 28 “OT 86° vp eh “weu -1ang ysV 99°6 |--~7 77 n nr nennn- SAIQOBAAX Oe) ll eee asorniyag 9g°g 0 [rrnnvon voce nnn wUsry Sl eee yoaBig ol ee esor0ng dt ll abana Eee esoon[y TOT Geen sprourumnqyy ee eas eurmorqoayy, Lb tpp [trcoccor cence cece yg "eryeg *sa0un0s sno1pa wolf ovopa fo nynp ynI44NjnUup—IA BIaV]L xm, A, 1 Brill: Fermentation of Philippine Cacao A In Table VI a comparison is made of the analytical data | obtained for Philippine cacao and a number of foreign cacaos. | This comparison places the former in a very favorable light in | so far as such data are indicative of the quality of cacao. | An examination of the cacao butter was made to determine what changes, if any, took place in it with the variation in fermentation. TABLE VII.—Properties of cacao butter from Philippine cacao. a? 1 oa rs | Acid | | pcoel ca re Sample No. Jet Bake Peach Color. | Odor. : | per tion / gm. oil. eee. | poe ee Oe ee ee Ee ee eS 191.5 | 0.10 | 1.4600 | Light yellow. Deeper | Pronounced; somewhat than straw yellow. harsh. (Cos See ne 191.1} 0.17 | 1.4599 | Somewhat deeper than | Similar to preceding. C-U. | (C= a 198.8 || 0.27 | 1.4582 | Same as C-2 ___-_- ..__---- | Better than C-2. Faintly } harsh. GAT. ee 194.3} 0.23 | 1.4580 |-_-_- Gow sate ecee oes eae | Good; not so pronounced as f C-4. | CGS ee 192.6 |} 0.33 1, 4579 |____- (= (eee oe eee Bea Pleasant; esterlike. ; (tHe ee 192.4 | 0.44 | 1.4579 |____- dO oe yee sas | Do. } (Oey Tey ee ee 193.9} 0.18 ) 1.4580 |----_ (1 (yee Ae Sk oh hea mee Mild; not so characteristic \ | as C-7. | SGP D pia. os. 194.8 | 0.15 | 1.4580 |_____ tel San eee Le 1. “De i DO ee 191.0 | 0.14 | 1.4580 | Slightly lighter than Do. i | C-6-TD. (Cte MB oS 191.4 0.14 | 1.4580 |----- do ree eae wees Do i CAO ee 1192.2} 0.15 | 1.4579 | Almost water white______ Very mild; slightly sweet. | Cer... 193.6! 0.21 | 1.4581 |-__-. ay RGR aed Se | Not so mild as C-7-C. SE ay eee ea 191.7 | 0.18 | 1.4582 | Deeper yellow thanC-7-C_| Pleasant; chocolatelike. } Uy Aen P8t S ha - 192.7 0.18 | 1.4585 | SameasC-U. Similarto | Pronounced; not s0 evi- i | C-2. | dent as C-U. H 1057) 2 eee | 196.5 | 0.26 | 1.4590 | Somewhat deeper than | Similar to F-U. | (Mee ten a Spal aa See 198.5 | 0.58 | 1.4585 |____- ope PI BRTRS 4 ras 5 | Slightly better than F-2. 10a sts 3 eee 195.9} 1.09} 1.4582 |__... dO) Fe Se ae | Good; better than preced- | ing three. ! LOES v=, see ene 196.6} 1.27] 1. 4580 | Deeper yellow than F-5 2 Esterlike; pleasant. | Rete eee ee OBEN 2808) h4bRt Week dole seo kie - Aee | tee aDo, | ORT S oaeeee poe 192.4 , 0.17 | 1.4582 | Slightly lighter than F-7_} Faintly esterlike; less so i | than F-7. | Jovi t) Dee ee Baal 198.7! 0.25 | 1.4581 Deeper yellow than F-6-y_} Slightly harsher than i | F-G-y. i V7 Oe eee ee | 193.6 | 0.22 | 1.4579 | Sameas B62 9 ees ee | Not pronounced; pleasant. | JOR il ie aie ee 197.0 | 0.49} 1.4581 |--__- Clee oe ere Very pleasant. i 12 eo) ee ne ASG HIB) 14582 (st dows 2.6. bee tt) Do h Average for C-U | 192.6 | 0.26 | 1.4586 |.--------------------------- | to C-7, inclu- | sive. H } mverare for H Uh |) 195-0) || Os 90) ls 4b 84) eee em een ne eee eee | to F-7, inclu- | | sive. | | | 12 The Philippine Journal of Science 1917 DISCUSSION The loss in weight due to fermentation is given in Table IV. The criollo has the greater percentage of loss from fermentation. This is more apparent because the fermentation of the criollo was more nearly complete than the fermentation of the foras- tero. If perfect fermentation could be induced in the latter, the loss in it would undoubtedly approach that for criollo. However, a difference in the selling price of the fermented pro- ducts would be made in favor of the criollo because of its superior quality, and this would still allow more profit to be made from the cultivation of the criollo than from that of the forastero. Then, too, the latter, because of its slowness in fer- menting, is in greater danger of being spoiled by molding or by sprouting than is the former, and losses from this cause would be more apt to occur. On the other hand, the criollo samples examined had a larger average weight for the fruit, 531 grams, and a higher average yield of seeds, 27.9 per cent, than the forastero, which had an average weight of 481 grams and an average yield of 24.6 per cent of seeds. This would make the yields of dry, shelled seeds compare, criollo to foras- tero, as 1,089 to 1066; consequently, regardless of a difference in price in favor of criollo, the profit from its cultivation would be greater than from the cultivation of forastero, since the absolute yield of dry, shelled seeds, or nibs, is greater from the criollo than from the forastero. The greater rapidity of the fermentation of the criollo is demonstrated by the loss in weight due to the fermentation. The maximum loss in weight has been reached at the end of the fourth day, while the forastero shows a maximum at the end of the sixth day. The intensity of the fermentation is like- wise demonstrated by these same figures, for criollo shows a maximum of 8.5 per cent and forastero a maximum of 3.8 per cent. The changes effected by fermentation should be much less in the case of the latter, judged by the change in weight, and this is borne out by the less agreeable odor of the defatted »° cacao and the cacao butter. The odor is most pleasant between the third and fourth days for the cacao butter and about the fourth day for the defatted cacao in the case of the criollo type, while the fifth and sixth days for the cacao butter and the * By defatted cacao is here meant cacao from which all the fat has been etherized. x A; 1 Brill: Fermentation of Philippine Cacao 13 iifth and sixth days for the defatted cacao show the finest flavored product in the case of the forastero. But the product of this longer fermentation period for forastero does not equal that from criollo in quality. The changes brought about by fermentation are hard to de- monstrate by an analysis of the finished cacao. The changes are largely characterized by an improvement in its organoleptic properties. Bainbridge and Davies" believe that an essential oil is produced during fermentation. In their investigation on fermented arriba from Ecuador, they obtained 24 grams of an essential oil from 2,000 kilograms of cacao. Ordinary analytical chemical methods would not suffice for the detection of so minute quantities. The theobromine shows no regular variation. Sack” claims that one of the results of fermentation is the splitting of a glucoside with the formation of theobromine and cacao-red. The results obtained in this investigation do not corroborate his conclusions. The glucose and sucrose content change with the degree of fermentation, the latter in several cases being zero, while the former first decreases and then shows a slight increase. This increase is due to the action of diastase on the starch. The sugar usually listed as glucose in the analysis of fermented cacao is doubtless largely maltose, the product of the action of dia- stase on starch. The percentage of starch does not undergo a de- cisive change. The apparently smaller amount in C-U and F-—U is partly accounted for by the fact that these samples have not lost juices through fermentation. I believe a change has taken place in the character of the starch by the fermentation and that this makes itself apparent in the so-called break of fermented cacao. A change in the percentage of astringent matter with length of fermentation is the most apparent change that can be demon- strated by analytical data. The amount decreases with the length of fermentation and accounts for part of the improve- ment in the flavor of the product. The superiority of the criollo over the forastero is apparent when a comparison is made of the quantities of astringent matters present in the two. The difference in the cellulose content of the fermented and unfermented samples can be explained by the fact that the former has lost juices by fermentation while the latter still re- tains these. The same explanation holds for the difference in extractive matter. Van Hall states that good cacao should “ Loc. cit. “ Bull Dept. Agr. Surinam, 10. * Loe. cit. 14 The Philippine Journal of Science 1917 show 12 per cent or more extractive matter. The Philippine product averages slightly more than this. The free acidity of the cacao butter increases with the dura- tion of the fermentation. .Criollo is superior to forastero in this respect also. In spite of the greater intensity of the fer- mentation, it shows less free acidity than does forastero, the ratio being 0.26 cubic centimeter to 0.90 cubic centimeter 0.1 N alkali, respectively. The slight change in the acidity of the cacao butter with the greater length of fermentation is confirm- atory of the conclusion reached by me* that Philippine cacao does not contain a lipase. For the purpose of making a further investigation of the fermentation processes, certain special samples were prepared. These are described on page 8. An extended discussion of these samples is hardly necessary, since in no case is the quality of the final product equal to that obtained by the use of the ordinary methods. Samples C—6-y and F-6-y had yeast added to them after they had first been sterilized to destroy the activity of the enzymes. In the sterilization of the seeds care was taken to prevent cooking and at the same time effectively to sterilize. The final product did not equal C—6 or F-6 in excellence of odor, color, or break. It would appear that yeasts alone do not pro- duce the desired changes. Bainbridge and Davies ** make the statement that wild yeasts from the pods and stems first act on the pulp and that in the latter stages of fermentation their place is taken by true yeasts. The terms wild yeast and true yeast as used by these authorities are rather confusing. I do not believe the yeasts alone account for the changes cacao under- goes when it ferments, and the above results corroborate my belief. The yeast used for inoculation was the yeast found growing on the cacao; consequently no error could have arisen from a choice of the wrong yeast. For purposes of comparison and control, C-6—TD, C-6-TD-S, C-6-y-S, F-6-TD, F-6-TD-S, and F-6-y—S were run. These were no better than, and in some cases not so good as, C-6—y and F-6-y; therefore they add weight to the above conclusion that yeast is not solely responsible for the fermentation changes of cacao. To determine, if possible, the influence of the enzymes on the cacao, samples C-7-C, C-—7-T, C-7-A, F-7-C, F-7-T, and F-7-A were prepared. Extreme care was taken to prevent inoculation of the seeds when the pods were opened and the “ Loc. cit. * Loc. cit. — ei, A; 1 Brill: Fermentation of Philippine Cacao 15 seeds removed. In this endeavor I was successful, since at no time was any alcoholic or acetic acid fermentation apparent. These samples were examined in the same manner as the pre- ceding. The quality of the cacao was better than that produced by the action of yeast and taka-diastase in the absence of the enzymes, but the odor was not so fine as C—6 in the case of the criollo samples so treated, nor so fine as F—6 in the case of the forastero samples. Judging by these results, it would appear that the enzymes already existing in the cacao alone do not bring about all the desired changes, but that their influence must be reénforced by the enzymes from yeasts and possibly from bacteria or molds. The superiority or the peculiarity of certain cacaos is probably largely due to the presence of certain yeasts or molds during the fermentation process. Itis instructive to cite the belief of Preyer ** in this regard. He has isolated a yeast, Saccharomyces theobromae, from fermenting cacao. He recommends its use in the initiation of the fermenting process. The use of a pure culture yeast would necessitate extreme care in handling to prevent inoculation of the cacao with wild yeasts until the yeasts used for inoculation had attained a good growth. It would be impossible to sterilize the seeds, since such treat- ment would likewise destroy the enzymes, and the resulting product from enzyme-free cacao would not be satisfactory. The seeds as they exist in the pod are free from yeasts and bacteria, but handling of this in such a manner as to prevent contamina- tion is hardly practical. However, care in fermentation will yield a good grade of material provided the initial product is high class, so there is no cause for disconsolation because of the apparent impracticability of using pure cultures of yeast. SUMMARY Philippine cacao is compared with foreign cacaos. A study is made of criollo and forastero cacao fermented under varying lengths of time, and the respective influence of the enzymes and of yeast is investigated. The conclusion is reached that the Philippine Islands can grow a good quality of cacao in large quantities and that the time seems opportune for such an innovation. The investigation leads to the belief that the fermentation is the joint result of the reaction of yeasts and of enzymes. * Preyer, A., Tropenpflanzer (1901), 5, 157. Dj ah ee Bri a + os : oe Aare 1 BAA one ie eet! ae i: i ate he Fi wa ' : THE INTERACTION OF CHLORIDE OF LIME WITH THE NORMAL CONSTITUENTS OF NATURAL WATERS AND SEWAGE ' By GEORGE W. HEISE FIVE TEXT FIGURES (From the Laboratory of General, Inorganic, and Physical Chemistry, Bureau of Science, Manila) In the course of an extensive study of the sterilization of water and sewage, parts of which have already been reported, (9) it became necessary to do considerable work on the decomposi- tion of chloride of lime (calcium hypochlorite) in water and on its interaction with waters and sewage. The work was done because of its practical importance, and no attempt was made to study in detail the chemical reactions involved; the results are presented at this time because of their possible application to sterilization problems involving the use of hypochlorite solutions. The value of chloride of lime as a disinfectant was first pointed out by Koch(12) in 1881, while its application on a large scale to the sterilization of water for municipal supply was first proposed in 1894 by Traube.(23) That waters containing hydrogen sulphide or relatively large quantities of organic matter are not readily sterilized with chloride of lime was shown by Lode(14) in 1895. Since that time hypochlorites have been so widely used for the disinfection of water and sewage that their decomposition and their interaction with the substances normally found in water and sewage have been much studied. Hypochlorites in distilled-water solution decompose, even in the dark, with measurable velocity.(2) Both chlorate and oxygen are formed, although the main reaction proceeds accord- ing to the equation 2NaClO —> 2NaCl - O.. The decomposition is accelerated by heat, proceeding in accordance with the equation: (2) 3NaClO — NaClO, + 2NaCl, and ZNaAClO) ->"2NaCl =="O; The results of Bhaduri(2) indicate that for certain concen- trations in the dark at 100° C. the reaction is monomolecular, * Received for publication December 1, 1916. 1468442 17 18 The Philippine Journal of Science 1917 although its order has not been determined experimentally. The photolysis has been studied quantitatively by Lewis,(13) who concluded that the reaction was probably monomolecular. When waters contain foreign substances either in solution or in suspension, the decomposition rate of hypochlorites is gen- erally markedly changed. Bhaduri(2) found that in the dark a sodium hypochlorite solution was most stable when the con- centration of sodium hypochlorite was 1.5-1.7 per cent; of salt molecules, approximately 0.4 per cent. In the light,(13) alka- line is more stable than neutral sodium hypochlorite solution. Concentration and temperature have very little effect(6) on the stability. Elements of the iron group accelerate decomposition ; the presence of magnesium and aluminium increases the instability when the alkalinity is low. Elmanowitsch and Zaleski(4) found that acids increased, while alkalies decreased, the amount of (calcium) hypochlorite decomposed (at boiling temperature) by natural waters. Such factors as temperature, alkalinity, and the presence of phenols and hydrogen sulphide promote the decomposition of hypochlorites in sewage. (5) The accelerating influence of a high organic content in water on the decomposition of hypochlorites has been much studied. Asparagin, peptone and allied products, (8) albumin and its decom- position products,(4) sewage,(5) urine, sweat, saliva, and body products in general(10) have an especially great effect on the chlorine consumption. Apparently there is no direct paral- lelism between oxygen-consuming capacity (as measured by the reduction of permanganate solution) and chlorine-consuming power, (14) this no doubt due partly to the well-known inaccur- acy of determinations of oxygen-consuming capacity in regard to both quantity and kind of organic matter present in water, partly to specific interaction between the substances in water with chlorine. At first the disappearance of available chlorine from chlorin- ated water or sewage is very rapid, but it soon becomes slow. The reaction proceeds as though there were present, in some wa- ters at least, substances which are so readily oxidized by chlorine that they take it up before it can destroy the bacteria present. Although the bactericidal action of chlorine occurs simultan- eously with the chemical decomposition, the latter might pro- ceed rapidly enough greatly to impede or even to nullify the former. After the chlorine is once destroyed, bacterial growth might proceed unchecked, which furnishes a possible explana- tion for the repeatedly noted phenomenon—the great increase Kil, A, 1 Heise: Chloride of Lime 19 in bacterial content of waters in municipal distribution systems at varying periods after chlorination. (15) Much work remains to be done on the substances formed by the interaction of hypochlorites with the organic matter found in water. It is because of these substitution pro- ducts (16,20) that chlorinated waters used for public supplies often retain a peculiar chlorine odor and taste after all chem- ical trace of free chlorine has disappeared. In such cases—(21) these tastes and odours are not occasioned so much by chlorine or hypo- chlorites themselves as by inorganic and organic chloramines, and possibly other chlorine-substituted compounds formed by interaction with the organic matters present in waters. * * * They [the chloramines] are all germicidal, and all possess a more or less disagreeable odour. * * * He [Rideal] proved that chlorine * * * was working by substitution for hydrogen in ammonia and organic compounds, yielding products [chlora- mine and hydrazine] of higher germicidal power than chlorine itself. Race(19) found that when ammonia was added to hypo- chlorites, in the proportion of 1 part ammonia to 2 parts of avail- able chlorine, the germicidal action was increased threefold. While the addition of alum causes an immediate reduction in. available chlorine, it has no apparent effect on the bacte- ricidal properties of the solution for twelve hours, according to the findings of Avery and Lye.(1) With waters high in organic matter it is probable that the main chemical change follows the course of a monomolecular re- action as in the case in the decomposition of hypochlorites in distilled water. However, there are, apparently, so many simul- taneous reactions that the accurate determination of the veloc- ity constant is not easy. From the fact that, in general, the amount of chlorine consumed by sewage in a given time is pro- portional to the amount of chlorine added, Glaser(5) concluded that the reaction is monomolecular. Race(18) followed the course of the reaction between hypochlorites and a colored water and came to the same conclusion. The effect of light, though a most important factor in the decomposition rate of hypochlorites, has been frequently over- looked or at least insufficiently emphasized, so that some of the work which has been done is not conclusive. The importance of this factor in the sterilization of swimming pools has already been discussed. (10) EXPERIMENTAL PART Determination of available chlorine.—For the work recorded in this paper, chlorine was quantitatively determined in the 20 The Philippine Journal of Science 1917 usual manner by titration with standard sodium thiosulphate solution in the presence of phosphoric acid, potassium iodide, and starch solutions, care being taken to keep such factors as temperature and concentration as uniform as possible to en- sure comparable results. Phosphoric acid was used instead of hydrochloric or sulphuric acid, because errors in titration due to the presence of ferric iron and chlorates are thus avoided. (11) The following graduation(4) of this determination, on the basis of the color of the iodine-starch reaction in the presence of hydrochloric acid, serves very well for the estimation of very small quantities of chlorine in 200 cubic centimeter samples: Doubtful, when Cl content is 0.11 mg. per liter. Barely noticeable, when Cl content is 0.12 mg. per liter. Noticeable, when Cl content is 0.18 mg. per liter. Weak, when Cl content is 0.17 mg. per liter. Distinct, when Cl content is 0.24 mg. per liter. Sharp, when Cl content is 0.4 mg. per liter. The decomposition rate of calcium hypoclorite solution in the dar/c.—In order to study the decomposition rate of hypochlorites, known quantities of standard filtered chloride of lime solution were added to water in large glass jars provided with ground glass covers. Aliquot portions were pipetted off from time to time and analyzed. Whether the reaction was followed in distilled water, natural (artesian or river) waters, in solutions of organic substances, or in sewage, the decomposition curve had the same general trend. At first there was a rapid disappearance of chlorine, followed by an abrupt slowing down of the reaction. This sudden change of velocity generally occurred within from thirty minutes to one hour, after which the reaction proceeded very slowly, but very regularly, showing no sign of reaching an end point, though followed for weeks. Therefore it appears probable that the main reaction between chloride of lime and dissolved substances quickly approaches completion, after which the curve of gradual decomposition in water is followed. The experimental data se- cured are shown in Table I. The results for sewage were the most striking, and as they are apparently tyvical, on a large scale, of the reactions occurring in the other liquids, they are shown graphically in fig. 1. For the sake of completeness, the data for distilled water are plotted in fig. 2 for the entire eight hundred ninety hours during which the reaction was under observation. The curve appears to be typical for all of the reactions in the table. Though the XU, A, 1 Heise: Chloride of Lime 21 reaction was carried on in a small dark room the daily temper- ature variation of which was probably less than 3°C., the temperature change no doubt affected the results somewhat. Experimental errors appear somewhat exaggerated on the curve, because of the large scale on which chlorine concentrations are Time in minutes. Parts per million. Available chlorine. shown. The abrupt change in velocity indicated in fig. 1 does not appear in fig. 2, owing to the small scale on which time is plotted in the latter. TABLE I.—Decomposition of chloride of lime in the dark.* 99 The Philippine Journal of Science 1917 IN DISTILLED IN 5 LITERS DIS- IN SEWAGE. WATER. TILLED WATER ; : PLUS 0.1 GRAM Tc ey AMMONIUM ceo Qs, ACETATE. eee S58 sefeon gi one ‘ ome 62 | Time. ir] 5 Time. cian) =r. SF Sie oa Bas mek | = PH eral Ti 2m < | < pe BES: = on oe | Sof | ain il | aE a Hrs. mins. Ars. mins. | | < 0 oO | b228.0 OF 0 Reet. r 0 21] 116.0 0 6 36.0 Hrs. mins. 0 6 | 100.0(2) Oven 35.5 | 0 0 | »86.0 one 38.0 0 15 35.1 0 =r6 35.0 0 95.2 ebiteaGor are! 34.8 | 0 2 34.2 0, 49 80.5 5 43 34.4 0 32 30.8 21 20 22.0 23 34 33.1 0 37 30.7 Pada 14.5 29° 15 33.0 BY) 5. 00 Bh kp oltapiay 48 0 32.5 5 (0) |) 495 Bieta | taato 7 0 31.0 5 35 4.47 HNO) danse are 98 0 | 30.6 22 «0 3.78 ed Ao My MeR Sate ie 194 0 | 29.6 46 0} 3.15 lo cy. | agi 890 0 | 26.6 73 0 2.8 0. gl apap 7 | 45 (0 2.1 0 1 | 102.0 | IN ARTESIAN PSS arig eae OP 48 7856). WELL WATER. IN 0.001 MOLAR 0 15 | 65.5 P ses OXALIC ACID.¢ apie Hh o o | bsa4 | - Ue MN | H | b: % | 0 4) 87.9 | Onn0 37.0 | 0 ee ay 8 0 10 34.2 eeu ad 9.6 (Weep. lias 35.5 0 16 34.2 0 9 4.5 oD a8 35.4 | 0 54 33.9 0 27 stl 0 32 33.3 | 5 0 | 83.5 0 55 | 24 1 haat ea tity 23 «0 32.7 3 46 1.9 ion 28.7 30 0 32.4 Simpl 2.0 1 Seige an 20.7. | 54. OO 31.5 23 «0 1.4 | Sa e | 7 oO | 381.0 peau ‘In this and subsequent tables some of the experimental results were verified by R. H. Aguilar, chemist, Bureau of Science. » Calculated. ¢ The decomposition of hypochlorite proceeded so rapidly in 0.1 molar oxalic acid solution that it could not be followed quantitatively. TABLE II.—Decomposition of a solution of chloride of lime in tap water in diffused daylight. | | | Available | Available | Time | Barteper | Time | Barto per | million. | million. | ataeacoy Hrs. mins. 0.8 0 10.0 0.6 2 9.7 0.3 45 8.5 | trace 1 25 7.9 be 3 45 7.0 <0, A, 1 Heise: Chloride of Lime 23 Time in hours. 4 ao azo 0 700 =240 280 320 =—380 200 864460 «8480 =6S$2?0 §=6$60 600 640 680 720 760 @00 840 860 Parts per million. Available chlorine. Fic. 2. The decomposition of chloride of lime in distilled water in the dark. The data at hand for the progressive decomposition of chloride of lime do not show clearly the order of reaction. The decom- position in sewage is probably a heterogeneous reaction. (17) Fig. 1 shows that for a time the reaction velocity was practically constant ( oa Ke Kee The decomposition rate of calcium hypochlorite solution in the light.—In the light the decomposition more nearly approached the typical rate of a monomolecular reaction. The data obtained in a typical series of determinations are given in Table II and are plotted in fig. 3. Comparison with fig. 1 shows clearly the difference between the course of the dark and the light reaction. As indicated in the curve, the photochemical decomposition pro- ceeded inaregular manner. As the experiments were performed in the diffused light of the laboratory, the light was a variable factor and caused deviations from the true course of the pho- tochemical decomposition. It is interesting to note in this connection that in measurements of the decomposition of chloride of lime in different waters in the dark and in the light the differences between the amounts decomposed in the light and in the dark were very uniform for any given light intensity, regardless, within the limits observed, of the specific chlorine-binding power of the various waters used. This is evident from the data in Table III. The last column shows that for any one day the differences between the “light” and “dark” determinations were nearly the same, though the waters under observation varied widely in their ability to de- compose chloride of lime in the dark. 94 The Philippine Journal of Science 1917 Time in minutes. 20 40 60 80 100 120 140 160 180200 220 Parts per million. Seas baie Available chlorine = Fic. 8. The decomposition of chloride of lime solution in diffused daylight. TABLE II].—Hffect of light on chlorine consumption; 200 cubic centimeter samples of different waters digested two hours at 28°C. j j | Available chlo- | rine consumed. Day. Sample. renee! In dif- Ditier added. fused In | day- | dark. | | | light. | fet |e au ee me = oes = ee mg. mg. mg mq. Y il es ees ee Se mY Oe ee PS LR got PPS NE es 8a! Ee 2.9 0. 28 0.11} 0.17 Bistvep faces Se iS. nee ne ee Sie, pe eee 2.9 0.47 0.25 | 0.22 BD GR ke EE ge ed a nas 2.9, 0.14 0.14 | 0.00 AD Oe een tes eee tani! 6755 GS es aha Meu a 2.9 0. 45 0.45 | 0.00 Bh Sse cee, Oe Sa Eee ee ond ae Pp eee ERE ELE FUSE. 2.7 0.50 0.24! 0.26 Bho dce oe See oe bon ee eee Me ee ee Poa | 0. 66 0.45 | 0.21 @ | Que oe wee eee 2 Le tn ae ok Ae ee ee ee 201 0. 65 0.28 | 0.42 Fh ena e See eee ose a ote SOE Re ee = Sina Pia 0. 87 0.43! 0.44 B | in 20 cd Bee Soe. 2k Ee. ES en 8 ke a ae 2.77, 0.53 0. 23 | 0.30 | Be th pe ae 2 0. 60 | 0.28 0,32 ® Sky was heavily overcast, and laboratory was dark. XU, A, 1 Heise: Chloride of Lime 25 The interaction of chloride of lime and organic matter as affected by concentration.—lf the interaction of chloride of lime with organic matter is a monomolecular reaction, it follows di- rectly that the percentage of chloride of lime decomposed should be independent of the initial concentration. In other words, the amount of chlorine consumed in a given time should be a con- stant fraction of the quantity added. For example, (5) when the addition of available chlorine to sewage is doubled, the amount of chlorine absorbed will also be doubled, within certain limits, a fact which has an important bearing on the economical appli- cation of hypochlorites for disinfecting purposes. A good illustration of this regularity is shown in the following series of determinations on the interaction of chloride of lime and urea. Different quantities of filtered chloride of lime solu- tion, varying in strength from 2 to about 100 milligrams of available chlorine, were diluted to 100 cubic centimeters, placed in glass-stoppered bottles, and digested twenty-one hours in the dark at 28° C. with 2 cubic centimeters of 0.01 molar urea solu- tion. At the end of the digestion period the samples were anal- yzed, with the results listed in Table IV. TABLE. 1V.—Interaction of varying concentrations of calcium hypochlorite with urea. eee add- | Available chlorine ed as— consumed. ] stain eRe OR, | Gust cc. mg mg. mg 1.0 2.3 il 2.2 1.5 3.4 3.1 3.3 2.0 4.6 4.3 4.4 3.0 6.9 6.5 6.6 | 4.0 9.2 8.8 8.9 | 5.0 1S5") 11.0 11.1 6.0 13.8 13.3 13.3 7.0 15.3 14.9 15.5 8.0 18.3 LATA LCN PEG 20.6 20.0! 20.0 TOL 2259 POxBINy 22:2 15 | 34.4] 38.5} 93.8 20 45.8 44.5| 44.4 25 57.2 55.6 55.5 30 68.7 67.0 66.6 40 91.6 88.7 | 88.8 | 2 From the values obtained with 6, 8, 9, and 10 cubic centimeters of solution. 26 The Philippine Journal of Science 1917 Almost without exception the experimental results vary from the calculated values by quantities well within the range of ex- perimental error. Apparently this regularity holds good for wide ranges of concentration with many different substances.’ Even with fairly pure natural waters similar results may be obtained under certain conditions. Thus 100 cubic centimeter samples of a clear river water, boiled with varying amounts of filtered chloride of lime solution for fifteen minutes in diffused daylight, reacted as follows: TABLE V.—The interaction of a river water and varying quantities of chloride of lime solution at 100°C. aan | Chloride | Chloride of lime of lime | added as— consumed | as— | lAvailente Available | Solution. _ chlorine. | chlorine. | } | | | cc. mg. mg. 0.52 1 S86 eae {0.98 | 2 6.72 | 0.8 | The ratio of the amounts of chlorine consumed is approximately the same as that of the amounts added, namely, 1: 2: 3. With sewage there is a similarity of reaction, with some curious differences. The percentage of chlorine consumed may increase with increasing additions of chloride of lime, giving rise to the peculiar phenomenon that the available chlorine left is greater after digestion with small quantities of chloride of lime than after digestion with much larger quantities for an equal period of time. This observation was repeated too frequently to be cap- able of explanation on the ground of experimental error, though some series showed these abnormalities to a lesser degree than others. This irregularity in chlorine consumption is also evident in the data of previously published work. For example, Glaser (5) says in effect: As a matter of fact, there are at hand several experiments which deviate from the regular order, for instance, the progressive decomposition with ? Avery and Lye (1) found that upon the addition of alum to water the available chlorine was apparently reduced, within certain limits, in direct proportion to the amount of alum added. XU, A, 1 Heise: Chloride of Lime 27 a concentration of chloride of lime of 1:1000 recorded in tables 28 and 29 * * * [but] * * * a similar marked decrease in available chlorine could not be detected on repeating the experiments with the same concen- tration. It should be pointed out that there are other small deviations from the theoretical quantities of chlorine. The analytical data given in Table VI show clearly that at certain concentrations the reaction is completely changed and that the irregularities noted by Glaser were not due to experi- mental error. TABLE VI.—Decomposition of chloride of lime in fresh sewage" (concen- tration of chloride of lime expressed as milligrams of available chlorine). A. EFFECT WITH VARYING PERIODS OF DIGESTION. Series 1.> | Series 2.¢ | Series 3.4 _ || Series 4.4 Con- -| Con- Con- || Con- Added.; Left. | Left. sumed.| Left. | sumed. | Added. Left. all | —— 3.55 1.14 | 3.61 1.08 2.93 1.76 | 1.17 | 0.5 0.7 |} 4.69 3.45 1.24) 1.84] 3.85 2.76 1.93 || 2.34 | 1.3 1.0 3.32 1.37! 1.30 3.39 2.82 | 1.87) 4.69 | 2.9 1.8 0.50 8.88 0. 85 8.53 0. 48 8.90 || 7.03 4.4 2.6 9.38 0.58 8.80} 1.08 8.30 0.78 8.60 | 9.38 2.0 7.4 0.53 8.85.| 1.82 8. 06 0.38 9.00 || 11.71 | 1.2] 10.5 7.40] 11.35} 5.80] 12.95| 4.11] 14.64 || 14.09 0.5 | 13.6 18.75 | 7.17| 11.68| 5.55 | 18.20] 3.55! 15.20]|| 16.43| 0.8] 15.6 7.24 |°11.51| 6.50] 13.25] 4.08] 14.72 || 18.75 1.3| 17.4 | 2 tina ba ae eka St Ue eb apa ae a Ya BAO) ake wpa eed ie tea eee attest lie lata et ea he ePBY 7) et CC nes nat Sea esl ete Sadie pate [Uae bal LA ae eee | 25.8 | 5.6] 20.2 as dee ere ek Ree eS A tonal [eee rere Dee iueeo7e5 | 006 | [ue alle ee (Sel Ro a HESS UNF av bw |r biel] atl «“ Sewage, 50 cubic centimeters ; temperature of digestion, 28° C. > Time of digestion, forty-five minutes. © Time of digestion, one hundred minutes. 4 Time of digestion, eighteen hours. B. EFFECT WITH SEWAGE SAMPLES OF DIFFERENT AGES. Series 5. Fresh sewage. | Series 6. Same sample, after 24 hours. | Added. | Left. Consumed. | Added. | Left. Consumed. in == | | 7 | } | Per cent.|| | Per cent. | 1.10 0.07 1.03 | 94 1.00 0 1.00 | 100 | 2.20 0. 47 1.73 | 79 2.00 | 0.26 1.74 87 | 4,40 0.95 3.45 79 3.00 0. 42 2.58 | 86 | 8.80 0.24 8.56 | 97 4.00; 0.64 3.36 84 hoe tele 1.7 15.9 | 90 5.00, 1.10 3.90 | 73 | oe 1gSb2 15.8 19.4 55 6.00, 1.20 4.80 | 80 | 70.4 47.8 22.6 32 7.00} 1.90 5.10 73 | 8.00 1.35 6.65 | 83 10.0 1.00 9.00 | 90 30.0 15.8 | 14.2 | 47 40.0 25.2 14.8 | 37 50.0 | 33.5 | 16.5 | 33 | 28 The Philippine Journal of Science 1917 TABLE VI.—Decomposition of chloride of lime in fresh sewage (concen- tration of chloride of lime expressed as milligrams of available chlorine) —Continued. Cc. EFFECT WITH CONSTANT VOLUME OF LIQUID (CONCENTRATIONS OF CHLO- RIDE OF LIME EXPRESSED AS PARTS PER MILLION OF AVAILABLE CHLORINE). Series 7. Series 8. | Added. Left. Consumed. Left. | Consumed. | Per cent. | | | Per cent. 4.6 | 1.9! 2.7 | 59 | 0.6. 4.0 | 87 9.2 | 3.7 | 5.5 | 60 | 3.2 | 6.0 | 65 | 18.4 7.3 11.1 | 60 | 10.6 | 7.8 | 42 27.5 | 13,7 | 13.8 | 50 | 18.1 9.4, 34 | 45.8 | 16.4 29.4 64 | 28.0 | 17.8 | 39 | 64.2 5.2 | 59.0 | 92 | 27.5 36.7 BT 82.5 | 3.5 | 79.0 | 96 | 8.5 74.0 | 90 no | 6.0 | 154 94 | 4.0 106 | 96 ised. 28K 13.0 125 | 91 | 6.0 132 | 95 184 | 41.0 143 78 | 21.0 | 163 88 | 275 | 108 | 167 61 | 91.0 | 184 | 67 | 368 | 197 | 171 47 | ripe 197 54 460 249 | 211 46 258 202 | 44 690 | 445 | 245 | 36 | A723 218 | 32 | 920 707 213 | 23 690 | 230 | 25 | | 1,885 1,385 | 450 25) 1,415 | 420 | 23 2, 750 2,093 | 657 24 | 1,925 825(?) 30 | 4, 580 3,615 | 965 21, 3,380 1, 250(?), 27 | i] The foregoing data show the peculiar fact that with increasing additions of available chlorine the amount left after digestion first increased, next decreased, and finally again increased. For certain concentrations the available chlorine left after digestion was greater with small additions of chlorine than with much larger ones. The different series listed above were obtained on different days with different samples of sewage, so that the agreement between the results recorded is as good as is to be expected. As a matter of fact, different samples vary greatly and the same samples change with time, as indicated by the differences between series 6 and series 7. Owing to the change in the volume of the digested liquid, caused by large additions of chloride of lime solutions, discrep- ancies in the analytical results'-may occur. In series 8 these deviations were avoided by keeping the quantity of liquid constant by the addition of enough water to the first members of the series to compensate for the differences in volume caused by the ad- dition of chloride of lime solution. Typical series in the foregoing table are graphically shown in XU, A, 1 Heise: Chloride of Lime 29 fig. 4, the experimental data from Glaser’s(5) Table XXIX for 20-hour digestion periods being inserted for comparison. For use in this figure, the data in Table VI were recalculated as parts per million. Available chlorine added. Parts per million. 200 400-500 «800 1000 1200 1400 ___ {600 1800 __2000 __ 2200 _2400 2600 _ 2660 3000 Available chlorine consumed. Parts per million. Fic. 4. The decomposition of chloride of lime in sewage in the dark. Curve a, results of Glaser; curve b, Table VI, series 4; curve c, Table VI, series 7; curve d, Table VI, series 8. Effect of the concentration of substances reacting with chloride of lime.—The more concentrated the solution with which the chloride of lime reacts, the more chlorine is used up. This is to be expected, and it has been pointed out so often that it needs no further proof here. There is, however, a curious anomaly which may occur and which may lead to confusion in the inter- pretation of the ordinary laboratory tests of the chlorine-binding power of a water. The interaction of urea and chloride of lime in the dark at moderate temperature furnishes an illustration of this, when the decomposition of chloride of lime is measured in the usual manner, that is, by means of standard sodium thiosulphate, in the presence of potassium iodide, phosphoric acid, and starch. In Table VII are the results obtained when the same quantity of chloride of lime was allowed to react with different quantities of urea. They show that, for very low concentrations of urea, increase in concentration leads to increased chlorine consump- tion; with higher concentrations, however, the chlorine con- 30 The Philippine Journal of Science . 1917 sumption decreases. The results are also shown graphically in fie. 5: The scope of the work does not warrant a detailed study of this reaction * at this time. The results are presented because they are sufficiently definite to show the disturbing factors that may be present in the tests of the chlorine consumption of a water or sewage. Probably different chlorine-substitution pro- ducts are formed with different concentrations of urea, some of which react immediately with potassium iodide, liberating iodine, some reacting slowly or not at all, so that the amount of Urea additions in milligrams. so 100 1s0 200 250 300 350 +00 450 Parts per million. chlorine. Chloride of lime decomposed in terms of available Fic. 5. The decomposition of chloride of lime in urea solutions of varying concentra- tions in the dark. available chlorine left in solution may not be a true measure of the reaction. Since these products may have even stronger disinfecting action(21) than chloride of lime, the determination of chlorine consumed is not necessarily an index of the quantity of hypochlorite required for disinfection. According to Hairi,(8) the liquids in which the disinfecting action of chlorine is greatly retarded show a strong chlorine- consuming power. Ina solution of peptone, for example, neither the chlorine consumption nor the inhibition of germicidal action varies in the same manner as the concentration. * After this work had been completed, I found that Dakin (8) had reported a similar anomalous reaction between hypochlorous acid and sheep serum. XII, A, 1 Heise: Chloride of Lime 31 TABLE VII.—Interaction of chloride of lime solution with varying concen- trations of urea. [Water, 100 cubic centimeters; urea, additions as noted. Five cubic centimeters of chloride of lime solution digested eighteen hours in the dark at 28°C.] SERIES A. ADDITION—11.0 MILLIGRAMS AVAILABLE CHLORINE. ~ r zs | Urea. | Available chlorine. he | md, Sea oe Solution) Weight | | added. | added. | Consumed. Left. | cc. | g. | mg. mg. | ral 0 0.05 10.9 (5) 0.1 | 0.003 | 10.3 0.7 0.25) 0.007 | 10.8 (6) | 0.1 (4) | 0.50 | 0.015 | 10.8 (4) | 0.1 (6) 1.00 0.030! 10.8 | 0.2 | SERIES B. ADDITION—11.8 MILLIGRAMS AVAILABLE CHLORINE. Opelet0 0.1 11.7 | 0.5) 0.01 (5) | 11.5 (5) | 0.1 (6) A085 | MM OLOS Millen Tae 0.8 2.0} 0.06 11.4 0.4 | 3.0| 0.09 11.3 (5) | 0.4 (5) 4.0] 0.12 11.3 0.5 | 6.0| 0.18 11.2 0.6 7.0| 0.21 11.1) | 0.6 () | 8.0! 0.24 11.1 0.7 9.0} 0.27 11.0 0.8 10.0| 0.30 10.8 1.0 11.0] 0.33 10.6 (5) | 1.1 (5) 12.0} 0.36 10.4 1.4 | 18.0] 0.89 1018 te dee 14.0} 0.42 10.1 (eal 15.0| 0.45 9.9 Vek) | | 16.0] 0.48 918) al) v0 GENERAL DISCUSSION Since there is no direct parallelism between the oxygen-con- suming capacity and the amount of chlorine a water or sewage is capable of taking up, the determination of chlorine-consuming capacity, in spite of its limitations, is an important test in the laboratory control of hypochlorite disinfection. MHairi(8) di- gested 100 cubic centimeter samples with chloride of lime solu- tion in excess (13 milligrams available chlorine) and titrated after an hour in weakly acid solution. If digestion is carried out at constant temperature in the dark, this procedure will give concordant, relative values for the chlorine absorption. Elmanowitsch and Zaleski(4) recommended the determination 32 The Philippine Journal of Science 1917 of chlorine consumption at boiling temperature, with carefully regulated constant heating, for fifteen-minute digestion periods, with lime water added to the water under examination. The authors obtained very concordant results by this process. The figures given in Table V were obtained without addition of lime water, but show that the method is accurate enough for labo- ratory use. However, this method is open to objection, because it does not take into account conversion of hypochlorite to chlo- rate at boiling temperature. Digestion in the dark at room temperature is so easily carried out, and gives such uniform results if care is used in keeping conditions constant, that it is to be preferred to the methods employing heat. Whether chloride of lime shows fluctuations in bactericidal effect similar to those noted for its chemical decomposition (Table VI, fig. 4) is not clear. The results of Glaser(5) indicate that it does not, but these observations were made with such high concentrations of chloride of lime that they are not conclusive. It is true that the data under discussion were obtained in ex- periments on sewage, but apparently similar fluctuations may occur with ordinary water as well and with small hypochlorite concentration. Thus Stokes and Hachtel(22) in their work on the treatment of Baltimore spring water by calcium hypochlorite report that— when 1.5 parts of available chlorine per million parts of water were used there is practically no residual chlorine in the water. In one case when 1.75 parts were used there was a large amount of residual chlorine, giving an average .... of .574. On another occasion, however, when this amount was used the residual chlorine was less, giving an average of 0.24 per million parts of water. When 2.0 parts of available chlorine were used there was an average .. . of 0.206, and when 2.5 parts of available chlorine were used for treatment there was an average of 0.62 parts per million parts of water. These results, therefore, are somewhat variable, and it is hard to explain the greater amount of residual chlorine when 1.75 parts were used than when 2.0 parts were used. From the evidence at hand it is clear that the ordinary pro- cedures for determining the amount of interaction between hy- pochlorites and waters and sewage are influenced by so many factors that, unless very carefully interpreted, they are very likely to be misleading. If it were only the available chlorine that had germicidal action, the analytical control of hypochlorite sterilization would be relatively simple. Even in this case, how- ever, the quality of a water would be an important consideration, since waters differ widely in their ability to liberate chlorine from hypochlorites.(21) Thus two different waters brought to XII, A, 1 Heise: Chloride of Lime 83 this laboratory were treated with chloride of lime solution and immediately titrated with sodium thiosulphate in the usual man- ner. Acidified, 100 cubic centimeter samples showed 6.5 milli- grams of available chlorine, whereas unacidified samples showed only 2.4 and 4.0 milligrams, respectively. Since the amount of chlorine taken up by water or sewage depends upon the amount and concentration of chlorine added, on the temperature and time of digestion, on light, and on the quality of the liquid studied, it is obvious that, at best, only relative data, available for laboratory control of disinfection problems, are obtained by the methods ordinarily employed. Such determinations do not necessarily give any indication of the presence of germicidal products formed by the interaction of hypochlorites and the in- gredients of waters and sewage; hence they lose much of their significance for disinfection problems unless they are studied in conjunction with bacteriological data. In all cases, the chlorine consumption should be determined as nearly as possible under the same conditions of temperature, illumination, and concen- tration that obtain in actual practice. SUMMARY The decomposition rate of chloride of lime in water, sewage, and solutions of organic substances was studied. In the dark, at 28° C., the reactions proceeded with almost constant velocity for periods of thirty minutes to one hour, after which they pro- ceeded very slowly. In the light the decomposition rate was greatly accelerated. In general, the amount of available chlorine consumed is pro- portional to the concentration in which it is added, as shown by the interaction of chloride of lime and urea solution. However, for certain definite concentrations of sewage this regularity fails. A study of the reaction between chloride of lime with varying quantities of urea showed that the chlorine consumption, as meas- ured by the starch-potassium-iodide reaction, is not necessarily proportional to the concentration of organic matter. The determination of the chlorine consumption of a water or sewage, though of importance in the control of hypochlorite disinfection, is not sufficient in itself and should be supplemented by bacteriological tests. 1468443 34 (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (18) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) The Philippine Journal of Science 1917 REFERENCES Avery, C. R., and Lyn, 0. G. Ann. Rep. Prov. Bd. Health Ontario (1914), 33, 150-155; Hap. Sta. Rec., 34, 885, through Chem. Ab. (1916), 10, 2780. BuHaApDuRI, I. Zeitschr. f. anorg. Chem. (1897), 13, 385. DAKIN, H. D. Brit. Med. Journ. (1916), 852-854. ELMANOWITSCH, N., and ZALESKI, J. Zeitschr. f. Hyg. (1914), 78, 461. GLASER, E. Arch. f. Hyg. (1912), 77, 165. GRIFFIN, M. L., and HEDALLEN, J. Journ. Soc. Chem. Ind. (1915), 34, 530. Grimm, N. Mitteilung aus der Priifungsanstalt fiir Wasserversorgung u. Abwasserbeseitigung (1912), No. 16, 297, through Chem. Zentr. (1912), 83, II, 625. Harri, E. Zeitschr. f. Hyg. (1918), 75, 40. HEISE, G. W. Phil. Journ. Sci., Sec. A (1916), 11, 1-18. HEISE, G. W., and AcuiLaR, R. H. Phil. Journ. Sci., Sec. A (1916), 14, 204, KEDESDY, E. Mitt. kgl. Materialprifungsamt (1914), 32, 534, through Chem. Ab. (1915), 9, 2044. KocuH, R. Mitt. a. d. kaiserl. Gesundheitsamte (1881), 1, 234-282. Lewis, W. C. McC. Journ Chem. Soc. (1912), 101, 23871. Lopr. A. Arch. f. Hyg. (1895), 24, 286-264. Lonciey, F. F. Am. Journ. Pub. Health (1915) 5, 918. MEISENHEIMER, J. Ber. d. deutsch. Chem. Ges. (1913), 46, 1148. MELLOR, J. W. Chemical Statistics and Dynamics. Longmans Green & Co., London (1914), 124 et seq. Race, J. Journ. Am. Water Works Assoc. (1916), 3, 489. IDEM. Can. Engr. (1916), 30, 345, through Chem. Ab. (1916), 10, 1565. RASCcHIG, F. Chem. Zeitg. (1907), 31, 926. RIDEAL, S., and RIDEAL, E. K. Water Supplies. D. Appleton & Co., New York (1915), 190 et seq. STOKES, W. R., and HAcHTEL, F. W. Am. Journ. Pub. Health (1916), 6, 1224-1235. TRAUBE, M. Zeitschr. f. Hyg. (1894), 16, 149-50. Fie. 1. . The decomposition of chloride of lime in distilled water in the dark. . The decomposition of chloride of lime solution in diffused daylight. . The decomposition of chloride of lime in sewage in the dark. Curve ILLUSTRATIONS TEXT FIGURES The decomposition of chloride of lime in sewage in the dark. a, results of Glaser; curve b, Table VI, series 4; curve c, Table VI, series 7; curve d, Table VI, series 8. . The decomposition of chloride of lime in urea solutions of varying concentration in the dark. 35 ’ pe ay y i gona bedbia Saale yo ah paves re ‘oral cohistn TD 9: ae ithe tyne eric opel Na ahs ‘dali taeap Bes Recreate: feeb tna usual ariatti cal oae RE Re, RGLA i: Ball SOOO IEG pee 2 isk a pu ’ ry Le i's ane eh, A CHEMICAL INVESTIGATION OF THE SEEDS OF PANGIUM EDULE AND OF HYDNOCARPUS ALCAL4? By Harvey C. BRILL (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) In an article? describing the investigation of the seeds of Hydnocarpus venenata and the properties of the oil from these seeds, announcement was made of the continuation of this in- vestigation on the oils from seeds of various related plants growing in the Philippine Islands. The examination of such seeds was undertaken because of the fact that they are closely allied to the genus Hydnocarpus, which is closely related to the genus Taraktogenos, in order to determine if they have properties similar to the seeds of the latter. Chaulmoogra oil is obtained from Taraktogenos, but without doubt much of the oil sold as chaulmoogra is obtained from Hydnocarpus, since the chemical properties of certain of these oils are practically identical with the properties of chaulmoogra oil, which would make substitution easy and practically impossible to detect. Data concerning the seeds of Pangium edule Reinw. and Hydnocarpus alcale C. DC. are herewith presented. PANGIUM EDULE REINWARDT Pangium edule is indigenous to the Malayan Archipelago and is found in various parts of the Philippine Islands. The seeds are flattened; their average size is about 5 centimeters long by 3 centimeters wide. They are embedded in a crustaceous peri- carp, which is about 22 centimeters long by 15 centimeters in diameter. Mature and immature seeds were examined. The Pangium edule seeds used by me were furnished by the Philippine Bureau of Forestry. De Jong * announces the isolation of a cyanogenetic glucoside from the leaves of Pangium edule that is identical in all re- spects with that found in Gynocardia odorata by Power et. al.* ' Received for publication November, 1916. ? Brill, Harvey C., This Journal, Sec. A (1916), 11, 75. 7De Jong, Awk., Recueil des travaux chimiques des Pays-Bas et de la Belgique (1909), 28, 24; ibid. (1911), 30, 220. ‘Power, F. B., and Lees, F. H., Journ. Chem. Soc. London (1905), 87, 349; Power, F. B., and Barrowcliff, M., ibid. (1905), 87, 896. 37 88 The Philippine Journal of Science 1917 and named gynocardin by them. As the glucoside is accom- panied by an emulsinlike enzyme, gynocardase, in the plant, any delay in working up the seeds or leaves entails a loss in the glucoside content, due to its hydrolysis by the enzyme. In order that this loss might be reduced to a minimum, instructions were given to the Bureau of Forestry rangers to heat the seeds in boiling water for one hour, insuring the destruction of the gyno- cardase, and then to dry them in the sun before delivery to the Bureau of Science. In spite of this precaution, in several cases an odor of hydrocyanic acid was noticeable when the seeds were received, showing that hydrolysis of the glucoside had taken place. These particular samples were not dry. Owing to the lateness of the rainy season and the prevalence of rain, it was impossible for them to be dried properly before shipment and they molded somewhat in transit. Dox* has shown that molds formulate all the known enzymes, regardless of the character of the substrase; consequently the small amount of glucoside present in some of the seeds received may have been due to the action of enzymes formed in this manner. As stated, both ma- ture and immature seeds were received and examined. The mature seeds in no case gave any large amount of hydrocyanic acid when tested for the presence of gynocardin. The failure of strong positive tests cannot be attributed to the hydrolysis by molds in every case, since of the several samples of mature seeds examined not all were molded. It would appear that the amount of this glucoside decreases as the seeds ripen. A de- crease in the quantity of glucoside would appear plausible if one holds to the theory that its function is to sterilize any injury received by the fruit and thus prevent further injury from the introduction into the wound of molds and bacteria. With the maturity of the fruit the need for this protection would cease to exist. Upon receipt, the seeds were immediately shelled, placed in the oven and dried, and then ground. In some cases the oil was removed by extraction in a large syphon-extraction apparatus, by means of petroleum ether; in others most of the oil was removed by expression as is done in the preparation of amygdalin from almonds; in some others the original ground seeds were extracted with alcohol, which extracted only a small amount of the oil, but removed the glucoside. By evaporation to dryness and extrac- tion of this residue with ether the oil could all be removed and the black gummy residue treated for the isolation of gynocardin. ° Dox, A. W., Plant World (1912), 15, 40. ee ee xu, A,1 Brill: Pangium edule and Hydnocarpus alcalze 39 Where immature nuts were being handled, the most successful method for their treatment was the following: The ground nuts were triturated with hot water, allowed to stand for some time, expressed, and the process repeated. The water was removed by distillation in a partial vacuum, the black gummy mass was triturated repeatedly with hot 90 per cent alcohol, and the alcohol was removed by distillation in a partial vacuum or more slowly at not too high a temperature at atmospheric pressure. The residue was repeatedly extracted, this time with hot absolute alcohol, and ether was added to the extract until a precipitate no longer formed. The extract was evaporated to dryness, and the residue was washed a number of times with acetone in the cold. In some instances this treatment left a semiviscous mass that: could be crystallized from water. In a few instances the residue was dissolved in hot acetone and the acetone evaporated. However, gynocardin is not readily soluble in acetone, and as a small amount of fat persistently adheres to the glucoside and this is dissolved by the acetone along with the glucoside, dissolving in water preceded by washing with cold acetone was found to be more successful in obtaining a pure crystalline compound. Crys- tallization will not take place in the presence of a small amount of the oil; consequently its removal was necessary. The com- pound was obtained in the form of hairlike, golden yellow crystals, with a melting point of 160° C. The yield of the pure substance was between 0.2 and 0.3 per cent based on the weight of the dry kernels of the immature nuts. In another sample of immature seeds a quantitative estimation of the hydrocyanic acid was made by suspending 4 grams of the ground seeds in water and hydrolyzing them at a temperature of 39° C. with emulsin. At the end of forty-eight hours the hydrocyanic acid was distilled into sodium hydroxide containing a trace of potas- sium iodide and the latter was titrated to opalescence with 0.01 N solution of silver nitrate. This procedure indicated a content of 0.0126 per cent of hydrocyanic acid corresponding to 0.156 per cent of gynocardin. PROPERTIES OF GYNOCARDIN The best known hydrocyanic glucoside is amygdalin.* Within recent years many new ones have been discovered, and their properties have been studied. The chemical properties of the cyanogenetic glucoside, gynocardin, have been noted by De Jong ° Abderhalden, Emil, Biochemisches Handlexikon. Julius Springer, Ber- lin (1911), 2, 707. 40 The Philippine Journal of Science 1917 and by Power and Lees in the references cited. For purposes of identification, the melting point and specific rotation of the compound isolated by me were determined, and comparison was made with those of the products isolated by these works. TABLE I.—Melting point and specific rotation of gynocardin. Source. Seeds of Gynocardia| | Pat id a | Leaves of Pangiwm edule, b | Seeds Ot Oe Melting point__°C___ 162-163 | 99° 160-161 | 160-161 Specific rotation in 210 [e] D (1.77 %)=+69.7° | An chloroform solu- [a] p=172.6° 28° [a] p (2.5%)=+63. 2° tion. [a] 5 (16. 885%) =+-62. 2° as * Powers and Lees, loc. cit. % De Jong, loc. cit. © Occurring in the Philippine Islands. The properties of the compound isolated from the seeds of Pangium edule are so nearly identical with those of the glucoside from the seeds of Gynocardia odorata and from the leaves of Pangium edule that no doubt exists as to their identity. De Jong found that the concentration of the chloroform solution had considerable influence on the specific rotation of the com- pound. This fact is apparent in the results quoted above from his publication. Gynocardin differs from the other members of this class of compounds in its marked stability in the presence of acid hy- drolyzing agents. It also hydrolyzed very slowly by emulsin. TABLE IIl.—Hydrolysis of gynocardin by means of emulsin. Suan, | t ChE RCs Quantity | time, | Selution | Quantity) ofother Clucoside grams in| emulsin. stance lyzed. 300 cc. | added: water. | H | Min. | ca. Crs: | | Per cent. 20 25 0.05 none | 0.68 40 25 0.05 none 0.72 | 60 25 0.05 none 0.76 20 25 0.10 none 0.96 40 25 0.10 none 1. 02 60 25 0.10 none 1.08 20 25 0.05 20.20 0.52 | 40 25 0.05 | 20-40 0.40 | 60 25 0.05 80.30 0. 48 20 25 j bl 2.05 5 | she b5 1.94 40 2 ie : 60 25 | -05 | 10 | 0.52 0.05 8 Glucose in grams. > Hydrocyanic acid in cubic centimeters of 0.1 per cent solution. xu, A,1 Brill: Pangium edule and Hydnocarpus alcalxz 41 Auld* has determined the rate of hydrolysis for amygdalin by means of emulsin. Amygdalin reacts much more rapidly with emulsin as well as with acids than does gynocardin. His results with emulsin in the presence of added glucose and of added hydrocyanic acid are in accord with the results obtained by me for gynocardin, namely, the glucose inhibits the reaction, the amount being dependent on the relative quantity of glucose added, while hydrocyanic in smaller amounts accelerates the action, but when added in larger quantities the inhibiting effect is apparent. He has also found that the law of mass action does not hold good in its entirety for enzymic action. A large excess of the substrase does not cause a like increase in the rate of reaction when this addition has proceeded beyond a certain limit. The enzyme appears to be capable of reacting with only a certain amount of the substrase in a stated interval of time, and as long as the amount of this substrase exceeds a certain limit, no acceleration of the reaction takes place on the addition of more of the substrase. On the other hand, an increase in the amount of the enzyme gives a corresponding acceleration of the reaction, if the substrase is present in excess to react with the original amount of enzyme present. In the preceding table addition of more emulsin has accelerated the reaction. The juice from the crab contains a secretion which hydrolyzes amygdalin giving hydrocyanic acid. To examine gynocardin in this respect, a series of experiments was undertaken. The juice of crabs, purchased in the local market, was obtained by ex- pression, and comparative tests were made with it on amygdalin and gynocardin. TABLE III.—Action of crab juice on 1 per cent solutions of gynocardin and of amygdalin. | Gluco- Time. | Glucoside. pater Wace ee lyzed. ‘Hours. pce. ce. |Percent.: | aa Wanye dalin\:.- sons seb ee ane tee a tee Sa Soe es ee oe 25 10 | 51.99 | PA Sop nora Ni eee se See De a SE aa eee ae eee ae a ae 25 10} 11.60 Oe EPR ITIV ERIN coe ota eee oe nena acne nena Gene 25 10} 69.10 ASHIRG ymacardinie 222 Seen ee LU eae S REN eas Le yl 25 10 | 13.16 | Alp Amy edaliny= == osee eo = San ek as tet beset oa esd re cd 25 10 | 75.67 | | 71 | Gynocardin----—----—- = ne 25 10 | 17.18 According to Table III gynocardin is likewise attacked more slowly by crab juice than is amygdalin. Toluene was added in 7 Auld., S. J. Manson, Journ. Chem. Soc. London (1908), 93, 1251. 4? The Philippine Journal of Science 1917 the above case for an antiseptic. The flasks containing the solu- tions were incubated at 39° C. In view of the hydrolyzing effect of crab juice it was thought that it might prove interesting to determine the effect of adding blood to similar samples. TABLE I1V.—Action of blood on a 1 per cent solution of gynocardin. | Gluco- Time. | Kind of blood. Blood, | Gluco-| | side side. | hydro- lyzed. Hours. ce. ec. |Per cent. 21.5 | Blood from apparently healthy person_____..--_.-.----_.. ------- 3 25 1.45 21.5 | Blood from tubercular patient (rather advanced case) @_________ 3 25 1.69 22,6 | Blood from syphilitic person seek = Se ee ey ee ee es 6 25 3. 63 45.5 | Blood from apparently healthy person____-_-.-_----_ _-_---.---- 3 25 3.15 45.5 | Blood from tubercular patient (fairly advanced case) 4__________ 3 25 6.14 46:'0'| Blood'from syphilitic personas) = - see eee oe eee ee oe eee 6 25 3.96 * This blood was kindly furnished me by Dr. J. W. Smith, in charge of Bilibid Prison. The above results indicate that blood from tubercular pa- tients reacts more rapidly with gynocardin than does the blood of the normal person. The blood from the syphilitic person apparently reacted more rapidly the first day, but the sample incubated two days reacted no faster than the sample from the normal person. The Bureau of Science has collected some further data concerning this property when amygdalin is used that substantiates the above evidence. Amygdalin has been found to be harmless when taken into the system unless administered in the presence of emulsin. Gy- nocardin, when given in doses of 0.25 and 1 gram to guinea pigs, was found to be without any apparent effect. At the end of twenty-four hours no further observations were taken, as the pigs appeared perfectly normal. GYNOCARDASE The enzyme gynocardase was obtained from the leaves of Pangium edule by grinding the leaves very fine and then pressing in a hydraulic press, adding an equal volume of alcohol to the juice and filtering. The precipitate was then ground under water with sand, filtered through cloth, and again precipitated by the addition of alcohol. The precipitate was nearly black —— ~~ xu, 4,1 Brill: Pangiuwm edule and Hydnocarpus alcale 43 and of gummy consistence. Determinations of its activity were made with amygdalin and gynocardin. TABLE V.—Activity of gynocardase on 1 per cent solutions of amygdalin and gynocardin. 2 = En- | Glucoside | Time. Glucoside. zyme. |hydrolyzed. Hours. | cc. |Grams.| Per cent. Bo) ATG RGN soc eee Shonen caer see top ee ce be seage sceoemec eee eee | 25} 0.2 25.57 iA eee Cleat oer Te Se ne PE 28 Ok 25 0.2 26. 02 SAU UOCALOI Sere ae ne oe rn ei a EE ee ie eo | 25 0.2 13.82 ore Lae Oe ee eae Paes eg yh Pelt | 25| 0.2 13.28 | Here again gynocardin is less readily hydrolyzed than amyg- dalin. Since gynocardin is hydrolyzed by emulsin, which is a B-enzyme, it must be a B-glucoside.® Gynocardase hydrolyzes both gynocardin and ne hee con- sequently it must belong to the class of 6-enzymes typified by emulsin. Several samples of nuts were examined for their oil content. TABLE VI.—Oil content and properties of oil obtained from the seeds of Pangium edule. | | Mature. Koma er cent. er cent. 3 ea Ne, aeemnel content Of air-aried NUts too. - = Sean eee a ee ea | 42.67 | 36. 38 | Dried kernel content based on air-dried nuts -__---------------------------- { 29.09 | 16. 28 @ilcontent based'on dried kernels! 22-222 2225-2 es oe oo eee | 21.09 | 24.11 Z \ pl | Free acids ree from oil of | 53) ¢ fre x 1 Oi RS cs ilfrom mature} from oil |Oil from imma- eceda seeds. of imma-| ture seeds. 7 ture seeds. | Mreltinic pointy --~ 2-8) Cees oe Clouds at|Shows_ some |-_---_-_--- No change 18°C. clouding at at 8°C. 2° C. SDECIHC OTRVIUY 6-2. enn on ones eaee ees 0. 9013 0. 9049 0.8955 0. 9092 Specific rotation in chloroform solution _ +3. 49 +4. 28 +4.72 | + 20.€5 Iodine value (Hanus) --.--.------------- 113.5 113.1 103.0 | 109.5 Acid value ce. 0.1 N alkali ---_---------- 36.7 0.52 34.2 0. 90 Saponification value__----------_-----___ 207.8 190.3 205. 4 188.3 Indexiof refraction®- ~~ -"=2245--=22--=-2- 1. 4582 1. 4665 1. 4595 1. 4675 e: ae ] * Fischer, E., Ber. d. deutsch. chem. Ges. (1894), 27, 2985. 44 The Philippine Journal of Science 1917 To determine the physiological activity of the oil, 2 grams and 2.5 grams, respectively, were administered per os to each of two guinea pigs. No ill effect was noted in either case. Owing to the limited quantities of the nuts available, no ex- haustive study of the oil could be made. However, enough was obtained to determine that palmitic and oleic acids and small quantities of an optically active acid are present. The latter may be either hydnocarpic or chaulmoogric or a mixture of the two. It resembles chaulmoogra and the hydnocarpus oils by the presence of an optically active oil. HYDNOCARPUS ALCAL C. DE CANDOLLE A sample of the fruit of Hydnocarpus alcale C. de Candolle ® was submitted by the Bureau of Agriculture to the Bureau of Science for identification and examination. It had been sent to the Bureau of Agriculture by Mr. T. Alcala, of Daraga, Albay Province, Luzon, under the local name dudu dudu. It was large, somewhat resembling a small unhusked coconut, about 20 centimeters long and 15 centimeters in lateral dimensions. Within the pericarp were numerous seeds, measuring 4 centi- meters by 2.5 centimeters. Mr. Alcala writes: It is said that the oil extracted from the seeds is a good cure for wounds. It is generally believed to be poisonous, and when I ate six or eight of the boiled seeds I had a slight sickness; however, many children eat them raw without the slightest ill effect. At the suggestion of Mr. E. D. Merrill, botanist, Bureau of Science, that this fruit belongs to the Hydnocarpus family, an examination was made for hydrocyanic acid. The presence of this acid would indicate the existence of a cyanogenetic glucoside. All such tests resulted negatively. However, the fresh fruit or the unripe fruit might contain such bodies. Our examination of Pangium edule has shown that a decrease or complete disap- pearance of the glucoside results when the nuts age, unless the hydrolyzing enzyme is destroyed, and that with the ripening of the nut a decrease in the glucoside content probably occurs. Con- sequently the inability to obtain positive tests in this one sample of seeds for hydrocyanic acid is not to be considered as sufficient proof to warrant the statement that no cyanogenetic glucoside exists at any period in the growth of the fruit. * De Candolle, C., This Journal, Sec. C (1916), 11, 37. xu, 4,1 Brill: Pangiwm edule and Hydnocarpus alcalz 45 TABLE VII.—Properties of nuts and oil of Hydnocarpus alcalzx. Average weight of fruit grams 420 Hulls per cent 59.68 Seeds do 40.32 Moisture in seeds do 60.50 Oil in dry seeds do 65.50 Melting point degrees 32 Specific gravity at 30° C. 0.9502 Specific rotation in chloroform degrees +49.60 Iodine value (Hanus) 93.10 Acid value ce. 0.1 N alkali 3.90 Saponification value 188.90 Index of refraction 1.4770 Reichert Meissl No. 4.43 The nuts and the extracted oil were administered per os to chickens without any noticeable ill effects. The free acids of the oil from Hydnocarpus alcale were examined. TABLE VIII.—Properties of the free acids of the oil from Hydnocarpus alcalz. Melting point degrees 59 Specific gravity at 30° C. 0.9342 Specific rotation in chloroform 30/D degrees 53.65 Iodine value (Hanus) 98.6 Acid value cc. 0.1 N alkali 37.4 Saponification value 193.0 The free acids were then treated as described by Power for the separation of chaulmoogric acid. More than 90 per cent of these acids consist of a compound identical in properties with the acid designated as chaulmoogric by Power. TABLE 1X.—Properties of the acid isolated from the oil from Hydnocarpus alcale. Melting point degrees 68-69 Specific rotation in chloroform 30/D do +59.69 Iodine value (Hanus) 89.7 0.3400 gram of silver salt gave 0.0950 gram of silver, equal to 27.94 per cent silver. 0.5040 gram of sodium salt gave 0.1206 gram of sodium sulphate equal to 7.75 per cent sodium. Theoretical for C.H: COO Ag=27.86 per cent silver. Theoretical for C,H, COO Na=7.62 per cent sodium. Only a small amount of the acids remained in the mother liquor. No hydnocarpic acid could be isolated from this. The latter exists in very small quantities in Hydnocarpus alcale if at all. Palmitic acid makes up the chief part of the remaining 46 The Philippine Journal of Science portion with only traces of oleic acid. Both of these oils differ greatly in melting points from the oils from chaulmoogra and Hydnocarpus reported by Power and his coworkers. Pangium edule contains a large amount of olein and smaller quantities of palmitin. If hydnocarpic and chaulmoogric esters are specific for leprosy, Pangium edule oil would be an admirable remedy to use, since it would be easy to administer because of its low melting point and consequent fluidity, but would probably be slow in its action on account of the relatively small amounts of these acids pres- ent. On the other hand, Hydnocarpus alcale oil would be much more difficult of administration because of its being a solid even at the ordinary temperature in Manila (30°C.). SUMMARY The report of an investigation of the oils from Pangium edule and Hydnocarpus alcale and of the cyanogenetic glucoside, gy- nocardin, is given. Their properties are discussed in some detail. REVIEW A Laboratory Guide | to the Study of | Qualitative Analysis | based upon the | Application of the Theory of | Electrolytic Dissociation | and the Law of Mass Action | by | E. H. S. Bailey, Ph. D. | professor of chemistry in the University of Kansas | and | Hamilton P. Cady, Ph. D. | pro- fessor of chemistry in the University of Kansas | Highth Edition | revised by | Paul V. Faragher, Ph. D. | assistant professor of chemistry in the University of Kansas | in collaboration with the authors | Philadelphia | P. Blakiston’s Son & Co. | 1012 Walnut street | Copy- right, 1916. Cloth pp. i-x+1-294. Price $1.50. The eighth edition of Professors Bailey and Cady’s book, re- vised by Assistant Professor Faragher, is essentially the same as the seventh edition except for some minor modifications, con- sisting in the amplification of some sections difficult of com- prehension by the student. The scope and volume of this edition is, in general, the same as that of previous editions. The introductory part covers 24 pages; 126 pages are devoted to the reactions of the cations and a table for their systematic analysis, and 117 are taken up with the anions, also with a table for their systematic analysis. None of the rare metals are treated, except gold and platinum. A table for use in the examination of an unknown substance and another table of solubilities close the text. The introductory portion is furnished with a brief and accu- rate discussion of electrolytic dissociation and the mass action law as it is applied to qualitative analysis. The experiments given for the reactions of the individual ions are well selected; the tables for the separation of cations and anions into groups and the tests for their identification includes some good tests, for example, the dimethyl glyoxime reaction with nickel ions; while such subjects as hydrolysis, oxidation, and reduction are treated clearly in proper places in the book, thus rendering it easy for the student to comprehend their practical application. The mechanical details of the book are good and misprints are few (p. 68, 4H,O instead of 4H,0O). The type is clear, and the illustrated tables are well gotten up. On the whole, the book is a good, brief laboratory guide for students in qualitative analysis. F, PENA. 47 F ae Cpa oh ee hie Ay rs i oe Sah i. alate ie: a as Ae Cee iy bane 4 9 Bokeh siti Ts ZpE SiNheh “era on bores ha ie 2 epee ses x batt “ath re “Maren, 1917. 5) > ey we -, ; ETBNOLOGY ey postbaid. ©. iat Mes sant ay ‘ coals Tees y. Siu ar ia Dialect sgt (63, pm The 88, 28. Fanta tte plates) ) xp boun “pect ae rs gover. : These twa p eee ate leaded. ee ‘on “over 141 pages, eves pos tpald. nh ss 3 tiers ‘of this: 7 vers ’ Christie Bho Fai = Rerlod of yh Meeks, or pies Phe: 3S ites in iaralh s. “work and .at plays a } altars: nett Jmpiemen hemselves: hats is dat, pi a aids a 40 dod ment | ae it gain 0 8. in. On} of Suhe Thin. be mea oros..in’-the- ‘Paine e THE PHILIPPINE JOURNAL OF SCIENCE A. CHEMICAL AND GEOLOGICAL SCIENCES AND THE INDUSTRIES VoL. XII MARCH, 1917 No. 2 THE STUDY OF COPRA AND OTHER COCONUT PRODUCTS? By ALVIN J. Cox (From the Bureau of Science, Manila) For several years the chemists, assisted by the botanists, of the Bureau of Science have been employed, as time permitted, - in a study of the products of the coconut. Many investigations have been made and published by the Bureau of Science on the subject.2 Coconut oil as such and in the unpressed copra ranks among the three most important exports from the Philippine Islands and, therefore, warrants careful study. There are two large operating vegetable oil plants in the Philippine Islands, * Received for publication February, 1917. *¥Freer, Paul C., On the water relations of the coconut palm (Cocos nucifera )—On the oil produced from the nuts—The factors entering into the rancidity of the oil—The insects attacking the trees—Introduction, This Journal (1906), 1, 38-5. Copeland, E. B., On the water relations of the coconut palm (Cocos nucifera), ibid. (1906), 1, 6-57. Walker, Herbert S., The coconut and its relation to the production of coconut oil, ibid. (1906), 1, 58-82. Walker, Herbert S., The keeping qualities of coconut oil and the causes of its rancidity, ibid. (1906), 1, 117-142. Banks, Charles S., The principal insects attacking the coconut palm, ibid. (1906), 1, 143-168, 211-228. Richmond, George F., Purification of coconut oil, ibid., Sec. A (1908), 3, 45-47. Walker, Herbert S., Notes on the sprouting coconut, on copra, and on coconut oil, ibid., Sec. A (1908), 3, 111-135. Gibbs, H. D., and Ageaoili, F., On the detection and determination of coconut oil, ibid., Sec. A (1908), 3, 371-375. Pratt, David S., Copra spoilage on a large scale, ibid., Sec. A (1918), 8, 439-441. Pratt, David S., The coconut and its products with special reference to Ceylon, ibid., Sec. A (1914), 9, 177-199. Brill, Harvey C., Parker, Harrison O., and Yates, Harry S., Copra and coconut oil, ibid., Sec. A (1917), 12, this number. Parker, Harrison O., and Brill, Harvey C., Methods for the production of pure coconut oil, ibid., Sec. A (1917), 12, this number. 149522 49 50 The Philippine Journal of Science 1917 and several small ones are now being erected or planned. The work of the Bureau of Science has been done from time to time in order to settle some special problem, and all of it has been beneficial in pointing the way to more extended problems. The studies by Walker * on the keeping qualities of coconut oil and the causes of its rancidity and notes on the sprouting coconut, on copra, and on coconut oil have been very helpful to the public, and his papers have been in great demand. For several years we have endeavored to find time to continue and extend this work and to accumulate information with regard to the com- position of the coconut, the hydrolysis and consequent destruc- tion of fat, the methods of drying, the methods for the most effective recovery of the oil, the methods of analysis, the detec- tion of adulterants -of coconut oil and of coconut oil as an adulterant of other oils, and the reduction to a minimum of the loss through deterioration of copra and coconut oil during transportation. Data showing the composition of many Phil- ippine soils have been published, and some of these concern the soils from the best coconut areas. In recent years I have been impressed by the large loss of coconut oil through spoilage and the unearned revenue that the Philippine Islands would secure if all the copra produced were of a high grade. Furthermore there is a loss in shipping poorly cured copra, not only in the deterioration due to mold and bacterial action, but also in the transportation of the excess moisture. The work begun by Dr. Paul C. Freer and by Mr. H. S. Walker has been continued by Dr. Harvey C. Brill and Mr. Harrison O. Parker, the botanical work being done by Dr. Harry S. Yates. In California large quantities of deciduous fruits are opened, treated with sulphur dioxide (the fumes of burning sulphur) to protect them from bacterial or mold action, and subsequently dried. The action of sulphur dioxide is to kill all mold spores and to soften the cell walls of the fruit so that drying is facili- tated. Enough of the sulphur dioxide remains in the meat to prevent the growth of new mold spores during drying, if drying is completed in a week or two. We have successfully applied this merical to the drying of coconut meat. Coconuts opened and treated with the fumes of burning sulphur at the Bureau of Science during a severe rainstorm, which subsequently received no artificial drying or . exposure to the sunshine, remained perfectly white for a period * Loc. cit. XII, A, 2 Cox: Study of Copra 5l of two weeks. Copra on hand after many months is still of excellent quality. The box in which the treatment with sulphur dioxide is made must be fairly tight, but not air-tight. There must be circulation enough to keep the sulphur burning. In the tapahan (Filipino grill for drying coconut meat) method of dry- ing copra the coconut meat frequently begins to mold before the drying is begun, and before the drying has proceeded far enough to inhibit the growth of mold, considerable deterioration has taken place. In the sulphur process the nuts can be sub- jected to sulphur dioxide before mold has started to grow. With proper organization and routing of the work, the labor cost when the sulphur dioxide method is used will not exceed that in the tapahan. Compared with the tapahan method the sulphur dioxide pro- cess is exceptionally clean: the copra is preserved and bleached by the sulphur dioxide and yields very white copra; there is no loss of oil during the treatment or during the drying; an ex- ceedingly uniform copra is obtained, and its keeping quality is ~ improved; and the oil expressed from the copra is practically colorless, is free from rancidity, is pronounced equal to, or better than, the best Cochin oil, and usually will sell for at least 10 centavos‘ a kilogram (2 cents or more a pound) more than ordinary oil. At 10 centavos a kilogram there is a difference of about 4 pesos per 63.25 kilograms (1 picul) of copra. Storage conditions and the problem of storage must receive careful con- sideration even with first-class copra; however, this will become less and less of a problem as more and more of the Philippine copra is consumed in local oil mills. Other experiments have been in progress in an effort entirely to eliminate the drying process and to extract the oil from fresh coconut meat. Lack of means for producing a good grade of copra or oil from the fresh nut has not been the only obstacle in the way of the improvement of the coconut industry. Most dealers have been contented with a poor copra and could not see any advantage to themselves in being able to secure a better product with a higher oil content. Dealers say that it has been their custom to put good copra with the poor, but the vegetable-oil companies will buy the good copra at a premium as soon as they can get enough to run a mill for a day or two once or twice a month. Many dealers now realize that properly dried copra is worth “One peso Philippine currency equals 100 centavos, equals 50 cents United States currency. 52 The Philippine Journal of Science 1917 more—not only in proportion to the reduced water content, but also on account of its improved keeping qualities and the higher grade and value of the oil that can be obtained from it. If necessary, it will be productive of great results for the Govern- ment to penalize smoked, colored, dirty, moldy, or imperfectly dried copra and to subsidize the higher grades of copra until dealers become aroused and demand them, which they certainly will do in time. Such action will not only protect the consumer, but will increase the revenue of the producer. In order to estab- lish definite grades and a certain market, a satisfactory system of classification and standards must be devised, as the Bureau of Science has long been advocating. At present no definite grades for a given region exist, owing to the unwillingness of the inhabit- ants properly to dry the copra. In the Manila markets the terms Cebu sundried, fair marketable Manila, and Laguna are known, although ill defined. Cebu sundried usually commands about 75 centavos per 63.25 kilograms (1 picul) more than Laguna. A step toward the solution of the question of standardization has been made by the Visayan Refining Company. Nine months of experience gave this company 65.5 per cent oil in the Cebu sun- dried copra used in its mill. The company has taken this as the average for a good grade of copra in the Cebu market, and for such copra it pays the market price and, in addition, when the copra is white, guarantees the consignee premiums for addi- tional oil content as follows: Oil in white copra. Premium per 63.25 kilograms (1 picul). Per cent. Centavos. 66 12.5 67 25. 68 37.5 By this system the producer cannot lose, and the possibility of receiving a bonus is an incentive to dry properly and to pro- duce a higher grade copra. In order satisfactorily to establish grades of copra, certain facts must be considered. Well-prepared copra is white, but the discoloration of black copra may be due to its being smoked when dried on the tapahan or to mold action. Copra is either wet or dry. There are various degrees of wetness. The follow- ing paper indicates the permissible amount of water if copra is expected to be mold-free in storage. The character of copra depends to a certain extent upon the variety of the nut and the region in which it is grown; therefore it is probable that it will be necessary to establish regional grades of copra. It is my opinion that on the basis of oil content in relation to moisture XII, A, 2 Cox: Study of Copra 53 content, cleanliness and freedom from dust, foreign matter or adulteration, free fatty acids, freedom from unripe nuts, and color and general appearance uniform rational grades for copra can be established throughout the Philippine Islands. The use of green nuts for copra in Samoa is prohibited. There is a law which provides that nuts for making copra must be allowed to drop from the trees. There are varieties of Philippine coconuts whose nuts do not drop when ripe. Oil content alone does not define a good copra, as the oil content of badly molded copra may be on a par with that of properly prepared copra, owing to the simultaneous destruction by molds of oil and of tissue in relative proportions. Also the oil content of the coconuts may vary with the region in which they are grown or with the variety of the nut. The enforcement of grading should be easy, for the color and appearance can be readily determined by inspec- tion, and an inspector should soon become sufficiently expert tc judge the quantity of moisture by feel. There are also several simple tests that may be applied to substantiate his judgment. If copra is excessively wet, it is usually hot; if sufficiently dried, a piece of copra breaks when the two edges are pressed together. The width of the dark line showing on the fresh broken edge is a criterion of the moisture content. An expert can also judge of the oil and water content by lighting a sliver of copra. If it burns readily, the copra is fairly dry and has a high oil content ; if it is moderately wet, the flame will sputter as the moisture is evaporated; if very wet, it will not burn. The studies that follow contribute to our knowledge of copra and coconut oil and outline the means of obtaining a less acid and less rancid oil; this will command a higher market price and will bring the Philippines to the front for the quality of its copra and its coconut oil; this, in turn, will increase the revenue from Philippine coconut plantations. | bat en soy kee Spee ne Caer ae Peg Wes Hy 42 a Gli cet eto We Cand: aggre | ; Penataleves: LRT PAL a a sacle slanekeoi | CES CAPEIETE CM INE CFOS GEE 0 FE arenas i 4 = ¢ é re & Fi ‘ “2 abot 3, ty pee ‘% ent thaw x , . ¢ - ; ‘ be ’ _ ' te age ; ~ : Whe, : s AP) ‘ 1p DAT PAR peta leek ’ s) ; TAN Pye every ; j ee 2 . 7 y . : r- ¢ ot Hae oe ® : oo ° ‘a 2 el aie ‘ b aitas ; time i — : 5 F 4 - % ’ = f ' ¢ wa . } toh COPRA AND COCONUT OIL * By Harvey C. Britt, HARRISON O. PARKER, and Harry S. YATES (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) Increasing demands for fatty foodstuffs have developed the vegetable-butter industry in the United States—an industry for- merly restricted to England, Holland, and France. Refineries and hydrogenation plants have been able to purify and harden practically all of the animal and vegetable oils suitable for edible purposes into either simple or compounded vegetable lards and butters. The oil obtained from the coconut ranks high in im- portance among these. However, an enormous amount of co- conut oil is at present being used in the soap and glycerin in- dustries, rather than for the manufacture of edible products, because of the poor quality of the commercial oil and its conse- quent cheapness. The production of copra constitutes one of the leading indus- tries of many tropical countries. In the Philippine Islands prac- tically the entire annual crop of about 431,387,000 nuts,? with the exception of those used for local consumption, is turned into copra. Copra exports from the Philippine Islands for 1916 were 72,277,164 kilograms, and oil exports were 16,091,169 kilograms.* The annual exports represent approximately one third of the world’s output of copra,* most of which finds its way to the mar- * Received for publication February, 1917. The isolation and study of the molds growing on Philippine copra were made by Harry S. Yates, of the section of botany, Bureau of Science. * Cox, Alvin J., Bureau of Science Press Bull. (1916), No. 54. Computed from the yield of copra and based on the experiments of the Bureau of Science, which show that for the Philippine Islands 1,000 nuts yield about 270 kilograms of copra. *Information furnished by the Insular Collector of Customs April 17, 1917. ‘Smith, H. H., Coconuts. The Consols of the East. 2d ed. Tropical Life, London (1913), 362. Lewkowitsch, Chemical Technology and Ana- lysis of Oils, Fats and Waxes. Macmillan & Co. Limited, London (1914), 22, 635. 55 56 The Philippine Journal of Science 1917 kets of Great Britain, France, Holland, and the United States. There are but three modern coconut oil mills in operation in the Philippine Islands. These, together with the native mills, exported oil to the value of 5,641,003 pesos * in 1915.® It is surprising to note that Philippine copra is quoted the lowest on the world’s market. By calculating the value of Ceylon copra exported from 1908 to 1911 and comparing the figures with the value received for Philippine copra during the same period, it is found that the annual difference between what the Philippine Islands received and what they should have received in 1911 7% is more than 4,000,00 pesos and for the previous five years is more than 15,000,000 pesos. The reason for the low price is found in the poor quality of .copra produced. Some attention has been paid of late years to the improvement of the quality, but concerning the cause of this inferiority only a little published data is available. Oil ob- tained from the usual Philippine copra is discolored and rancid and contains free fatty acids varying from 5 to 20 per cent (oleic acid). These conditions favor even further deterioration of the oil. The quality of the oil depends primarily upon thé condition of the copra at the time it is milled, and poorly pre- pared copra deteriorates rapidly with loss of oil and impairment of its quality. The poor quality of the copra is due to insufficient drying and unclean methods used in its production. It is the purpose of this paper to bring out analytical and botanical data relative to losses in copra and oil due to the faulty production of copra and to suggest means for improvement. Unless coconut meat is dried, immediately after opening the nuts, to a moisture content of approximately 6 per cent, it is attacked by various micro6érganisms, which causes a loss in oil content. The extent of the loss depends upon the length of time the meat retains sufficient moisture for mold growth. It was determined by experiment and observation that molds grow most luxuriantly upon copra with a moisture content of 10 per cent or greater, which, as shown in Table I, is common in commercial copra. °*One peso Philippine currency equals 100 centavos, equals 50 cents United States currency. *Annual Rep. P. I. Bur. Customs (1915), 17, 18. "Pratt, D. S., This Journal, Sec. A (1914), 9, 186. * Walker, H. S., This Journal (1906), 1, 141. . xu,a,2 Brill, Parker, and Yates: Copra and Coconut Oil 57 TABLE I.—Moisture content of copra samples from various localities in the Philippine Islands. eet rts citi gal obaderag. 326) mi Dene] ring wate o>] Locality. Maxi- Mini- | mum. mum Per cent.) Per cent. | Reatial a DIG HR PUN seo meen ae nee la ais Sas oe se eee caeacven saoate 2951 18.8 CSET MEO) NC ee ee oe ee eae Ree aes ae 23.1 14.5 2 ony. De. oo BO ee a Se ee ae eee ane ne Se ee aa ae eee 22.2 17.6 } ELAS) VE, LOE OA 2 ete es pe at al ee ls a 20.7 14.4 | IEEE EES ey WEN YO i ae a en ee 24.7 15.5 ,; | Boron, SENTECH ao ee rae § SSR eee ek SOL. ea ee 14.1 10.4 It was deemed essential to determine the loss in weight of commercial copra stored and handled under ordinary conditions, especially as laboratory experiments conducted on copra under the most favorable moisture conditions for mold growth (10 to 20 per cent) showed a loss of 25 per cent in total oil content. Table III gives losses for copra stored in bodegas. The data in Table II were obtained by analysis of partially dried copra stored in a container at room temperature for fifteen days. The moisture conditions were regulated throughout the experiment to favor maximum mold growth, that is, from 10-20 per cent water. The loss represents the combined action of green, brown, black, and white molds. TABLE II.—Effect of the four common molds—green, brown, black, and white—growing together on copra. = ee ————EE | Oilin oie Acidity Series No. ERS Batons ae Logs of oil. ae mold action. mold action. action.® g. g. g. g. Per cent.| Per cent. 1 a eo Ee ee 17.10 5. 0838 3. 8138 1.2700 24.9 15.6 ju cS a = 17. 50 5. 2027 3. 8882 1.3145 25.2 12.4 Bee eee atc ree ee oe ke LS 16. 62 4.9411 3.7369 1, 2042 24.3 13.0 Se Ns ih Se So 15. 96 4.3571 3.3167 | 1.0404 23.8 9.0 Been ee ae ee SS 16.14 4.7984 3. 4468 1.3516 28.1 11.4 Cran ee ene See mea tobe 84.20 | 25.0326} 18.6020 6. 4306 25.6 10.0 | ® Acidity of oil expressed from fresh coconut meat is always about 0.2 per cent calculated as oleic acid. 58 The Philippine Journal of Science 1917 It is obvious that if there is a loss in oil there must also be a loss in weight of the copra from this source. Buyers of copra recognize that a loss in weight occurs when copra is stored, and they are governed in their purchase by this factor. The loss in weight when commercial copra is stored is shown in Table III. TABLE III.—Loss in weight of copra from various provinces when stored in commercial bodegas. : Days Loss in | Place of production. stgresda Vicor Hiae Albay Province: | Per cent. TLermaspil (tcl eb ee a hE ee aD eet re RL 29 9.61 DO2cces Seen sees ses Bisel ay open e las ee oe eae eee 10 6.00 1D [oe ee ee es en ee Ree teens eae See ee 22 1.00 Camarines Province DaGtin- ans bose ees ae eS oe ee ae eee 28 0.00 D032 ee eee a ae ae to ogee Gan aa ee a ae ee ee ea 31 6. 25 Doone a a es et ee A ee 12 2:5 Dos. 2a oes ce REE es ee eee Ee eS eae see oe ee 26 5.0 Capiz Province: | Calivolsnc 22025 Socks es see 0 ene a ea ee ee ay 29 8.77 Dos... ese es Be Bee Se a ee ee eS 26 10.07 Doses Cee Se SAR wae e BR eae 20 4.5 GOO os 2 eed Re Sek ee ee eee | 20 1.5 Laguna Province: | Pagsanjan’ - 242 22.-2 Saeed es ee REE cee oes oo, Spee eee } 19 16.60 Dots ison 25 ee ek Sa See ee a ee 28 8.41 Do ice honed ee ER ee ee eee ne | 14 2.0 lB Ys Fea Se nN pe ne PUN a MORES) em hes Ueoere re ert ho oe ot ee Oe | 25 10.25 Oe ees oe ee ee ee ns Se a a | 25 5.5 | Doe? cot Fe RE eS Ste a ae eres | 20| 12.25 WO kh enetee seen a cote eee onc See ee I aE eee ee 9 7.00 San: Pablo 220-2. = eee eee ed ee et ee ee ee | 28 10. 48 DO nose oseacesendcnda dd eeste cos ceee stabs cee nee eee eee Cone a eee | 26 12.71 D0! so 225s esi toe een bee A ee ee es ee eee 1 11 9.25 Pangasinan Province: | Darnpan - 20220. te ee Se ee eee ee eee | 19 | Harel San Carlos) <2. 525.5255 eee = sete aoe eee mee nee ne tear comes | 10 | 10.00 Romblon\.2222-255),-s2cc ecb eoscete esos coe eee oe ee eee see een ee 29 3.87 DOs doses nccnsncscks Coen ee kets sess ed cee ee ae oe et ee cee eens 29 7.5 Dor 5 25se veel oa eae Oe We geal ren ane eee a eee | 25/ 11.5 Marallanes:-. =o 22 see conn een a coe ree oe ee en ea SOE eRe Eee 28 2.86 | Doi23. So sohbet esos ese sks ieee a nao ae ea ceed Sane eee 4.22 Samar Province: : Catarmian(2..2 2282-25 -2 22 2565-5 vcd cel eo awe at seeks 28 0. 86 Cathalowan -o5o<- ie een oc a a ea EE 20 2.5 Sorsogon Province: Bulan ses cans ae~ Se seae cc can nds coca eee e ee ene eee ee eee ene Deere 14 1 DO. poe sses ak cans Ses a a en cocoa ane 21 1.5 Gubat .25= ssses0cc2 52 od cbs eh ke eee ee aeceon asec 28 0.91 DOe2acsencsese nse ssa = a EAS as Se re me eee en ee 24 10. 22 | DY a eae ey eS Oe ere ee 18 6.38 DO nasaaeesshatescscn cee eseeel be cca nS oe ence so eae ea semeeee ose aeeeeee 18 8.15 Surigao Provinces 22.62202- senses so anes ee nea esnowee tees aareeee eeeenenes 23 5.5 xu,a4,2 Brill, Parker, and Yates: Copra and Coconut Oil 59 TABLE III.—Loss in weight of copra, etc——Continued. i Place of production. | Daya. wn Tayabas Province: Per cent. | CAT PRTELET A 1 OR, OP SRE LS RE a ee Oe Sa Re ene ee | 25 1.00 LDC jam sued, SUS wpe Oe BU a eng ah ati ea a 30 0.4 117 i SRE Ey Dees CUSSED kb oe Ae eee cee ee ee ee | 28 17.74 Doe eee eee SOS OO eee ee eee er ee eee eee ee oe, 26 | 12.97 LOPE es ag Se Sa ee ees eee ee eee 19 | 1.76 [SEs ENE sn ln oe I yates a em ae aa EB ay ey apap ls aye A aR 20) 12.07 De Se ee eee fae LE xy Sipe SS A Cs 29 14. 58 SDT ee oe ee eee ae ee ee a ee ee 28 2.90 on Dorit) 1 2 ee La ae ee Se eee ee Se eee 18 | 1.75 TENT Sit pene Sag oS Bt Se alan ep 49 I ea de | 18 | 6.53 DT = Se os Se = BR Se a ae ot a eh os 7 a ee ao 31 | 18.69 ID): Satie cedceusnce seed eee es ps en eee ee 18; 9.09 ID 2 oS cee bende conceded teenie cate Sods eees SES eS eEe Hace E ee Sere 12 | 14.05 1 SS a ee er ee 14 9.75 Geen cease lanecantenbesasuesccsensese cosh see cc beesel cde cece 24 | 8.00 DY eee UR a ee US ee is GMS es | 23 | 10.00 LLCS Oh eee Eis ee SS Ee en ee ee ee eo se re ee 29 | 7.50 LB 3s aE eee a ae oe ae | 15 8.06 REA Velen ee a ne eee ee he oa Se eee sabe Ee Ee bw 25 12.5 There is a further loss in weight of copra on shipboard, which the copra dealers estimate at from 3 to 6 per cent, depending primarily upon the length of time of storage before shipment. With the high freight rates that have prevailed for the past year for copra shipments to the United States, the loss due to paying freight on loss of weight alone is considerable; even under normal conditions this loss is too large to be ignored. Freight rates at 50 pesos per ton with loss in weight of 6 per cent amount to 3 pesos for each ton of copra. When the product is not completely dried, there results not only an unneces- sary expense of handling an excessive amount of water, but also the conditions are most favorable to mold growth with conse- quent loss in quality and quantity of the oil. It is the producer who suffers,® for the purchaser reduces the price to cover not only the extra water, but also the extra handling and transporta- * While the price paid to the producer is less for his poor product than it would be for a higher grade product, some question exists as to his suffering any excessive monetary loss. Consideration should be given to the fact that he has no great amount of money invested in apparatus, that he can employ unskilled labor, and that he expends no great amount of care in the preparation of his product. The difference in the cost of producing poor and of producing good copra is hardly made up by the present discriminating price. The production of poor copra should rather be considered an economic loss to the Philippine Islands. 60 The Philippine Journal of Science 1917 tion expenses. That these losses incident to storage and ship- ment extending over periods of from two to four months are not due entirely to the evaporation of water is evident from Table IV; showing temperature, carbon dioxide, and weight loss relation- ship of stored Laguna copra. It is obvious from these figures, which show an increased temperature with a corresponding in- crease in carbon dioxide over the normal atmosphere condition, that slow combustion is taking place with the formation of carbon dioxide and water, necessarily at the expense of the meat and the oil. The increase in temperature of the copra parallels the in- crease in carbon dioxide content of the atmosphere surrounding the copra, rises to a maximum at the same time, and decreases along with the decrease of the carbon dioxide concentration, proving that the heat is produced by the combustion of the copra. TABLE I1V.—Temperature and carbon dioxide relationship of commercial, stored copra. Temperature of atmosphere, 29° C. Carbon | : dioxide | Tem- | (COz) in | Copra. Date. per- atmos- ature. | phere over stored co- pra. °C”. Per cent. September 20 40; 0.4 TiGb Tne ee Ae ie Ce ar September 23 40} 0.4 September 25 38 0.3 September 26 38 | 0.2-0.3 September 26 50 1.0 September 27 65 1.6 September 28 55 1.4 September 29 53 1.2 September 30 50 1.0 October 2 48 | 0.8 Teer, bet Se AO ee Oe SE ae ae |; October 4 48} 0.8 October 6 45 0.6 October 7 41 0.4 October 9 40 0.4 October 10 38 0.4 October 11 38 0.2 October 12 36 0.2 |\ October 138 35] 0.2 |y September 26 45| 0.8 September 27 44| 0.8 September 28 42 0.6 [os Scie 7 RA OU.” oR Gan ae i ee ee || September 29 40} 0.6 | September 30 40| 0.4 ! || October 2 38 0.4 || October 4] 38] 0.2 om |‘ October 6 36} 0.2 xu,a,2 Brill, Parker, and Yates: Copra and Coconut Oil 61 The data in Table IV was obtained by measuring the average temperature of a lot of copra with a moisture content correspond- ing to the commercial samples described in Table I. The quantity amounted to over 200 piculs. The carbon dioxide measurement was made by withdrawing air from the center of the pile and determining the percentage of carbon dioxide by means of a special absorption apparatus. The average temperature of the air outside was 29° C., and the percentage of carbon dioxide in the air was always less than 0.10. Five bags belonging to lot II were weighed before and after storage in the general pile from which the carbon dioxide and temperature determinations were made. TABLE V.—Weight loss in commercial copra stored twenty-five days i bodegas. | Weight. | Bag No. 5 ae | eptem- cetober \ ber 26. | 19. Loss. | | Kilos Kilos. | Per cent. | U Leen 1 eee eee ee a eee a ee | 57 50 12.4 Se ie oe aE ae cian eee eu abaaanckanaw aw dandaneunnonades 45 40.5 | 10.0 | Ne en an ano ea a catoue nace sun awewetudvaceteawtowcsadcce 56 48.5 13.4 orn Be RS a ee airs See eee ee en rer 78.5 66.5 9.5 Veneto ee Se 0128 | ioe co aes a a ee eT a ef at ee tl ee 1.26 0.71 0.88 0.80 (Re Ose eee See ne RP EEE SERRE CO Se once Se eee 1.82 1.98 Be eae ee a et el a cee 3.14 2.13 2.18 2.25 (Bec ie oe breech Sere teccccemaet erento ter car SSsnke ase 3.64 2.61 2.19 2.30 (RRR es eS ieee Hes een tence ac Seabed’ Soto se eecbtinecese! 4.24 3.20 2.41 2.87 Pe Se Ss ee Se eee as cs ect ee eee Sareec ess 4.48 3.28 2.49 2.78 | eee ce cer emen sr cron fer SHC OME ee ese sere ne rere recereme Sera eee es 8391 . | Fh oe eee TUNES sees bse sn eee Seetine ane Sasso sine sossode sec sssl seeciscce 4.05 2.69 3.19 [YA 6 dose Sa eS aS cee eestor roc eee sce octets sot S525 Abt. Se ae eee Original weight_.----------- pieeete push eel ety grams..| 83.51 | 92.76 | 64.50| 85.99 Total increase in weight2...2-------~- ssess- sees aos percent._| 5.3 4.9 4.2 3:7 Original total water-_---------- a te a yw tn EE dors 2.6 3.4 3.9 5.0 Bind total watere ces spa ence doi 7.6 8.0 7.9 8.4 In one case mold appeared on the eighth day, in two on the tenth, and in the remaining one on the twelfth. TABLE XIV.—Change in weight of copra stored in open air at atmosphere temperature. | | Relative Change in weight of sample—> humidity ez eer eee Days. in Manila | { eerie TS a iv | v —_——— g 0 gd. g 9g Dies ee Tn a ch ee oa 91 | +0.13] 0.22} +0.10} +0.07} +0.02 Bi ers Sana ee a ae RO ee cee 98.5} 0.02} 0.85] +0.11 | +0.07 | +0.02 BR ELAM SE Sa eee 94.5} 0.85} 145) 0.11} 0.18 0. 22 1 See OG Se Sn Peeing ate a ore cee eer 78.5 | 0.85] 1.44] 0.07] 0.13 0.21 Ca a OR HENS AM NGOS Ls 94.2] 0.37| 1.81! 0.16] 0.18] 0.98 5) oe CO ie OE 88.6} 0.47] 2.138] 0.16] 0.24 0.45 6 EES OEE DIU ee ee os A 85.9} 0.37/ 1.90] 0.12] 0.18 0.10 Total lone tote eee aes ee eee ee percent..| 1.2 | 6.0 | 0.47] 0.76; 0.40 Original totalwaters-<2-22-222e-co nce eoee nee do...-| 6.8 11.7 5.37 5. 66 6.70 End: total water =2us-.54. This is marked +, where an increase in weight resulted, but no mark is used where this change was a decrease. xu,a,2_ Brill, Parker, and Yates: Copra and Coconut Oil 75 In Table XIV are recorded data relative to weighed pieces of copra kept in the open. The weight in grams is recorded under series number of samples. At the end of fifty-six days no mold growth had formed. The last ten days were a period of wet weather, during which mois- ture was absorbed by the upper portion of the meat as shown by comparison of the upper and lower portions. This change of moisture content of the upper layer when calculated on the total weight shows a relatively small change in the percentage moisture. From this it is seen that copra stored in the open air will lose or gain water until it is in equilibrium with the at- mospheric moisture. This equilibrium point is about 5 per cent moisture for copra. The copra in Table XIII had developed a fair growth of mold © by the end of two weeks. There are only short periods during the rainy season when the air is practically saturated with mois- ture, and unless dry copra were stored in containers in a saturated atmosphere, no molding would take place. It will be ‘noticed that the total moisture content of each piece is extremely low, but if, on the other hand, copra containing from 7 per cent to the amount of moisture contained in fresh méat had been stored under like conditions, the mold would have practically de- stroyed the copra in the course of several days. This would also be the case if copra of 7 per cent or more was stored without air circulation, the damage due to mold depending upon the moisture present. In Table XV data on good quality of machine- dried copra without mold, stored in five sacks, are recorded. Temperature readings of the copra and outside atmosphere were noted from time to time. Weights of the lot before and after were not recorded, as insects destroyed a part of the copra. Table XV indicates no temperature change where no deteriora- tion of meat and oil occurs and, further, that copra once properly dried does not develop mold when stored. Copra which has been machine-dried and not cooled before be- ing placed in a large pile becomes hot and later often shows mold growth. We believe this to arise from a breaking down of oil and cellular matter from heating (the heating is similar in character to the spontaneous heating of oily rags) into carbon dioxide and water vapor. The moisture of the surface of the copra is raised in this manner to a point where it will support mold growth, and thus microdrganisms appear. The temper- ature at which the copra is stored is a factor in this heating. When the copra is carefully cooled, the oxidation at the lower temperature is so slow that no appreciable heat is given off and 76 The Philippine Journal of Science 1917 it escapes without any rise in the temperature of the pile. The theory of some of the copra men that the moisture content of the copra is increased by the condensation of moisture from the cool air surrounding the warm copra is absolutely untenable. TABLE XV.—Data on machine-dried copra stored in sacks, Sample. | Date. iL Ii. Il. | Vis | We | | Copra.| Air. |Copra.| Air. |Copra.| Air. |Copra., Air. |Copra.| Air. aot OG al imcG wal OCs °C: 26: ' °G. | °C: °C: °C. °C. March!20 2222 - eee cee St) ais 30 30 29.5 | 29.51 30 80 30.5 | 30.5 April 322 ee 30 30.5 | 29 30 29.0 | 29.0} 30.5] 30 April 25. 2 eae 30 30.5} 28 29.5] 30.5] 380.0} 29.5] 30 April'20 oes csaneseemae 31 30.5, 29 29 81.0 | 81.0} 32.0] 82.5 May tiie. 52 ee 32 31.5} 29 29.5) 80.6) 81 29.1) 28.5 May16i > - >> -- "~*~ Opm-=--| BT --gsa[1O[Oo A[[Boryoeag |~~~~ 77777777 axyl[anosg | gt a ee PAO TOMA SIT | Geen tenes OD men eanS L ~“sSa]10[O9 A[[BoIWOBIg |-~~~~ ~~ expse’yT | gt cera a OD sees | caoae oa OD TES ae ie iia ar Op-2e-5|teas cee cae OP as aIl6 eee cae AOT[PA BYBYT [Oo HOHOUS | § Tea anit ot OD seses | cae eae ACD nek alee. --S89[1O[OD A[[BoIyoBAg |~~-~~7-~-- 77 Dinas € Pee AO]eA YsjumMorg |7~-~~~"~-------- op----"| g --gs9[10]O0 A[BoIWOBIg |-~~-~- ~~" 77 ~~ axI018q | g sy,UoWy ‘a3B “10109 '10PO Se ora ae “(9T6T “AON) 919909 [IMJ ‘pezez1y pus ‘pessoid ‘palip A[ysery ‘yeoUl pojeis WIOIZ [IO “(Pro i884 Z B1Id09) BIdOd PolIp-sUIYOBUL Wor [IO -------== (g[6q “[I1d'y) [lo a[qipe sse00rd-aanen, ETE «[f0 plouBd,, “gT6T “349g ‘[10 uefuesseq qo peqeredes ,.2}8D,, ‘SIG, “3deg ‘sjlo uBluesseq or ‘oN a[dures e870 4NU0909 snotwpa fo UoLIDaL pun sa1ysado4g—] ATAV\, 101 Coconut Oil ippine il Ph Brill and Parker XI, A, 2 *A[O] BIPOMUN! UOW][eS Eagiring® tase pent ee auoNn 3°2 SOG ilies ss sea Sasso OD iaaia SOs. lor ae tea a ODassas UG pe el peer ae ory GOD Seen “Sulpueys Zuo] UO JO[OIA JUIBT AOA |---~7*~ ~-"OS{pul uLe.T SOMO Ni capcicssaa ronnie euoN *UOOS JOJOIA JULBYy ~~ ~~~ “oZIpuy O(tae ce soe qeajora deaq “£197 81P “gg UBYA JoPULByT -OUIUIL JO[OIA H1Bq | JByYMoUIOS oZ1puy “4197 81p “JO[OIA JULIET | -9UIUIL YsOUL]Be OS1puy ‘od ie eee a ~--"- BUONT *A£[9}81p "OuUON | -OUlUlL WsOW|e OsIpuy *ZO[OIA JuLBy AIBA |~-->~ 7-7" Q2]01A Jule SOC a ee ee Oprs=>- LOTT RS ha arate OD reas ‘og ots a PEenc et Op ess (and £°% LT 9° 80 20 *queSBe1 Iot{},9 YIM 489} IO[Od OU oABZ [IO 4NUOdOS [eUIZIIO oy, > ‘requinu siq} ‘ZT ‘(LI6I) WV “99g ‘wurmor sryt “Te 18 “DO “H ‘Iq ee8 ‘uolydisosep 10g q *LIGI ‘9 [ludy Uo epeur araM 83590} oso, v FrRSRasseee asec Op--~77 [7777777777 >> axLTax0UIg Goan AO][e4 YStUMOIg |-~~--~-----~-- axIPANOS pee Sa canna aaa an OPesecalasar cise: hares OPT sacs eR ENT Oprnmrprrrn m= OH PVT a et ee ODE SS icy eageaiens west sigs eine OD gcptrics roe SCG.) «aie teta bate ter ai) acs Taaaead euou Al[BoIyoVrg |--------"-""-"-- goo phorronsaoeste ss Opis alee ace ---ayLaNog ---"> moy[adé ystumorg |--7-->----~ Sa 20D aa 4 Een eae Opres sero re" ST OM paeT eeaas euou Al[eoIWOBIg |-~-~~--~-""----- qaamg RRS soteers torte oprrt rnp on orn" = axl 1978qy in aa opens ieee \) Jeep iaummmmanpe ampere UES Ia PEC E ER EEE ODe wal aay oreo peo = eR Ia Ge none ODtssasieccssos cos -s= Opie ss Guenther shee cos an wanes aman earn nn Oh meme § or ce mosSseo eos dso andes: a eAqeU ‘[I0 ppuRy -doys “INT de[eep wioIzs [10 Joyjadxq “sso001d [IO ynuoD0d jBloTeUIUIOD *81930q persed “qBoul painyd[ns woz [io pezeyiy *91990q peteddozs ‘[[nq 4BeuUr Ysery WoAZ [10 perzey{ LT “"""peylaeo you 4nq ‘LZ “ON Ul 8B sse001d oUIEg *sinoy X1s-A4}114} YSno1y4 perqqngq ues “AXQ “ODO G0T 38 SInoY 4YZIe paziiwayg “pa ~AO7[F PUB YZTBO 8. TO][N YT YI poyMely “pe -sseid pus polip A[yseaz ‘4ywour pozV13 WIOIZ [IO “9 [10 JnuODOD vind ‘Ysera WOAZ Splow A74LF 90I,q Pate siatal ekt tahoe [10 ynU0D09 plo WOT Splow AWWQBF OI ape So. ee ee yo gnu tid : (uoIs_nuS JO woljwrodeae Aq peiedeid) sa[vep wory [IO *raulezUo. uedo ‘paseq[y pus *‘pessoid ‘palip Ajyseay yRour payers worz [10 ~ (pez}jeajyneu) widood Apjour woIz [io payoway xg aSSrs “-"===--==-= gidod pooOS WOIF P9}081}.XO [IO “Sera 7777 =="-======-gs9901d BUIZeaIy Aq [IO “(LT6T “UBL) “DO oOOT 38 sanoy PAPA} P2ZI]I10}8 {s9]}930q Usdo ‘paseq[y pus ‘passeid ‘pelip A[yseay ‘your pazvi3 wosz [IO “(916 AON) 998ds 418 Spa “88010 pus pojIp A[Yseay “QUOUI po}BIB WOIT [IC os Ts 08 62 83 L@ 92 92 ve &% (4 TZ 02 6T 8T ut 1917 rence Journal of Se ippine al The Ph 102 ‘og “OuON “A[OVVIPOULUL! JOTO!L A. *A[O7BIp -9UIW] 4o[OJA doaq *ZO[OJA QUIET ‘og *UOOS JOIOIA FULT “Buipueys Buoy ~--£[oyBIpourUM 4a[O1 A “£1278 IP -9UIUII 4BOUI[B OBipuy UO JO[OIA YULey AI@A |--~-~~--7------- ODacaas (ONON © aelgese sesamiae ODssass SOS: jFS> Set saasescs<5 ODesaas “BUIpUuB IS Zuo] UO JOJOIA Juyey AlaA |--~~~ 77777-7777 => auoN “UOOS JO[OIA BULB |---- OB(pul yuLey ATO A 0Gge Wea sar ae Ae auoN ‘au0N |->--— OSipuy yulez AIO A 198 DIUOYd]Nns auez -UaqozeIp YZIM IO]OD |-[Ns-uIsyony yy 10]09 *ploe snoanyd 9°0 La) oan £0 “plow d19]0 se 4} “Iploy Sede ttere a Co) Nota a -- qa0Mg ie ~"~ MOTIPA FYBUT | ---- >>> BHLOOWG aecdeiaht apie seas OP sse alr aan cores = rispagire, (e) We Giegtbio kee *) oa aie I eas mamaeeeatemte 1942) 39 ¢ i ae hh Oe oes (0) So Se ae rein a ODte eelnn saat ate He BOpT aes ESSrar Scns nens op --7- 7-77 2-222-2-- Opy-en | Soe eas lODaane | oa 2 sn ss AOS SUOULAIIRO ORI 7 tae sae oon ae pp == 3 MO|[9A4 YstuseIy fa —mm nm n mmm nnn ox prey | AO[[OA YSlUMOIg |~~~~~~-> >> =~" > q2aMS Shia Rae Re ce aa OD Berea |etenmnnn eee ON lO 1OU1 PAO OAR cp |G sao 22 es === == ODzaana auou A[[BoIyOBIg |~-~- 77-777 q28MS “10po 8T ve “98937 e10Jaq yen Inoy oUO pa][[qJsIp-Uree18 “TT [1D | *pereqy | pus peysem “HO@N YIM poeziyeqyneu “zg [IO | *([f0 4aA0 908ds ale) po -sse1d pus palip A[Yyseay “Boul pozeas Worx [IQ “(plo 81894 J[BYy-ou0 pu 9u0 eidod) Bidod palip-aulyoeuL WoIz [IO “TouLe}UOD UddO UL ‘pazi[i4e}s Jou ‘YyzIve 8 JOT “(NY Ysnoty} saul? 9914} pejez[y ‘passoid pue pelip Al[ysety ‘woul peers wlorz [ICQ *(LIGT ‘0¢ ‘UBL) pesserd pue Pep A[yserz “Guoul poyeis Woy [10 pasoqyi *(LIGI ‘ST “Q29.q) pessezd pus pelp A[Yyseaz ‘yeour poyvis wloJj [10 pereq[yup ~~ Wl001010}8 aDUeIDg Jo NveINg WoJJ [Io 1038eg “w004 -210}8 2DUSIDG JO NBeiNng wWIoIZ [10 paas u07}09 é “u100.1010}8 eoueldg JO n¥aAng wWoIFZ [10 AO eSZnT oang ~-~“sesodind ArBul[nd doz “[1o aAllo easy sang Src eal eg Wee oa [JO JnUod0d [e1IDIEULUIOD Paha peie3z[y :8}7NU YseIy Woz [10 ynU IG “9[990q peseddojs *][ny “jveUL Yseay wOTZ [10 paszeqy iy ‘ajdures Jo uol4diaoseq “penuljUoj—sj10 7nU0909 snoruva fo Uo IDAaL pun sayiado1g—T]] AAV, 9p gb vy &P a ly OF 68 88 Lé 9& 98 vs && ‘oN ajduieg 103 Coconut Oil ippine Phil Brill and Parker XII, A, 2 “£197 BIp “OW! 4alOIA dead “oq | *A[2381P | eu! yajorA deaq | og | es ayrexous | g | | | | “4803 er0yeq 4sNf pasojz[y pue peysem ‘aqyByd -[NS8 UssoIpAY umNipos yIIM payeery ‘pe [IO “4894 lel | eIOJeq 7SNC sinoy de1y44 pel[i7s{p-wiwe4s ‘TT [IO | Lr | 104 The Philippine Journal of Science _ 1917 not give any color with either reagent, and Nos. 4, 12, 20, 21, 23, 24, 25, 29, 30, 31, 35, 48, 44, and 48, which show color with both reagents and possess a high acidity and rancid odor. Ina total of forty-eight oils with four tests for rancidity being used, one or more of these tests do not agree with the others in thirty cases. The organoleptic properties are the most dependable tests for rancidity. In Table III the relationships of the other three tests to the organoleptic properties are given. TABLE III.—Relationships of rancidity test to the organoleptic properties. Dinaree:| Agree- Test. | ments. ments. Per cent. | Per cent. Acidity .2222..sc5ed -2sccscsdesatns se8 Sas ek Sos a eae eee eee eee 21 79 Diazobenzene\sulphonic acid\-.---222-..s-sesesee a= Soe eee none nee eee eee 29 | V1 Decolorized fuchsin). 2s. 3:2. s2aaccsccc cee e | oae ae ee oan ee eee een 33 | 67 From Table III it appears that high acidity is a more reliable indication of the rancidity of an oil than the reactions with diazobenzene sulphonic acid or decolorized fuchsin, but this does not prove that rancidity is coterminous with acidity. They occur simultaneously in many cases, but the one is not a neces- sary corollary of the other. When oils of high acidity are steam- distilled, the residue no longer possesses a rancid odor, but has lost very little in total acidity. Samples 46 and 47 bring this out very prominently. The acidity in these samples remains high, but the rancidity, judged by the odor, has been lost. Sample 45, which had been neutralized with sodium hydroxide and carefully washed, was not freed of its odor though freed of its acidity. Sample 48, which was washed with a solution of sodium hydrogen sulphite to rid it of any aldehydes that might be present, still retained its rancid odor. If rancid odor is due to the presence of aldehydes, this sample should have lost its odor. Issoglio ** describes a confirmatory test for rancidity in olive oils, which he calls the ‘‘oxidisability value.” He states that when the oxidisability value exceeds 15 it will be usually found that the oil is rancid or has undergone some other change. Table IV contains some oxidisability values and some acetyl values, together with other data on Philippine coconut oils before and after distillation with live steam. *Issoglio, G., Ann. chim. applic. (1916), 6, 1. 105 Coconut Oil ippine il Ph Brill and Parker XI, A,2 ‘jooMS SuBOUL — ‘!plouBI sUBOUT + q JI e981, Jo sisquinu e[dures 0} puodsaii09 sisqumu a[duiug »y “JO[OJA BULB POO ee Ope =e. || ce LOD oe let eae mas Pager “OP agen | Wea pera Xa wozipuy | §°0 PO 0°9 L@L OO Faiee | eeeseoeaae: gnuos0) + Ld Tia ee beeen 2] Srnaget ac C | Ses aeete eae AGIONAG Sensmer Srncas Opa aal Vale mea (KOT ak paar SAL | AZ Pe i0}s8Q | — | 68 FOCioe if age ener Opis = SS JOD sala aeanas qurey Ado AQ [77-7 op----- 20 SiC h caaay Oh | 9% |--""paasu0y0g | + | 88 sO: —s|Eer a oes Obra alte OPra |g es aaa ASIONAG ees eS ae Cpa BB. IAI PRS OAS Gh [Rae Oper + |L8 “aUON [7777777 alae OD aan "@U0UW ||s—soeoaac Galet (+) Sutctal eee en[q ysiueedy | 0°Z bab ad | eat Gr2T BPO! ae aca PATIO a 98 T0 ames at JOTOLA FULB AT [OO ORoe a 0°9 tg $°8 8°6 OESE S| Ha coe ynuos0y + g§ “auOU {~~~ JOOLA JuLey Aa A [>On SUuON | 6°T Gita tna mal 9°ST 9°L amet mend KLASL] Eey _ rs 11 (0) a JO[OIA quIByy |-- OBIpul UBT | Z°0 20 g's 0°8 BO ee) | rae re OD iano — $8 1 | a ae © ABIORAY |e ee as oe euON | 8° =| 8s | F8 196 |OTR [----- Opas = + | 2 20 ~~" JOLOLA Furey ATA |----- ~~ OSIpul ulBy | Bp 6°P SL OL oneal | > pati Op Ts + 1§ TOP> JIG Stee a PLOT ACs |g a OBS ipa || Sate a | Cuber (Sg) a0] S721 RUk Dae |e CDs + | 08 "QUONMisscsacaes ---" guON | ‘euoU |-~~-77"7 77 SOPs tes" ie a ae ane oZtpuy | pT o'T 9°9 OfZ0 a6. 0 ee qnuos09 ab 62 "qo]ora quyeg |----- == BARTOLO le aae ga FOLOV AN |peee me anid ysiueery | O°8T | BLE [--- ra) quia | + «| LO Ni ents = ae eUuON | “euou [oo ommmn JO[OIA JUIBY |-----*-- JolOIA BUIBY | 60 8°0 QL 9°9OL ORS S| Sa es () pee — 61 "qafora Jules Ata |-~----~ Bea ODEs One sk sag ee QE]OPAM |eekomcs et a op----~ td PN OR WAG OWE Peres SOPs + | 9 “ZO(OlA Jule j---- ~ ZO(01A QUIGA | 8°00 JOOVA FUIB YT [~~ mmo ostpuy | 9°% 9°% 0° SrOTes | ORLi Soa ar ne OD ear +b PL COG ai Gea ae ora oprss* O:ORe ale ceca “ASV MONO Ae Paar = 55-5 SORES ag OTS PA ENA IIS Raa ps aetoss OD Eras + |It SOUON IPS" ae a GHORT ZO) “Fe oaan a qofoya quywy |---~=--= amo euoN | 8'2 |9°% |6°8 |S%0r | OTe |-~-~-~"gnuoo«oQ | + | Fh 49g 4o'q | 99 'd “plow ojuoydyns auez “ulsyony pazt Baia “plow d1u0ydins ouez ‘ulsyong pozt Dea aia. -U9QOZEIP YZIA\ IOJOD | -10[ODap YyIA IO[OD AUpIOY -U2EqOZBIP YI AO]OD| -10[ODap YALA I0J[OD Auproy| se po |-onea|onyea pores Ves q eens PT e a Wa aaa es ATE if)80) "| prouey *qUdUIZ BI} UBEzs WOT 97¥BI[1981G *7U29UI} 891} UlBE}s UOT [10 [BNplsey AIPPY "8710 snoiwpa fo senjpa aurpor pun 1fj20n ‘AqyiqgnsypxOQ— AT AIaVd, 106 The Philippine Journal of Science 1917 The oxidizability value for the coconut oils exceeded 15 (the maximum value given by sweet olive oils according to Issoglio) in samples 4, 11, 14, 32, 35, and 44. All of these samples were rancid, but samples 15, 30, 31, and 37, which were rancid, gave values lower than 15. It is possible that a limiting value of 15 for coconut oil may be too high, but the limit cannot be brought low enough to include all the rancid oils examined by us and still exclude the sweet oils. The test appears to be a good confirmatory one, since no sweet oils gave high results. The acetyl values of several oils were determined in an endeav- or to ascertain if any relationship exists between them and the rancidity. The lowest value, 7.0, was given by No. 31, a rancid oil, while the highest value, 21.7, was shown by No. 11, also a rancid oil. The value of the acetyl number is dependent on the presence of the hydroxyl group. Lewkowitsch makes no mention of the presence of hydroxy acids in coconut oil. The only unsaturated acid generally accepted as present in coconut oil is oleic, which exists in comparatively small quantities. It is possible that when rancidity takes place one of the reactions occurring is the formation of oxy or dioxy stearic acid from oleic acid, but this would not account for an acetyl number of a magnitude of 21.7 for coconut oil. The residue of the increase must arise from the freeing of the hydroxyl groups of the glyceryl radical. A high acetyl number should be, therefore, associated with a high acid value in the case of coconut oil. A study of the contents of Table IV proves that this relationship does not exist in all instances. It is possible that where the hydrolysis of the oil takes place in the copra itself much or all of the free glycerol remains in the press cake or is further de- composed, resulting in a low acetyl number along with a high acid number. The iodine number of an oil with a high acetyl number should be correspondingly low if the increased value of the acetyl nume ber arises from the oxidation of the unsaturated acids. The data in Table IV do not prove the validity of this assumption, since no definite relationship appears to exist between the values of these two chemical constants. Further tests were made on four oils. These data are re- corded in Table V. _—* 107 ine Coconut Oil Philipp Brill and Parker XU, A, 2 ‘UOI}RITMSIP Wea}S 0} UODarqnS 1o}Je [IO SUBST _,f,,, ! [10 [BUISIMO suEUT .,O,, q “1opo ex1[pie[ Sessessod MON ‘eind pue Jaoas AT[VuIsIIQ “vadod Uva[o “YysetJ WOT, GdUSIOS JO Nvoing Aq epeuw [IO uv | fe Spgs iicos-°2 aaa (es es Olea es Ope jn es osrpuy |7--------~ osipuy | ZZ | at | ZT |o'% | 98 | 0° | LOL | Lar £0 Cf a llesces seo auoN |-----~-- (6) aegis aoa ee QUON. Waeaca se @HONS |: = saan euoN | 8°0 | PT |9'2 |8'3 | 82 108 | F6 | 96 | “oB1p | PG aie ae was | opera |" qofora UBS | -ULIUSIS AOA ~~ OMPULISHS | LT | 9°0 | 970 | 8:0 | 82 | TS Ly | 99 “euoN a GION i" SUONE Sam ea’ =o =) C1 Gl ai a oa OUONS aa a oe asUuON | 8°0 | TT -|9°9T 18°11} 0°8 | 88 | 9°96] LTS (as |_ e ~ ol BEA SAA olE | Ee pe ees lh, om | uorynyos | f “u01y , | snosaby 0 -njos snoanby uo | AF [LOM TP iis th CO) lee are (0) eat | 0) | ns L (9) cia A peat Ba = 2 ) ae “St cet a c *O1TAgNG *a10]0 ‘ F | i ON ISSIOIN an[ea uoIjBUIUIAAJep plow 444 9[qQN[os Woy oNpise’ sv plow 47 se plow PP F eTqN] F ONPIFIy ~jey o[qnjog| 444¥y o04,7 qa YOY [4.207 “UISYONJ Pazito[Ovep YALA IO[OD ‘$710 ynuov09 snof fo szunjsuod aarjzospdwoj— A ATAV I, gy |0°9 | 0¢s TL | 8 | 2 p99 | 9°L | 6L OL Seas ape qL | 40 “(enyea snueH) | od auipoy | "Ss i 108 The Philippine Journal of Science 1917 Sample II was sour in odor, No. 19 was a sweet oil, No. 32 was smokelike in odor, while No. 50 was lardlike in odor. The iodine values of the steam-treated oils are lower in all four cases than are the iodine values of the original oils. Ap-. parently the unsaturated compounds are either volatile in the steam or they are partially changed to saturated compounds by the live steam. The acetyl values in three cases are lower for the treated oils. The hydroxy compounds appear to be somewhat soluble in the live steam. The higher value in the case of No. 11 probably arises from the hydrolysis of the glyceryl esters of the fatty acids by the live steam. The free fatty acids which are present in com- paratively large quantities in this sample act as accelerators of this hydrolysis of the neutral oil, or the mono- and diglycerides may be further hydrolized to free fatty acid and glycerol and © to the monoglyceride and glycerol, respectively. The Reichert Meiss] number shows the variation one would expect with the steam treatment of the oils. No difference in its value was found for the sweet and the rancid oils. The free fatty acids and their relationship to the rancidity have been already discussed. This constant is included here in order that the acid value for No. 50 might be tabulated. The relative values of the soluble fatty acids vary for the orig- inal and treated oils in a manner difficult to explain. Further data will be necessary before any conclusions can be drawn from this constant in regard to the effect of steam distillation. Dakin ?* has shown that when oleic acid is oxidized with hy- drogen peroxide azelaic acid is formed and all fatty acids from formic up to and including stearic are oxidized by mild oxidizing agents. If the formation of rancidity is caused or accompanied by an oxidation, one of the first changes to take place would be the breaking down of the unsaturated acids into simpler acids with an accompanying increase in the value of the soluble fatty acids. Consequently the value of -the soluble fatty acids of rancid oils should be greater than the value for the sweet oils. This generalization holds true for the original oils that have been tabulated in Table V. The milk from the coconut contains both oxidase- and perox- idaselike enzymes. These enzymes are not found in the pure, fresh coconut meat, and their presence in such meat is probably due to contamination from the milk of the meat. However, ** Dakin, H. D., Journ. Biol. Chem. (1908), 4, 68 and 2387. XII, A, 2 Brill and Parker: Philippine Coconut Oil 109 copra which has been attacked by molds or copra with milk adhering to it has oxidasing enzymes present, and when such copra is ground and pressed, some of this enzyme may be sep- arated with the oil. If such enzymes were present, they would in all probability have an important influence on the formation of rancidity. The oils described in this article were examined for oxidizing enzymes. No. 5 gave a faint test, No. 15 gave a fair test, and No. 28 gave a strong test for peroxidaselike enzymes with tincture of gum guaiacum and hydrogen peroxide. All the rest responded negatively for oxidizing enzymes with these reagents. No conclusion can be drawn concerning the cause for the pres- ence of the enzymes in these samples and their absence in all the others. No. 5 is a commercial sample of oil with a smoke- like odor, which indicates that it was made from tapahan-dried copra. In method of preparation and history it is very similar to Nos. 1, 2, 3, 4,5, and 7. No. 15 is an oil made from a machine- dried copra. This sample is very similar to No. 14 in history. No. 28, made from fresh copra, is pure and sweet and similar in most respects to No. 27. The enzyme here must arise from contamination from the milk of the nut. The activity of the other two must arise from the molds that grew on the copra before it was milled, the milling temperature not being high enough to destroy their activity. Why only these three gave positive tests is difficult of expla- nation. The color appeared in them only after the sample had stood in contact with the reagent for a short time. Tests were made on the fresh coconut meat for lipase, but we were unable to confirm the positive results reported by other investigators.17 Walker *® reports no lipase or zymogen pres- ent in the fresh meat, and our results are in accord with his. Where the meat of the coconut is subjected to a comparatively high temperature during the process of drying, the activity of any enzyme doubtless would be greatly decreased if not totally destroyed. But the hydrolysis of oils in the presence of mois- ture undoubtedly takes place to an appreciable extent at rela- tively low temperatures. In the experiments recorded by Deming, where comparatively large amounts of mineral acids were used “to activate the zymogen,” we believe the acid alone is sufficient to bring about the hydrolysis recorded by this observ- De Kruff, Bull. Dept. Agr. Indes Néerl. (1906), 4, 8. Deming; H. G., Phil. Agr. For. (1914), 3, 33. * Walker, H. S., This Journal, Sec. A (1908), 3, 111. 110 The Philippine Journal of Science er. Acetic acid failed to give like results when used by us, and were a zymogen present this acid should activate it. CONCLUSIONS - The color tests with decolorized fuchsin and with diazobenzene sulphonic acid are not reliable tests for rancidity. High acid- ity of oils is not coterminous with rancid ty. Steam distillation removes rancidity, but makes very slight changes in the acidity; neutralization with alkali and washing removes the acidity but not the rancidity. The Reichert Meiss] number in the few cases studied indicated no close relationship between this constant and the rancidity. No conclusions could be drawn from the magnitude of the iodine value. The soluble fatty acids show a relationship which indicates that this constant might be of value in an estimation of the rancidity of an oil. The acetyl value may be of value in indicating rancidity, but is not a meas- ure of the degree of rancidity. The oxidizability number ap- pears to be a good confirmatory test for rancidity, but a few samples of oils undoubtedly rancid gave low oxidizability values. However, where the value was high, the oil was always rancid. © Further work on the acetyl value, the oxidizability value, the soluble fatty acids, and the test for the presence of oxidizing enzymes and their action should yield valuable data. Control samples have been stored for the study of these constants. Pe pts uTHNOLOGY ‘ st | “A Yooaputany OF THE igoRo7 et: ees & : OS SPOKE "eh a Gece been oe Baia anata 9a, Bit me : rs RA: “The Vocabulary. = gi OCOD, $0.75 postpaid. “Ab * rar. and ies tess “This. volume. Sdeale ie ‘ * writ an of aha thie oft ato of. es in Tecord sete th nee to ding diagrams: c 0 No. 403) Paper; $02 : a ‘ i ‘ a $0,755" foe ie és Sale his - Pa Slee ih cooiewani BAe ‘history’ and present ly Pe ys 5a ca andar in the Philippine 3, $0.80, poctoald : “Order 'No.: 406 Peder 275 panes ‘maps, 2: Santa 0.75; postpal “An. the prepara tion ¢ ass ‘manusoript for Robs hd 3 the History. of Sulu, | tor “Saléeby” spent Red gees Rie ots Sintusle tims,” and. Be at gaining vaccess g Pe REP Meagtey,-)s decuments ins ee deep of Hoey ate mou See ae! ear Ane eee yee RS es : os In a rom the ai shee Ao’the Me Satoh egeuration THE PHILIPPINE JOURNAL OF SCIENCE A. CHEMICAL AND GEOLOGICAL SCIENCES AND THE INDUSTRIES MOL. X11 MAY, 1917 No. 3 DESTRUCTIVE DISTILLATION OF PHILIPPINE WOODS * By A. H. WELLS (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) In the United States and other countries the destructive dis- tillation of waste wood has become a large and growing industry. In order to furnish some idea as to the possible introduction of such an industry into the Philippine Islands, certain classes of woods were selected and the relative yields of products wer® de- termined on representative specimens. TABLE I.—Classification of commercial woods used for destructive distillation. r - Specific! yrois- | Botanical’ name. Commercial name.|Group. Hardness. ® grav- | a aele ity.b ; P. cent MED ROTEL BD» -—_ = ----+------- Bacsuane o=)- 4 | Very hard ____-___ 0.925 8.1 Bruguiera parviflora W. & A-__-| Langarai --_----_- AA ae Soo dor ga 5 eS 1.053 9.0 Avicennia officinalis L _______-_ A DIAAD Tost Ae ee 75 (3) ea ee Sea 0.754 To Intsia bijuga (Colebr.) O. Ktze _| Jpil _--_--_--_--__- De iblard = 222225. ded 0.933 6.7 IR DME Dea ee os oS Weacal eee iss Uh pees (3 Open eee al 0. 930 1.2 Shorea guiso (Blanco) Blume ---] Guijo -___-_--___-- DA ees doee-2s) 2. 0.716 7.4 Dipterocarpus sp-___-------- ---- Apitong2-3-=25-= 3 | Medium hard_-._--| 0.721 | 10.0 Shorea polysperma (Blanco) Merr]| Tanguili -_________ Si mea Cn) ae ee 0. 492 7.8 PEPTUCORDUSSD oo aon eee NAYS ooo oe a Ee See doy ea 0. 630 6.3 Pentacme contorta (Vid.) M.& R_| White lauan-_.___- AsltSoftees-5-- 382-2 0. 458 8.6 Anisoptera thurifera Blanco___-| Palosapis_-____--_ Balser Gole= == 2 0.711 8.4 Pinus insularis Endl__-------__- Benguet pine_-_-_-__ All ae, (5 (Cf eee 0. 687 9.2 ® Group and hardness are taken from Annual Reps. P. I. Bur. For. (1906-1914). » Specific gravity and moisture determination were made on the specimens used. The percentage of charcoal made in the Philippines from wood other than that cut for such specific purpose is very small. There exists in the Philippines a vast amount of wood of a waste nature, the possible utilization of which might be a great benefit to certain industries. Throughout the Islands in the timber * Received for publication January 30, 1917. 149517 ila ae The Philippine Journal of Science 1917 regions the annual production of waste wood about certain mills has so increased that the question of its disposal is now a problem before the mill men. Another possible source of waste wood is that from the cutch, or tan bark, industry. During the fiscal year 1914 there were taken from the public forests of the Philip- pine Islands 2,793,295 kilograms of tan bark.2 The highest percentage of this bark comes from the mangrove swamps. These swamps cover extensive areas in Mindanao, Palawan, and other islands in the southern parts of the Archipelago. If means for a profitable utilization of the wood from these trees could be devised, it seems probable that a stimulus would be given to © a larger tan bark industry. The woods selected for distillation are representative of the timber trees that are found in greatest abundance and also of the trees furnishing tan barks. Bacauan, langarai, and api-api represent classes of woods which comprise the greater portion of the forest areas in the swampy regions of Mindanao. The bark stripped from trees of the bacauan family is especially of value as a source of tannins, while the wood itself is little used as lumber and offers a ready supply for distillation. The area of these mangrove swamps is approximately 207,200 hectares.* Apitong, tangili, guijo, yacal, white lauan, and palosapis belong to the Dipterocarpacese and are representative of some of the principal timber trees that are milled in the Philippines. The dipterocarp forests are estimated” by the Bureau of Forestry as covering 70 per cent of the total area of the commercial forests of the Islands. Ipil and narra belong to the Leguminosz and are representative of that class of timber trees. Benguet pine, Pinus insularis Endl., is the com- mon pine, found principally in the Benguet region. It is milled particularly in northern parts of Luzon, where it extends over an approximate area of 518,000 hectares. The specimens of wood used for furnishing the analytical data were taken from several sources. The bacauan, the api-api, and the langarai were identified and cut in Mindanao swamps and were shipped to the Bureau of Science, where they were allowed to season for five years. The pine logs were obtained from the Benguet region through the courtesy of the Bureau of Forestry. The other specimens were identified and purchased from reliable lumber dealers in Manila, care being taken in selecting samples that seemed to * Rept. P. I. Bur. For. for 1914 (1915) and ibid. for 1915 (1916). * Cox, Alvin J., This Journal, Sec. A (1911), 7, 2. XII, A, 8 Wells: Destructive Distillation 113 show a likeness in size, color, specific gravity, and apparent moisture content. A separate lot of each kind of woods was kiln-dried until the moisture content seemed uniform. The whole specimen was then placed in a tight container, and from this the daily charge was taken and distilled.’ From eight to thirteen charges were made from each specimen and specific gravity and moisture de- termination made.on each charge. The averages for these de- terminations are found in Table I. The specific gravities were taken by the usual method. The measure of the moisture was not that of the total volatile substance below 108° C., which in many cases would contain oils, but a measure of the volatile part taken up by pure calcium oxide. The determination was made by passing the volatile matter through a tube of calcium oxide, afterward heating the tube for three hours at a temper- ature of 185° C. sufficiently high to volatilize all oils present and yet not to drive off water from the partially slaked lime. Destructive distillation was selected as the method for distill- ing the woods, the reason being that it seemed to give the highest yields of the commercial products—methyl alcohol, acetic acid, tars, and charcoal. Steam distillation might have shown interesting results regarding the resinous products obtainable, and this method may be applied later to certain classes of woods that are known to be high in resinous content. The destructive method is that in general use in the distillation of hard-wood waste, and for that reason also it is used here to furnish experimental data of comparative value. In determining a laboratory method for the distillation, it seemed advisable to have a temperature control. During 1913 experiments were made in this laboratory by utilizing an oil- jacketed retort. In the use of the oil-jacketed retort a heavy hydrocarbon oil was heated and kept in circulation by the aid of an electrically controlled Kinney pump, which was connected to the retort so that it supplied cold oil from the storage tank and also accelerated the circulation of the hot oil about the retort. Coils of various sizes and forms were tried as heating - surfaces for the oil. The most satisfactory surface seemed to be that of a piece of iron pipe 17 centimeters long by 13.5 centi- meters in diameter, capped at both ends, the caps being bored to accommodate a 1-inch circulation pipe. The heat was furnished by two Meker burners connected to the laboratory gas supply. The loss of heat by radiation was cut down by placing a heavy shell of asbestos cement over the 114 The Philippine Journal of Science 1917 retort. But this method gave neither the close temperature control nor other results desired. Also the cylinder oils sub- mitted for the bath gave unsatisfactory results under high tem- peratures; consequently the method was abandoned. In June, 1916, an improved experimental plant was set up and operated. The plant consisted of a cylindrical iron retort mounted at a suitable height and heated electrically in such a manner that the inside temperature could be closely controlled over a range in temperature of 500° C. The capacity of the retort was from 10 to 15 kilograms, varying with the specific gravity of the wood. The four heating coils were made of No. 18 “ni-chrome” wire arranged to give an approximate reading of 10 amperes for each coil. The wires were wound about the retort connected in parallels, insulated from the sides of the retort by a layer of asbestos board, and covered on the outside by a shell filled with a layer of asbestos powder 6 centi- meters thick. This outer layer left slight chance for loss of heat. The control of the temperature was effected by inserting re- sistance and by breaking the main circuit. Each coil in the resistance cut from the circuit gave a rise of 2 amperes current. This arrangement gave a very satisfactory temperature control. The condensation of the distillates and the scrubbing of the noncondensible gases occurred in a coil made of lead pipe 2.5 centimeters (1 inch) in diameter fitted inside an ordinary barrel of strong material and connected on the outside to a small tower from which extended pieces of glass tubing 400 centimeters long and of diminishing diameter. This tubing aided in condensing the lighter product and carried off the noncondensible gases. The tar trap for catching the heavy distillates was placed between the retort and the condenser. It consisted of a piece of iron pipe 10 centimeters (4 inches) in diameter, capped at both ends and fitted with a pet-cock at the bottom. Standardized thermometers were used in noting the temperature changes, which were taken at the center of the charge. Corrections for the emergent stem of the ther- mometer were made in accordance with the common formula 0.00016 (T—t) N. In order to get comparative data, both fast and slow runs were made on the lots of woods. In operating the still, the weighed charge was placed into the retort and the current was applied. The fast or uncontrolled runs were made with 35 to 40 amperes of a 110 volt direct current and occupied about nine hours before practical completion. No effort was made to control the heat except at the beginning of the exothermal reac- XU, A, 3 Wells: Destructive Distillation 115 tion, which began between 265° and 275° C. During this period the current was shut off until the reaction subsided in violence and was then immediately applied. The current was shut off to prevent a loss by overtaxing the condensing system. In the slow, or controlled, distillation the current was so ap- plied that the apparent moisture was first driven off. The moisture was considered driven off when a temperature was reached at which there was a decided pause in the distillation. This pause occurred at different temperatures for different classes of wood and varied between the temperatures 121° and 180° C. at the center of the retort. Later the passage of more current was allowed so as to afford the minimum temperature for dis- tillation. At the beginning of the exothermic distillation the main circuit was broken, and no current was allowed through until the rise in temperature ceased and distillation lessened. The rise in temperature during this period seldom exceeded 20°C. After passing this period of exothermic reaction, the distillation dropped off rapidly and the application of current was gradually increased up to a temperature of about 330° C. and was increased rapidly to 550°C. In collecting the distillate, graduated cylinders were used. _ Samples of pyroligneous distillate from each distillation were analyzed for percentages of wood alcohol and acetic acid. Such analyses taken on fast runs were compared with analyses of products from controlled runs, and the results were tabulated in averages. TABLE II.—Showing the average percentages of wood alcohol and acetic acid obtained from a fast and from a slow distillation. | | Slow distillation. Fast distillation. Wood. Methyl | Acetic | Methyl | Acetic % alcohol. acid. alcohol. acid. BENET LOND ee aa Renee eon enews. Kon ee ee 0.91 3.80 0.72 3.91 AMET) ie a ae Ie es ee 1,238 2. 92 1.10 2.85 LAN Thr SSSR eo Ree ee Soe es ee ae 1.20 2.90 vein 2.63 (Citi (i a Ses Sey 8 ce ae a es eee ee seen eee S 1.55 4.70 1.31 5.18 NEON [se Be Ee ee ee ep es ee, ae 0. 93 4,61 0. 92 4,25 (PALOSA DIS Mee soe ree nee en epee cre RL 8) 0.74 3. 83 0. 62 3.62 Lh E SES Beales se a ee ol Ete ee Se See CE eee ee 1.61 4,40 1.41 4,42 INSITE 2 eae no a oor aa eee nee ean ese 1.36 4.37 1.24 4,77 Berietiet pin ease sn ae a ee ee eee le 0. 82 2.12 0.80 2.51 (IBacanan Ss. 22S Sea ok es Po ee oe 3 2.12 5.16 1.56 4.84 ASV EETN a) (ppl ae te na Ns Gea pt aes a eee abi al 4.66 1.42 4,27 TRAN ORYA LC Sos se sees tas eee eee 1. 84 4.95 1.17 4.50 Coconutishellit- <5 Fe. eee: 2 Se Se eee ee 1.01 6.31 1.00 6.16 116 The Philippine Journal of Science 1917 The percentages in Table II are calculated on the moisture- free sample and not on the sample as kiln-dried wood. The figures expressing wood alcohol also include slight percentages of acetone present. Klar’s* method was used in the chemical analyses, together with those used by the United States Bureau of Chemistry ° and the Philippine Bureau of Science. The results expressed in Table II show that a distillation pro- ceeding under controlled temperature condition gives in most cases an increase in yields of methyl alcohol; that is, the average percentage of alcohol obtained by slow distillation is in all cases higher than that obtained by fast distillation. The mangrove woods bacauan, api-api, and langarai gave the highest yields in alcohol and acetic acid. Of the twelve woods distilled, those highest in resinous content gave the lowest percentages of these two products. The figures obtained for the yields of acetic acid do not show a relationship constant enough to warrant the state- ment that the controlled distillation gives higher percentages of acetic acid, although the greater number of distillations high in acetic acid are those carried out under the controlled distillation. : In most cases the distillate began passing over at 110° to 117° C. and continued at approximately the same rate up to 265° to 275° C., when the exothermic action of the decomposition tended to accelerate the flow. The clear liquor passing off below 180° considered as moisture gave no qualitative tests for the presence of alcohol, but did show an acid reaction toward litmus. Distillation under temperature control on certain hardwoods in the United States shows interesting results.* Lowering the temperature of the reaction and decreasing the speed of the dis- tillation in the laboratory at the period of exothermal reaction in- creased the yield of methyl alcohol 45 per cent. The application of this method to a commercial retort indicated possible yields of alcohol 30 per cent higher than by the usual methods of firing . and an increase of 15 per cent in yields of acetate of lime. The best results were obtained by first rapidly removing the moisture content of the charge and later decreasing the heat at a period just before the destructive distillation began. This method of temperature control gave promise of being entirely applicable in the commercial plant. *Klar, M. Technologie der Holzverkolung. Julius Springer, Berlin (1910). - * Cire. U. S. Dept. Agr., Bur. Chem. (1907), No. 63. * Palmer, R. C., Journ. Ind. & Eng. Chem. (1915), 7, 668. XII, A,8 Wells: Destructive Distillation 117 The yields from the destructive distillation of various Philip- pine woods have been tabulated and placed below. All of the calculations are expressed as percentage yields based on the moisture-free wood. The pyroligneous distillate represents the acid liquor free from tars. The percentage gas is taken by difference. TABLE II].—Percentage yields of various products from Philippine woods. a “ a a of 3 i s = ED 3 t gs E 3 5 3 el le 2 < A os] ue Wood. Gs aa 3 e ES 2 me | 8 2] SE | Bete. le leat eee |) ge | Se poe si) BF se) & 2 2 oa | & e ‘Saag | 5 Ay n Q & Zz Sy re < Z ek — ae psa pitong ------<2-----= 39.7 6.2 5.6| 8 15.1| 32.6 91] 3.80 13 Bempnite st e-2 ace 39.8 4.8 ert | ade Fe 18.8| 33.9 1.23 2.92 8 Lane 36.6 3.6 SUN eee eae 23540) 3352 1.20} 2.90 8 Cictitye el ee ee aa 35.5 3.9 DESH. Acme tl 20.0! 88.3} 1.55] 4.70 8 | pepe ea yf ft 34.6} 3.4] 21] 11/| 203) 385 93| 4.61 8 IPBIDSA DIA 24-8. sh 39.9 2.6 1 yA ee ene IEE) 36.6 74 3. 83 8 Tinh = Agee ea $2.4 3.9 2.0 Ole Oeil atere inet G ie |ss04eA0 8 (Navrdye see eee 39.4 5.7 Deli seoeree TEXON |e S658i |e te Son 4) Si 8 | Benguet pine ____-__!_. 38.9 5.5 3.6 iby 15.1 85.7 . 82 2.12 8 ACAMAN i Se) oe oe 39.5 Pat | a ay: Pee eee 21.2 35.2 2.12 5.16 8 engarai =.=". ----.-23- 40.8 2.9 13) | Sees "22.9| 82.1] 1.84] 4.95 8 PID InE Diet ere ae 43.4} 3.4 Saf Wl ae 19.0} 932.4] 1.71] 4.66 8 Coconut shell _________- 41.3) 6.9 B22) es 16.2} 32.5] 1.0 6.31 5 3 | The pyroligneous distillate as it comes from the retort ranges in color from pale straw, given by palosapis, to a deep brownish red, given by narra. Titrations were made on ten fractions covering the periods of complete runs. The fraction showing the highest percentages of acid varied with the class of wood dis- tilled, but fell between the temperatures 285° and 325° C. ‘Tabie III gives the yields expressed as 100 per cent acetic acid on dry weight of wood based on a slow or controlled distillation. Bacauan, langarai, and api-api give the highest percentage yields of methyl alcohol and acetic acid. The woods giving the lowest yields are woods known as soft woods and woods containing resin. Results obtained in the United States showed? yields of acetic acid for maple, beech, and birch (three hardwoods) as high as 6.30, 6.28, and 6.96 per cent, respectively, the percentages being based on per-unit weight of the oven-dried wood distilled. It may be that distillation of other classes of Philippine hardwoods will show higher percentage yields than those obtained from the woods already examined. "Palmer, loc. cit. 118 The Philippine Journal of Science 1917 Determinations of acetone in the pyroligneous distillate were neglected except for qualitative tests showing its presence. Many of the distillates, especially those from the resinous woods, contained aldehyde and higher ketonic bodies and substances influencing the reduction of the iodide. For the determination of the alcohol the method suggested by Stritar and Zeidler * was used, but was afterward replaced by the modified methyl iodide method. With the hardwoods free from light oil the percentage could be taken from the specific gravity of the dis- tillate according to the methods of Klar.°® TARS The tars were classified as settled tars, dissolved or “boiled” tars, and floating tars. The settled tar was the portion taken from the tar trap added to that which settled at the bottom of the pyroligneous liquor. Dissolved tars are those lighter portions dissolved in the pyro- ligneous liquor, but separated by boiling off. The floating tars were very light products found floating on the surface of the distillate and in the scrubbing tower. They gave tests for methyl alcohol, acetone methylated compounds, ketones, terpenes, and neutral hydrocarbon oils. The total tar included all three of the classes, and as such it was used as an analytical sample in the case of each wood distilled. The composition of oils originating from fhe destructive distillation of wood has been thoroughly studied by Fraps.*° Working on tar from hardwood, he arrived at the following results, which show the complex nature of a hardwood tar: (1) The wood oil examined is a mixture of a homologous series of dif- ferent classes of compounds. (2) It probably contains the series of aldehydes CnHmO, corresponding to the series of saturated acids CnHmO2z, found in wood vinegar, which goes up to and includes caproic acid. The quantity of aldehydes is so small that only one could be positively identified, valeric aldehyde. Acetic alde- hyde and propionic aldehyde have been found in wood oil by other investi- gators, and these facts justify the first statement. It contains furfural in minute quantity. ; (3) It contains the series of ketones CnHmO, of which dimethylketone, methylethylketone, methylpropylketone, and probably methyl-n-butylketone and diethylketone have been detected. (4) It contains the ring ketone, cyclopentanone, and other ring ketones. e * Zeitschr. f. anal. Chem. (1904), 43, 881. * Loc. cit. “Fraps, G. S., Am. Chem. Journ. (1901), 25, 26. XII, A, 8 Wells: Destructive Distillation 119 (5) It contains no mesityl oxide nor methylcyclopentanone, (6) It contains nitriles in minute quantity. (7) It contains the methyl esters of the saturated acids, CnHanOz, found in wood vinegar, including methyl acetate, methyl propionate, methyl _ n-butyrate, methyl n-valerate, very probably methyl caproate, and methyl heptoate and possibly methyl isobutyrate. The acid corresponding to methyl heptoate has not yet been found in wood vinegar. The percentage of ethereal salts decreases as their boiling-points rise, the lower-boiling ones being present in considerable quantity, the higher ones in very small quantity. One might conclude from this that the quantity of the corres- ponding acids in wood vinegar decrease with increase in boiling-point. (8) It contains the esters of unsaturated acids. (9) It contains methylfurane, and furanes which can be hydrolyzed by cold, strong hydrochloric acid to diketones. The furanes include dimethyl- furane, trimethylfurane, and higher furanes. (10) It contains no dimethylacetal, nor appreciable quantities of pyri- dines or alcohols. _(11) It contains compounds which take up hydrochloric acid and bromine, and are therefore unsaturated. (12) It contains the aromatic hydrocarbons, toluene and xylene, and probably cumene and cymene. (18) It contains creosote. (14) It contains phenol ethers in minute quantity. (15) The higher boiling oils, freed from ketones, aldehydes, ethereal salts, and creosote can be separated into two parts by glacial acetic acid, the one soluble in that substance, the other insoluble. Both absorb bromine readily. Samples of tars from the Philippine woods were fractionated in a high distilling flask without the use of the Hempel column, and the results obtained are tabulated in average. TABLE IV.—Showing average percentage of light and heavy oils passing over in fractionation of the various tars. ® [Numbers give percentages. ] bi Wood oil| Light Heavy | Distillate Name. below oils, 100°-|oils, 150°-| above 100°C. | 150°C. | 250°C. 250°C. | US COATT ee se ge et A Se Sore Sine Bel 0.5 6.0 19 15 LOG ERENT Si i se eee es enone Ries Se aaa 0.8 6.2 20 15 JSS EES) eS Se SS SE ee ee eee ee 0.3 0.6 20 16 eee eo. See ep pe eee PE hiya ee as tel 2.5 2.3 32 RV Al etl feet eee teh So ee a ae ee ae 3.0 6.0 35 0 UT Ota ea arse ae ea oe ee ee. ee 2.0 5.0 40 0 PAD ICON $2 aa ty ee eee ee Pa pak eee as EON Te 2.2 2.2 28.0 0 oD) aA A Re Le eh 1.8 2.6 21 14 IN AY Se Ses Se od ak a I Fn pa, 2S! 2.4 2.5 54.0 0 Wns Ce annie nn ee eee te nae een ee nae et ane 2.0 1.5 20 0 Palosapists 252 s2s8—. coe eee eee meee ae ee Ne Ie | PV2 2.6 20 18 Beng netpines: =~ 3456 2 o eo ee a ee Es | 2.8 6.0 29 11 x Coconut shell___________ RE yeah ery A io cae Ee 2.5 8.0 50 7 120 The Philippine Journal of Science 1917 The samples taken for fractionation were freed from water by settling and by repeated use of separatory funnels. Yet on fractionation a high percentage of water was found dissolved in certain of the tars. In the cases of palosapis, white lauan, pine, and guijo the percentage of water ranged from 20 to 34, while in the others it seldom was above 10 per cent and was even as low as 2.6, as in api-api. The fractions passing over below 100° C. have a specific gravity of 0.958-0.998; are colorless, quickly turning yellow to brown; are very inflammable; and have a strong, characteristic odor. They gave reactions for aldehydes and ketones by the acid sulphite method. Attempts to form terpene compounds from the fractions from the resinous woods gave slight results. A few crystals of terpene hydrate were obtained. The fraction passing over between 150° and 250° C. and con- taining the creosote fraction ranged from pale yellow to brown. All specimens quickly darkened. The specific gravity varies from 1.010 to 1.028. The green and the blue oils began passing over at 230° C., accompanied by a small amount of water, indicating ' decomposition of some of the compounds present. This decom- position and liberation of water was greater with the tars from the apitong and other resinous woods than from the bacauan and less resinous ones. The green anthracene oil preceded the blue coming over in distillation. The fractions from each of the tars showed marked reaction with caustic soda and gave rapid reaction for esters. Two cubic centimeters of the oil added to 100 cubic centimeters of a 20 per cent solution of sodium hydroxide set to a heavy, flocculent white precipitate. About 70 per cent of this compound decomposes upon washing free of alkali or treatment with solvents. The percentages of oil unacted upon by the sodium hydroxide seemed very low. No further work was done on this portion of the tars. It is pro- posed at a later date to fractionate larger quantities of this fraction, getting the exact creosote fraction and the percentage of phenolic compounds present. The fractions passing over above 250° C. are semisolid and usually red. They contain the highest fractions of the wood tar, together with certain high boiling fractions of the wood resins and their decomposition compounds. The residue after fractionation is a vitreous black pitch, having a conchoidal fracture and rather high melting point. It is slightly soluble in alcohol, chloroform, and ether and is moder- ately soluble in carbon disulphide, acetone, benzol, and xylene. XII, A, 8 Wells: Destructive Distillation 121 The charcoal taken from the retort is steel gray to black. It has a metallic luster and a conchoidal fracture. The charcoal from all the specimens, excepting tanguili, lauan, pine, and palo- sapis, is heavy and has a decided metallic ring when dropped upon a hard surface. The yields are from 32.1 to 41.7 per cent, calculated on the moisture-free sample. All of the specimens are hard to ignite and burn without flame, smoke, or odor of tarry matter. This class of charcoal would fill all the requirements of a charcoal for domestic purposes, while some of the woods would furnish an excellent. charcoal for the iron industry in the Philippines. : Table V shows the results of an analysis of bacauan charcoal that came from a charge heated to 550°C. The sample was taken from an old lot of bacauan charcoal that had stood in the laboratory for a year. TABLE V.—Analysis of bacauan charcoal. CHARCOAL. » Per cent. Moisture (110° C.) 5.71 Volatile combustible matter 23.79 Fixed carbon 67.21 Ash : 3.29 Total 100.00 Available calories 6799 Gross calories 7242 ASH.2 Per cent. Silica (SiO.2) 2.98 Tron and aluminum oxides (R:0:) - 2.95 Calcium oxide (CaO) 61.81 Magnesium oxide (MgQO) 2.72 Potassium oxide (K.0) 2.43 Sodium oxide (Na:0) 8.93 Phosphoric anhydride (P.0;) 1A Sulphuric anhydride (SO;) 2.29 Chlorine (Cl) 0.12 Carbon dioxide (undetermined) 14.56 100.00 4 Analyzed by A. S. Argiielles. The volatile combustible matter seems somewhat high. The calorific values are excellent and probably higher than any value that could be obtained on charcoals made by the Filipino process of burning. The analysis of the ash indicates that bacauan charcoal might be unsuitable for the manufacture of 122 The Philippine Journal of Science 1917, pig iron for use in the foundries in the Philippines, due to the high percentage of sulphur which it contains. Cox !! has shown that there are many woods in the Islands from which the charcoal obtained is entirely free from sulphur and is suitable for use in the smelter. Certain features shown in the analysis of the ash, such as the high percentages of calcium and sodium oxides, may be possibly explained by the fact that the mangroves are distinctly salt-water species occurring in tidelands. The high calorific value places bacauan charcoal as a high-grade fuel for all domestic purposes, and for such purposes there is a great demand for charcoal in the Philippines. Coconut-shell charcoal possesses remarkable absorptive prop- erties. Such charcoal was used by Wright and Smith ” for filling the absorption tubes used in their quantitative determinations of radium emanation, The matter of first cost and operation expenditures is one of individual calculation, depending upon certain local conditions. The production costs, costs of installation, and production values received in the United States in the distillation of hard- woods have been discussed in some detail. French * finds the production cost to.be approximately 17.70 pesos and the production value of crude products 19.82 pesos, giving a profit of 2.12 pesos per cord. He places the cost of installation, eliminating the cost of wood supply, at 4,000 pesos per cord per day production. These figures are for a plant producing crude products from hardwoods. In determining whether a plant may prove profitable or not, many factors must be taken into consideration. Through the courtesy of a manufacturer of wood-distillation plants ** this Bureau has been furnished with a few of the leading questions that should be considered as important factors in plans for a wood-distillation industry. 1. How much wood, and of what quality, is to be worked per year, and in how many working days? What is the price of sufficiently split wood at the place where the factory is situated? ™ Cox, A. J., Philippine firewood, This Journal, Sec. A (1911), 6, 10. “Wright, J. R., and Smith, 0. F., This Journal, Sec. A (1914), 9, 54. * Klar, ‘loc: ‘cit, “French, E. H., Journ. Ind. & Eng. Chem. (1915), 7, 55. * One peso Philippine currency equals 100 centavos, equals 50 cents United States currency. * Mr. F. H. Meyer, Hannover-Hainholz. xUyA, 8 Wells: Destructive Distillation 123 2. What is the weight per cubic meter, or what is the form of the wood used? How long does it lie before it is put in work? 3. What products are principally intended to be manufactured: Charcoal. Anhydrous tar. Charcoal bricks. Tar oils and creosote. Brown acetate of lime, Crude wood spirit of turpentine. Gray acetate of lime. White deodoriferous pine oil. Crude wood spirit. Pine tar oil. Refined wood spirit. Crystallized acetate of sodium. Pure methyl-columbia spirit. Acetate of sodium, free of water. Acetic acid in all kinds of quality. Formaldehyde. Acetic acid for vinegar. Paraformaldehyde. Acetone. 4. Is there a market for charcoal, and at what price? 5. Is there a market for tar, and at what price? 6. What kind of fuel may be had and at what price? 7. Is cooling water to be had (state whether fresh or salt water), and what is the mean temperature? 8. Is running water in the neighborhood? 9. Describe the local conditions (distance to nearest railroad station or steamship landing place, harbor, etc., as well as character and condition of roads, etc.). 10. Is there any:junction for railway or ship? 11. What is the freight for the products as far as the next place of consumption? 12. What is the freight for apparatus and machinery from manufacturer to place of factory? 13. Are there any buildings to be utilized? 14. Are there any repair shops and how large are they? 15. Are there gratuitous plots of land existing? 16. What are the prices for building materials, such as brick, wood, mortar, etc.? 17. What is the price for finished buildings above the ground: in brick, in framework, in sheet-iron roofs? 18. What is the price for high-furnace-masonry, of brick stone, or chamotte? 19. What is the price for iron-fittings for furnaces per hundred pounds? It may be readily seen that many of these questions might be answered favorably to the installation of a plant in the Philippines, while at the present time others make it seem impossible as a commercial success. From a study of the statistics of the Islands it seems probable that a market for the products of a wood-distillation industry could be found in the Philippines and near-by ports. Wood alcohol is used commercially as a denaturant and as a solvent for fats, oils, and resins. It is also used in the manufacture of aniline colors, smokeless powder, and formaldehyde and in 124 The Philippine Journal of Science 1917 various other chemical industries. Acetic acid is used in the manufacture of compounds used in the dye and paint industries. Acetone is also made from the acetates formed in the process. Acetone is used commercially as a solvent for resins and other compounds; it is also used in the nitro cellulose industry and in the preparation of many pharmaceutical compounds. The tars obtained by destructive distillation can be treated and certain fractions used in turpentine substitutes, cheap varnishes, lubri- cating oils and greases, inks, leather, soap and cement industries, and for impregnating timbers and ropes. The crude tars from the Philippine dipterocarps, being high in percentages of resins and oils, should prove very satisfactory as an impregnating or coating substance for ropes and calking used in ship building. Also, as many are high in creosote frac- tion, their use as a disinfectant or spray for sanitary purposes would furnish a reasonably cheap and efficient substitute for the more expensive mixtures now employed throughout the Islands. The pitch can be used for coating purposes. Certain conditions are essential for the successful operation of a distillation plant. The first essential is a supply of the raw material of the proper quality and in large quantities that are easily accessible. This not being obtainable, the plant should be one accommodated only to the needs of the mill for clearing away the accumulation of waste wood and sawdust, which may hinder proper operation of the mill. However, in this case it must be observed that the use of small retorts of a capacity of 0.25 to 1 cord would require a disproportionately greater ex- penditure for wages, for fuel, and for repairs than would the larger retort systems. Likewise the percentage yields are greatly reduced, due to the overheating in the small retort. A plant erected for supplying products to the Philippine market would probably manufacture charcoal, gray acetate, refined wood spirit, tar oils, and creosote. All of these prod- ucts have a market and could be used in Philippine arts and trades with the possible exception of the gray acetate, for which use might be made by its conversion into acetic acid or acetone. CONCLUSIONS Specimens from twelve kinds of wood have been submitted to destructive distillation. A furnace, heated electrically, has been devised to furnish controlled as well as noncontrolled distillations. XII, A, 8 _ Wells: Destructive Distillation 125 The yields of methyl alcohol, acetic acid (100 per cent), charcoal, and tars have been tabulated to show average per- centages of products obtained by laboratory practice. Controlled distillation has shown results higher than those of the noncontrolled distillation in average percentage yields of methyl alcohol and acetic acid. These results are analogous to those found by Palmer.” A short discussion of costs and operating expenses is added. * Loc. cit. end 7 \ pe (Oly Voi OT Ray Gling iG caaiane tere Tee) Wea iads (A aati | p osibotenty We Deer A at cof sh bane : Lae | iy iiyae eee 0 ae Aly Ca rr ents Pi sy oh een te Pe aa ae mee “iphiahabhait.d ees, alia aa ye ea". Aaa Ht ee - cy ‘ rin oe oni Cosel toage sani ti in ideubiatri,5 f “sh kaaeeoat ‘eae me hae lve 2 ve ) iy has ‘ ts ae inal veg) nih ee oe eho : : ay 4 : ‘ TE OSE tobe) D4 np; B +e (ey ras, ¥ Way, j oak ahi AD ‘se tyey hk sch Seagull 16 lea nares : OR IEW a Sy ae Caan “iF wae ar \ ; ere ak ies ’ ‘7 ree 0 \ WV PR ge er sae TMG Rpg pte ae pete aes | mp | wy , eee nit | é : r OT) : (a, isi j he rian Te $ aa ‘ vs we ane’ “_wite nts cin 4 a-yeedt Viggl O : : bey 7 a : : 4 . eet a ya elvis aia Me J Tee \/epPia fa erry iv 5 4 ea. ee ; 4 “ “¢ ‘ 5 4 AT . ¥ vee 7 | ; I Fits i’ p |e a “ty ’ ¥ } < r < ; oY 7 * f rf te 3 a 2 i i. 7 * é > wi J yatta pte me shat) Oe ee, Pade Tata he, THE POSSIBLE MAXIMUM VITAMINE CONTENT OF SOME PHILIPPINE VEGETABLES * By Harvey C. Britt and CEcILIO ALINCASTRE (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) Recent investigations have proved that a diet composed of the proper proportions of fat, protein, and carbohydrates is not necessarily an adequate diet for the maintenance of health and growth. Other’ ingredients must be present; for example, in- organic salts must be present in sufficient quantities.” The absence of certain either-soluble * substances is prejudicial to health. This substance has been named ‘fat soluble A” by McCollum,* because of its presence in certain natural fats. Besides the above-required constituents, another substance, known under the various names “vitamine,” ® “oryzanin,” ® and “water-soluble B,’’* is necessary. No reliable quantitative methods for the determination of this vitamine constituent have been perfected. In the processes used for its isolation, much of it is undoubtedly broken up into simpler substances,* or the antineuritic principle may be due to the presence of a number of bodies. The latter assumption is con- siderably strengthened by the results obtained by the use of various substances * in the treatment of beriberi. A further * Received for publication April, 1917. Osborne, T. B., and Mendel, L. B., Feeding experiments with isolated food-substances, Publ. Carnegie Inst. Washington (1911), No. 156, Parts I and II; and Science (1911), 34, 722. McCollum, E. V., and Davis, M., Journ. Biol. Chem. (1918), 14, 40. Hart, E. B., and McCollum, E. V., ibid. (1914), 19, 378. * McCollum, E. V., and Davis, M., ibid. (1918), 15, 167. Osborne, T. B., and Mendel, L. B., ibid. (1918), 15, 382. *McCollum, E. V., Simmonds, N., and Pitz, W., ibid. (1916), 28, 153. °Funk, C., Journ. Physiol. (1912), 43, 395. ° Suzuki, U., Shimamura, T., and Odake, S., Biochem. Zeitschr. (1912), 43, 89. "McCollum, E. V., and Kennedy, C., Journ. Biol. Chem. (1916), 24, 491. *For_a brief bibliography of methods, see Williams, R. R., This Journal, Sec. A (1916), 11, 49. ° Williams, loc. cit. and Journ. Biol. Chem. (1916), 25, 437. Williams, R. R., and Saleeby, N. M., This Journal, Sec. B (1915), 10, 99. Williams, R. R., and Seidell, Atherton, Journ. Biol. Chem. (1916), 26, 481. 1495172 127 128 The Philippine Journal of Science 1917 confirmation of the probability of the existence of a number of antineuritic substances in rice polishings, yeast, wheat, and bran, which are antineuritic in character, is the recent discovery by Williams *° of the peculiar action toward polyneuritic pigeons of the hydroxypyridines, when they undergo dynamic isomerism, and of the similar action of the vitamines isolated from autolyzed yeast." _ If the vitamine content of foods does consist of a number of distinct chemical compounds, the difficulty of quantitatively de- termining it is readily seen. However, some attempts have been made to make such an estimate. Phosphotungstic acid in alka- line solution gives a blue color reaction with the antineuritic substances.'* Phosphomolybdic acid gives a similar color reac- tion.4? The intensity of the color is dependent on the concentra- tion of the vitamine. The handicaps attached to these methods are that no standard exists that can be used for comparison and that other compounds give similar color reactions. The quantitative isolation is unsuccessful because of the pres- ence of nitrogen compounds, which either accompany the vita- mine or are the result of its decomposition. Vedder and Williams '* report that three successive extractions of rice polish- ing with alcohol did not extract all the antineuritic properties of _the polishings. Funk © has made an attempt to determine the vitamine con- tent of milk in the following manner: The milk was distilled in a partial vacuum at 30° C. It was then powdered and dried to constant weight. The powder was shaken with alcohol for two hours and filtered, and the filtrate was evaporated to dryness. The residue was extracted with water, acidified with sulphuric acid, and treated with phosphotungstic acid. The nitrogen of the phosphotungstic acid precipitate was determined by the Kjeldahl method. By this method Funk estimates the vitamine content of milk to range from 1 to 3 centigrams per liter or from 0.001 to 0.003 per cent. * Williams, loc. cit. 4 Williams and Seidell, loc. cit. * Drummond, J. C., sine Funk, C., Biochem. Journ. (1914), 8, 598. Rolin O., and Macallum, A. B., Journ. Biol Chem. (1912), 11, 265; (1912), 13, 363. * Folin, O., and Denis, W., ibid. (1912), 12, 239. Funk, C., and Macallum, A. B., Biochem. Journ. (1918), 7, 365. “ Vedder, E. B., and Williams, R. R., This Journal, Sec. B (1918), 8, 175. * Funk, C., Biochem Journ. (1918), 7, 211. XI, A, 8 Brill and Alincastre: Philippine Vegetables 129 In a subsequent communication Drummond and Funk *° report that all the nitrogen of vitamine is not obtained by means of the Kjeldahl method; so the results recorded above for milk are probably low. Compounds containing the pyridine ring possess this same property of resisting digestion with sulphuric acid for the determination of nitrogen.'* Approximately three fourths of the nitrogen of such bodies were obtained by this method. A method based upon this property of pyridine derivatives has been employed by the authors for the determination of the pos- sible vitamine content of some vegetables grown in the Philippine Islands. DETERMINATION OF THE VITAMINE CONTENT OF VEGETABLES A portion of the fresh vegetable was dried at a low temperature and very finely ground, and 100 grams of the ground foodstuff was exhaustively extracted with methyl alcohol. The alcohol was evaporated at low temperature, and the residue was taken up in water and filtered. The filtrate was acidified with suf- ficient sulphuric acid to make a concentration of 5 per cent. Phosphotungstic acid was added to this solution to precipitate the antineuritic substance. After standing for from four to eight hours, the precipitate was filtered off, washed with 5 per cent sulphuric acid and finally with alcohol, and dried in a desiccator over sulphuric acid. The nitrogen was determined in this residue by both the Kjeldahl and Dumas methods. Weighings of the precipitates and nitrogen determinations were made to serve as checks. These determinations are in- cluded in Table I. The calculations were made on the vege- tables 1* as they were prepared for the table. The values for the vitamine content of Philippine vegetables found by this method are usually higher than the results found by Funk? for milk. However, they are presented here because they have comparative value and for the purpose of stimulating further investigation in quantitative determination of these constituents. * Drummond, J. C., and Funk, C., Biochem. Journ. (1914), 8, 598. * Brill, H. C., and Ageaoili, F., This Journal, Sec. A (1917), 12, Kjeldahl process. - * For description of Philippine vegetables, see Agcaoili, Francisco, ibid., Sec. A (1916), 11, 91. * Funk, C., loc. cit. 1917 rence Journal of Se ippine al The Ph 130 2980 0 8820 02 92002 0800 °0 0220 0 9100 0 *2Ua0 aq q’90u0 “10H 1d 8P10 0 09L0 0 9PF0 0 8890 0 9280 °0 910 °0 P810°0 0&F0 0 $200 0 02200 8200 0 "quad Lad |"7U99 Lad ‘sung | 14yeplPery 8600 0 P2000 2980 '0 88200 920 0 vPro 0 8900 0 p9E0 0 ¥900 0 vPLO 0 8220 °0 ¥200°0 »—Aq ueso1j1uU WOIj pozB[No[eo soyduies [BUISZIIO Ul BULUIEIL A 8L°S 29 “81 GL” 4Wao Lag €L8°0 | L06°0 80P LT | 682°T quao “q\'7U20 “qd 96°0 90°0 GPT 8. 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A method based on the different values for nitrogen in py- ridine ring bodies obtained by the use of the Kjeldahl and the Dumas methods is presented. A table with some results. for Philippine vegetables is given. THE EFFECT OF CALCIUM SULPHATE ON CEMENT * By J. C. Witt and F. D. REYES (From the Laboratory of General, Inorganic, and Physical Chemistry, Bureau of Science, Manila) Calcium sulphate in the form of either gypsum or plaster of Paris is almost universally used to control the setting of cement. The practice has led to extensive research in the attempt to determine the reaction between the two substances and the amount of calcium sulphate that can be added without causing harmful effects. As a result of these investigations some points are fairly well established. A number of writers” agree that the retardation of set caused by the addition of calcium sulphate is proportional to the amount added, only within certain limits; that is, the setting time cannot be increased without limit by adding more and more of this substance. On the contrary, after a certain point is reached, further additions cause an acceleration of the set. Many believe that the permissible amount of calcium sulphate added to a cement should depend to some extent on the condi- tions to which the concrete made from it is to be exposed. Several countries, among which are France,? Japan,‘ and Argentina,’ specify that a cement, intended for construction exposed to sea water, shall have a lower sulphuric anhydride (SO,) content than one to be used under ordinary conditions. The German Portland Cement Manufacturers’ Association ° recommended that “a uniform permissible maximum limit of SO,, namely 2.5 per cent, be generally adopted in Specifications for Portland Cement, whatever may be the purpose for which * Received for publication November 138, 1916. *Carpenter, R. C., Hng. Digest (1908), 3, 385. Rohland, P., Stahl wu. Hisen (1908), 28, 1815. Reibling, W..C., and Reyes, F. D., This Journal, Sec. A (1911), 6, 225. *Ciment (1912), 17, 218. ‘Mitt. Zentralstell. Ford. Deut. Port. Zem.-Ind. (1912), 1, 167. "Ibid, (1912), 1, 305. * Report of the International Association for testing materials (1912), Sec. 2, article XVII, 1. (Translated by G. Salter.) 133 134 The Philippine Journal of Science 1917 the cement is intended.” This recommendation was made’ on the basis of results obtained with only two cements: The materials used consisted of a Portland cement (S), containing 1.19% of SO; and employed for all purposes, marine structures included, and another Portland cement (B), which contained only a very small proportion of SO;:, namely 0.57%. In both cases the raising of the SO.-content to 2.5% by the addition of gypsum, increased the tensile strength, both in fresh and sea water. In the summary of the paper it stated that— From these results it follows indubitably that the presence of up to 2.5% of SO; in Portland cement, produces no injurious effects of any kind, whether in sea water or fresh water. No matter how conclusive these results appear, or how care- fully the work was carried on, it is impossible to settle such an important question by the behavior of only two cements, par- ticularly in the face of contradictory evidence obtained by other investigators. It is generally conceded that an excessive amount of sulphuric anhydride in a cement is harmful. All specifications mention an upper limit, though not all agree what this limit shall be.’ Meade ® says:- Although the presence of calcium sulphate in small quantities is bene- ficial to cement, there is no doubt that a quantity exceeding 4 or 5 per cent is injurious. According to Ktihl,® the sulphuric anhydride content of a cement should not exceed 2 per cent. Rigby *° states: In making some experiments with cement by adding plaster of Paris by mixing the two materials in different proportions, I found that if I exceeded 4% per cent of the latter the briquettes subsequently made from the mixture either broke up after being placed in water for a time, or, if they retained their shape, they were very much cracked and gave a very poor test. Bates '! found that while higher sulphuric anhydride content “Though the specifications of various nations for the upper limit of sulphuric anhydride are often taken as directly comparable, this is not the case. For instance, in the British specifications, 2.75 per cent sulphuric anhydride does not refer to the sulphur present as sulphate only, but means the total sulphur calculated to SO;. (See British Standard Specifications for Portland Cement. Revised, March, 1915.) * Meade, R. K., Portland Cement. Chemical Publishing Co., Easton, Pa. (1906), 31. * Kiihl, H., Mitt. Zentralstell. Ford. Deut. Port. Zem. Ind. (19138), 2, 108. ° Rigby, J. S., Journ. Soc. Chem. Ind. (1890), 9, 254. “ Bates, P. H., Proc. Am. Soc. Test. Materials (1915), 15, II, 126. xu,A,3 Witt and Reyes: Calcium Sulphate on Cement 185 (up to 2.5 per cent) in some cases increased the strength of neat briquettes, it caused considerable expansion. In attempt- ing to compare some of the papers on the subject, considerable confusion arises from the terminology of various writers. Some of them refer to the percentage of gypsum added to cement and others to the percentage of plaster of Paris; as a rule, they do not state the percentage of sulphuric anhydride. Others mention simply calcium sulphate, and the reader has no means of knowing in which form it was added. Although the effects of the two substances are similar,’? there is a considerable dif- ference in the amount of sulphuric anhydride in the commercial products. Different cements require varying amounts of calcium sulphate for the purpose of controlling the set. However, there must be some limit specified for the addition of material sub- sequent to calcination to avoid adulteration by unscrupulous manufacturers. The specifications state the maximum amount that can be allowed with safety. It remains to investigate the region between this amount and that definitely known to be injurious. It seems likely that the specifications of the countries that make allowance for the conditions to which con- crete is to be exposed show an advance in the right direction and that in addition to this there should be some relation be- tween the composition of the cement and the sulphuric an- hydride allowed. Until the subject is better known, safety demands that upper limits should be kept well below the amounts known to be harmful. The present work was undertaken to determine the effect of various amounts of calcium sulphate on several cements on the local market and to study in some detail the behavior of a cement made from raw materials available to the Bureau of Science for investigation. The finished cements investigated are from five different factories and are herein designated as A, B, C, D, and E. Each contained a certain amount of calcium sulphate placed there by the manufacturer. Various amounts of plaster of Paris were added to each, giving increasing amounts of sulphuric anhydride up to about 10 per cent. Investigation of the other cement, designated by F, started with the clinker, which contained only a trace of sulphuric anhydride. The set- ting time on each sample was determined as a preliminary test. These were used as a guide to determine the percentages of sulphuric anhydride best suited to extended tests. Tables I and ™ Meade, op. cit., 307. 136 The Philippine Journal of Science 1917 II show the analyses and the physical tests made on the cements as received. TABLE I.—Chemical analyses of cements as received.* [Numbers give percentages.] Cement— i A B. Cc D ILOSBONUENILION . a nos oooh ee ence eno 2.50 2.80 1.50 2.40 Ensoluble residue sesnese en. sea eae eee 0.30 0.60 0.30 0.80 Silicax(GSiOp) i: See 2 ees ety. pr aes eee 21.10 | 20.00! 22.50; 18.80] 18.95 | 22.82 ATuminaiCAle Os) cas ese eee oe 8.76 8.86 7. 58 9.18 9.52 | 8.21 Werric'oxide (He2@3) =ac-—2noe- eet ee 1.42 1.34 1.12 1.12 1.38 | 3.64 Caleiumoxidel(Ca@) eae eee 63.10 | 63.00 Magneésia\ (MeO) a: 2 er a a 1.26 1.34 Sulphuric anhydride (SOs) ._---___--__--___--__- 0.67 0. 86 Potassium and sodium oxides (K20, Na2O) _---- 0. 98 1.16 ® Most of these analyses were made by Francisco Pena, inorganic chemist, Bureau of Science. TABLE II.—Physical tests of cements as received. Fineness. Specific ane fe Brand. 8 Pagnings Passing | gtavity. Initial set.| Final set. 200-mesh | 100-mesh sieve. sieve. Per cent. | Per cent. H. m. | A. m. ey epee SN id eR em 87.6 99.0 3.12 5 15 PD sobocdeaeoeues aokee SIS ee ee 81.6 99.0 3.10 3 55 6 40 oa ee ee ey wee eects See 89.6 99.0 3.16 4 32 7 16 Soe PE Ss ee Re aa ee ae 85.6 98.6 3.10 4 26 ea SSR UE a ee in ee 88.2 99.0 8.10 4 14 6 36 Tensile strength>—kilograms per square centimeter. Brand. Neat cement. Mortar 1:3. 1 day. | 7 days. |28 days.|60 days.| 1 day. | 7 days. |28 days.) 60 days. 24.8 41.8 48.1 47.3 7.0 16.8 23.4 25.3 23.6 43.5 45.7 45.7 7.0 17.5 21.7 22.8 23.2 41.2 47.8 45.3 9.3 19.8 26.7 30.1 24.5 44.5 50.7 47.5 8.7 20.8 28.8 30.9 27.3 44.2 51.3 50. 6 10.8 23.2 28.5 29.1 2 Brand F, without any addition of calcium sulphate, was quick-setting; consequently no test was made on the original material. > Each result is the average of six briquettes. United States Government specifications were followed. xu,a,3s Witt and Reyes: Calcium Sulphate on Cement 137 TABLE II.—Physical tests of cements as received—Continued. l ur Tensile strength—pounds per square inch. | Brand. ® Neat cement. Mortar 1:3. 1 day. | 7 days. |28 days. (60 ese. 1 day. 7 days. Ps days.) 60 days. H | a2 eee ee eee eee eset 353 595 | © 685 673 100 238 333 360 eee eee oa Same eddae ne 337 617 651 649 100 248 808 825 eee See SER Eo ee 330 586 679 644 133 282 380 428 a: eg chee eee tee Ce eer 348 633 722 677 124 294 409 441 <2 eR 388 628 731 720 154 331 407 414 ® Brand F, without any addition of calcium sulphate, was quick-setting; consequently no test was made on the original material. The plaster of Paris contained 55.88 per cent sulphuric an- hydride. Each cement was analyzed, and the approximate amount of plaster necessary to give a certain percentage of sulphuric anhydride was calculated. The two substances were then placed in a ball mill and thoroughly mixed. In the case of sample F' the clinker was crushed to pass a 20-mesh sieve, mixed with the plaster, and ground to the fineness indicated in. Table III. This table shows the effect of sulphuric anhydride content on the setting time and on the tensile strength for va- rious periods up to ninety days. The results in Table III are not entirely uniform; however, as the results were obtained from more than 1,000 briquettes, general conclusions can be based on averages as follows: Setting time.—In conformity with the results, already men- tioned, of other investigations with calcium sulphate, most of the cements show a maximum retardation with 2 per cent or less of sulphuric anhydride and a shorter setting time with a higher or lower percentage.'* In general, the initial-set curve obtained by plotting the percentage of sulphuric anhydride against the time is parallel to the final-set curve for the same cement, * Calcium chloride, sodium sulphide, and several other electrolytes have somewhat the same effect. [See Carpenter, R. C., Eng. Rec. (1904), 50, 769. Witt, J. C., This Journal, Sec. A (1916), 11, 273.] 1917 Journal of Science ippine a The Ph 138 622 £12 6h bP9 £99 GaP 208 6°22 |6'PL | POL | 2°oh | 6°88 | 862 | S12 198 | 0°86 |0E 9/0 F OLP 282 T9T 829 GLg gap 986 Oss | 8'6L | SIL | Tr | 2Or | 6 TS | 9°Ss | FPS | 816 | 99 9/02 g 697 668 192 882 8L9 8h9 ELE g’ze | 0°82 | 88st | GIg |9Lr | Soh | 3°93 | 9°78 | 9°46 |O 9) 01 Sg O&r 188 196 199 629 999 668 208 | 3°12 | L°8l | 9h | ZH | Lh | 08S | S98 | BLE | St 1/08 SG Dae gal 60P ¥6Z || GO £89 id) leas APNEA ARIA WSS SSNS eae Wage Hesse Mts} a Pa 2 vPS OLT aus 9p9 T6p 868 10s TLE | 6 TE | 62 rsp | G'P8 | 6°Le | TTS | 8°68 | 8°86 |G L)08 F 2st L8T 861 TTL 699 OTP Ss Lat |} 08. | 06 00S | 0°;OF | 262 18°22 | 016 | 986 | SE 4) 08 S 92P OPE £16 189 029 S67 9Té 662 | Zhe | OST | °8h | 9's) | LPS | ots | 8°88 | 9°86 | OS 9) G9 & 60F 198 Ths 989 0s9 969 vLe 18g | Le | OLE | Lh | Loh | SLE | 2°93 | F838 | 986 | Ol L/S PF Shida 088 8a || «BL 989 O8Ge oll saaene | gO ee ScObe a ean anal Wehbe CCuL Pan cn eon |) OnGSme OxOGie lO hyerean ich 97 OLT 181 SPT 869 209 £29 PPE 6IL | 0°8E | O°OL | 9°Sh | Sep | 9°98 | LPS | 8°28 | O16 | G3 9) 08 & 988 8&6 9&T €19 p89 609 898 Oe | LOT | 96 Osh | TTh | 2°98 | 0°83 | 018 | 9°26 | 9% 9) 98 & 8c& Lbs 892 S89 £19 ashe) SéP 19a |b #2 | 8'8l | 9 PF | TSP | 8°88 | G08 | 8°28 | 286 | 0 9/ GE & 182 G82 902 #89 089 gq Z9P 8'6I | 86L | 8 Fl | Th | 8 Or | SLE | Fes | OF8 | 066 | 92 9) G8 & bette 008 £12 009 219 699 L0¥ p'Se | LIS | O'S | 3h | Osh | 00 | G°8G | 2S8 | 266 | $6 9] OF & 922 L6L raas 169 £69 gor oss 6ST | 8°S— | 6°6 66) |9'Ih | 9°28 | 97S | 3'S8 | S46 |0 9,0 & Shs 02 ae 069 £29 8IP S08 GS | 9 LT | 66 G8h | Leh | F'62 | P12 | 018 | 786 | 06 9) OL & 068 608 881 €hL 189 90S 098 PLZ | GZ | OSE | 3°29 | bP | 9°SS | ESS | 9°98 | 0°86 | 0S LST F pos £86 912 BEL 8h9 £19 £68 9°St | 6°6L | 2st | 819 | Soh | 2°0F | 9722 | 9°98 | 926 | SS 4) ST F LLE 982 922 SPL 0g9 Lea 16s G92 | 0°02 | 6°ST | 2°2S | SF | OLS | 9Le | 8°98 | 4°86 | OF 9) OL & org | oa | mec | wc ‘sAep | ‘sep | ‘sXep | ‘shep | ‘sXep | ‘sAep |. Kep T ‘shep , ‘sep | ‘sXep | ‘sfep | ‘sAep | “sep |. ep T 06 8z L 06 82 L 06 | 8 L 06 | 8 L -ysour| -ysout | eapbyeraray — — “006 | -OOT z a “E:T 1B I0yy *juoUeD 4BON "E:T 1eqI0 *quouled 489N “youl o1enbs Jod spunod—y33ue}s eyisuay, gS} OU UBS “ssousUL | ‘ew Buy3eg eaenbs Jed surerZ0]1y—q Y}SuUeI}s [1ISuay, *AYL “Avia ayo -adg qd pusig O pusig q pueig. eae V puerg *yuaulag vsquamaes fo ou Buyjes pun yybuaws ap18u07 04} Wo yUazU00 apiiphyun nunydjns fo souenyujJ—TII FIAVL 139 Sulphate on Cement Calcium Witt and Reyes XI, A, 3 “so}eNdLiq aAYy JO aBvAVAT ay} SI O1BY UMOYS A[NSet YouNT q LTs Tes 088 892 ore 43) § LST v6 £83 T8T Lia Le P81 628 912 Tee | pag £29 g8L Tes £09 663 299 68h 8F9 SIL PIB 829 Lig T&sg 289 p99 18h SEs 144 FLO 89L 0s9 807 g9F 269 189 829 218 Sop 687 687 VIP 988 188 SLY 6hP 888 2°08 9°86 £716 6S &°96 at) § £°22 £786 6&6 8°8T 6°26 £1 9°82 £798 6°98 6 OT G°8L vor La 6ST 9°6 8° 1&3 P6L 2°83 “ALOJOIBISIBS PUNOF puv XLUI You UO ap ata S}SA} SSaUpUNOY » 612 9°68 €°Lp 8°89 Loy £86 9°28 9°8P 8 PP 3b 612 618 8's SPs 0°62 0°22 1°92 8°88 o"18 Z'lZ 6°98 08 0°6L v'PL 0°88 6°68 v'88 9°18 8°98 3°88 v'96 2 °¥6 8°88 b°26 0°66 0°86 9°86 0°86 0°86 0°66 ST ot ovuvuvuonornrvo o rH HOaOntdt MAAN 90°€ 60°S OL’s OL’ OLS 10's 10°8 80° 80°S OL’s IL6 00°S 69°S 00°% oP 'T 896 6L°P §L°% 90°% rT J puvig @ puvag 140 The Philippine Journal of Science 1917 Tensile strength—When 1.50 to 2.00 per cent sulphuric an- hydride has been added, the strength both in neat and mortar decreases with increase of the substance. Four of the cements show a maximum strength with approximately 1.50 per cent sulphuric anhydride, while two show a maximum with about 2 per cent. The 90-day briquettes develop maximum strength with a higher percentage of sulphuric anhydride than do the briquettes for the shorter periods. Additional neat and mortar briquettes have been made for periods ranging from six months to five years. No final conclusions can be drawn until the long-time tests are available. In making the calculations, the strengths of briquettes made with the cements as received were taken as 100 per cent,’* and the comparison of results were made on the basis of the percentage loss in tensile strength. The per- centage loss in strength caused by placing plaster equivalent to about 10 per cent of sulphuric anhydride in each cement was then studied. The following points become apparent: 1. With one exception, the percentage loss is greater with mortar briquettes than with the corresponding neat briquettes. 2. As the age of the neat briquettes increases from seven days, the percentage loss decreases. No definite conclusions can be drawn from the results of the mortar briquettes at present. 3. No relationship between the chemical composition of the cements and the effect of sulphate is apparent. INFLUENCE ON STORAGE FACTORS It often happens that a cement is satisfactory at the time of manufacture, but becomes quick-setting or develops some other fault during storage. These alterations may take place grad- ually over a period of several weeks, or in as many days. Some writers are of the opinion that there is some relation between these changes and the sulphuric anhydride content. Accelera- tion tests have been devised to determine in advance some of the changes that may take place in cement during storage. One such test is to spread the cement in thin layers exposed to the moisture and carbon dioxide of the air and test from time to time for soundness and setting time. gills ath Gtsee inmate 6 iad asvate al abi atte od ies, LaF atlas d er eid IA Pe Was Pat iy tivmiert ce ‘ ‘ : ~ 2aj poy ye Te aysulaaiht Ns oo ) d . i F fa es ‘ / , : a a?” y iy “f' i ‘ : ns - ‘ ie f 4 ota + " rn 7 J ' »? ' * ? ~ 4 ne ¥ é - i * : = ; 1 : cal Wee EN fe bale : : s 2 ' i. oe, une Ul eo va Atlee genie aaa iar sh ’ v1 . PR “ai ae © et et ae Grriecrhas can - ; ‘ei a Phd) 3 es ee Wats ius, ny fe Coty. Fae fe ee 7) eel as we sl en we," Mi ak fo agen Patt a ita i v2 a A. i me a 7 nwt". “ie hots } 4 4 = . o) % y © Aebi : ° kris A Wes \ae Ps |, gl alle allie a a Be Fin j a a «a alee hk on : we : hie 1 UNA ET E ayohaa rer : : . : iS, 7 nf ? bores ‘ ' arte ees |) F THE ,RADIOACTIVITY OF PHILIPPINE WATERS * By J. R. WriGHT* and GEORGE W. HEISE (From the Bureau of Science, Manila) ONE PLATE AND TWO TEXT FIGURES In recent years there have been so many investigations of the radioactivity of waters that comparative data are now available from many parts of the world. It is the purpose of this paper to present the results of similar work on the radioactivity of typical Philippine waters.’ Up to the present time our work on radioactivity has been limited to the determination’ of radium emanation and actual radium content of typical springs and deep, drilled wells. As yet, no attempt has been made to study the radioactivity of the deposits or residues from springs, or of typical rocks, or of the gases evolved from springs or wells. All of the work was done on Luzon, most of it in Mountain and Laguna Provinces. The majority of the places visited are shown on the accompanying _maps (figs. 1 and 2). The geography and the geology of the country in and around Baguio have been described by Eveland,’? and of the remainder of Mountain Province by Smith.‘ Owing to the difficulties of travel, equipment for provincial expeditions had to be reduced to a minimum; in consequence comparatively few data on the chemical composition of the waters were secured. EXPERIMENTAL PART The testing apparatus was one of the Spindler and Hoyer aluminum leaf electroscopes used in previous radioactive meas- * Received for publication January 29, 1917. * Professor of physics, University of the Philippines. * The only previous attempt to determine the radioactivity of Philippine waters was made by R. F. Bacon [This Journal, Sec. A (1910), 4, 267-280], but his results were only qualitative, being obtained under conditions which made even approximately accurate results impossible. *Eveland, A. J., Notes of the geology and geography of the Baguio mineral district, ibid Sec. A (1907), 2, 207-233. *Smith, Warren roe Notes on a geologic reconnaissance of Monntein . Province, Luzon, P. I. , ibid, Sec. A (1915), 10, 177-209. 145 146 The Philippine Journal of Science 1917 urements *® in the Philippines. The instrument was provided with the usual equipment of tripod, shaking vessel, and cir- culation system necessary for field work (Plate I, fig. 1). 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og ou &Z “Hol S PANTBAOCOIO TOY Tae Mg tat Wasa ga ae Grace ect cme haa gen oe nt » Butdg uesunquing |--uevluesseulg ‘ueluesseg ‘eunsey |--- op----| zz 1) 028 OsNHRIBMOIS AT OSSMAe | sR a tae ce, BR | cena eae bel [[o“ UBISezIB [[BUIg |-~--~ umne[ney] ‘ueluesseg ‘“eunsey | 1Z “Ady | Iz "Ty eQiSG OANGecOCUIAT, Pcie ss Nile oceaeecee re sete eee corn et AGEN SSH LEG (2 CONS) PS teats a gist SS ar op----- 2 “Ady | 02 nie GI09 RUD COO Th | OS eee lcde a tee en era nee ene EKo oe ee. o [[94 UBIsez,1B OdIBT [~~~ >>> uvlussseg ‘eunsey | [zg “ady ! 6T 1917 Journal of Science ippine ab The Ph 154 ‘od « Sa SW lier tae ODGS os oom te Buiids dures Areyiueg |------ >> 7-7 omnseg ‘uysjyunop |; 1Z “Ady FTeOnTanI HON |F@ondy - 9) | digtosooeosooeas Sess ausepuy aa Rae RS MOAN BDU s|(cecachtese artes Lpldun ne sate ake 0) see eo (8) oa “Ajddns [ed -d1UNUW OJ posn ‘yeulTeyZUON | SOT “yoo peuleid-ouy ‘snoausy |------~ Bulids 1ozue9 quewusaa0r Ppa ti lak ebatcign 14 Fale ODnens a 9g “idy ‘ ‘apisdoy, i puoseq pozBoo] {[eulteyjJUON | LET CANCE) AQ 1A | ier cata a as = SUIAAG Ss lo[Iepaly IR H=25" Ase Seti pe lees te opis 7 gg ‘Ady “Bulpling west j seUA UERLG) CESSES T COLE SS ix J EA ECECECD D'S CLO INT NDS Bi ec ci | Pere AUIS TE OBO KT 8 Sha aaa sea Opin 92 AB -queyd VATE AC LET KOC) tlh | [linge ten er aes = ate cn Op=- = = COV ELE) Beet sy TOY Celi O ig y [Reo al SS ia Opa OD aes “*S19}OUL 00Z‘T UoleAs[e ‘AeyY uyor durey soiyddns ‘jeumeyjuoN | P6T “Yo01 poulvis-ouy ‘snosusy |----sulids [ “ON ‘Aepy uyor durey |-------------- eR ae eee Opescee 6z ‘Ady “s10}OeUr 0SZ‘T wolzeAsje *Ajddns [edi -OIUNUI JOJ pesn ‘yeuLIeyUON | SOT ayisopuy |----~ PHO UBM SHO SULTS AVI essa a aos on son onan ‘Ops- "5 LZ ‘Adw “9701p ‘od e081} pus a}isepue pesodulosag |--~~~~------ g Joqoulo[Iy ye Buladg |-----------~ eng ‘oinseg ‘ulejyunoW | pz Ae “pny *S10JOUL (90*T UOIZ BulA[IaaAo J9zUIS D1UBd “OULU S1OJBMpPeoTT -BAQ|9 asudoes ‘jBuliey}UON | [iu -[OA ‘o}IIOIp puw ozIsopuy | je ABA YOuNuUy “Bultdg |--~--—-~ 7 Wott mmm mmm mm = ‘CD aaes IT Avy "S10}OUL OZB U014 *QULUL pazBpll[osuoy jJonsucg -BAO[a osedeos ‘{jeultoyJUON | G6 ayisopuy | ye AgyeA Youjuy ‘suridg |---~------- Suggs SIRES O SEES S Opes LZ ABI “oulur SIOJeMpBsy 9AOqe 19j}0UL : “OPT T yNoqe ‘yeumeyzUON | [2 Tren nnn= (j) e718epuy |---~ 7-7 >> AQTVA YOUNUY ‘BuLIdg |---~ ~~ Tom omnseg ‘ulejuno_ | [ AeW “9T6T “er 0L x "seus erence *UO1}BUIIOT D1Z0[OI4 *a01n0g ‘oldIeq pue ‘UMO}Z ‘9dUIAOIT a7e8q -eula WINIPEy *penurju0j—suaqnm aumddywygq fo hjayonovppy—y] 2g Tg 0g 67 8P ly oP oP vy &P (a7 IP a1av L 155 Waters ippine al Ph nd Heise an Wright XII, A, 3 *“ILOAIOSOI [[BUIS B wlody U9HB} SEM Jnq ‘adi1no0s Woigy AljjOaJIP paindes oq jou p[nod a[ dures ‘[BulIayzUONT *S10]0UI (ZB UOT] BAIT A *8.10} UL 028 8}9]9NO0 Om} YIM Suysds auo Ajquqoad § ‘jeureyqUON ‘og “$104 -9UL OL UOIWBAV]A ‘[BUIIaYUONT “-- o0f 24njgBisduoy, “F ooh oanjzeseduiay, ‘azed -908 Ajquqoid ‘yeurteyyUON “S107 0UL 00F'Z UONBAZIO ‘]BUlIEyJUON *sIoJoUul (QP uoBAI|a “+ oop 24njBreduisy, “dey ad1Ades Wot *g10}0UL ())), uolyBAgle “F.0G eanjearoduiay, od ‘od od “8.104 “OUI (G8 UOINBAV[O ‘[BULIAY UO NT *S.10]0UL {[BULIOYZUON *s19j0ulL {[BULIEy UO NT 060‘ UuonBAsla OOL'T uwonease [a [tu ta “sou [yu “sou ED i:nGt 188 682 ~---- ---~-+----- (i) a18s9puy -----------~------- ozISepuy aannaan= o}IsepusB PUB 93/1017 *pBOl BABIZIA BAONN UO ‘[ooydSs jo 4sve Buladg “BuIpling [elourAoid jo 4sBoeyjiou sulidg Pee BA0ge 0} JUsDel[pe BuLIdg “BUL -pling [BiourAoid jo 4sve duladg Pee oa aaa eAoge igeu Sulidg “sulpping [BiourAoid surdjddns surdg ~-~+------------- uieq 1eveu Sulidg se==----~ SuULyULIp JOJ posn Suradg ---------------------- » Sulids 4oFT wn ---~----------- Ajddns jedrorunyy “UMO} 0}1S0d -do ‘yuBq JeAIt uo Bulids 4ox7 “sutids [edio1unu 0; jUecefpe suladg ---- 914818 [BIoUIAOId Iv98U Zuladg --- ssnoyjooyos aveu BZulsds [[eug paprassenne, esnoy sed rv8U Buladg oo SOR ad ae ee pe 2 ae OD anion ieee OD eee PE ee ee Ee OD iaeen eee OD aaa tea oP arr so teuee eR ETS OD eciea | siete O Dneeians Fle ee ae "~~ op----"| 6T ABT RGISE ee ee oe OD ieee panel O Daas ae Batra uvsuely ‘UlBjUNnOy, | gT AB ~~ sueqn'y durep ‘uoxsojy ‘urezunoy | 1Z ‘00q po as 2a en eae oe uo0d0qj ‘ulejUNOy | g— “90q Rit 2 Ra pat ne ee pen ee ta op-----| 9 AB Mpc Pak 87Y4sley ‘ureyunNOP, | e@ ABT eect SBI[IWIOD “BeJUBAIID “ULBJUNOP |--~ op---- pees SNR eT lee a eee Op-----| 6 AB Cargere tess ae SoJUBAIOD ‘ULBJUNOY, | OT ABI Pit ae ee OD iter | eee OD ene alae a3 Lypouleg ‘o0JuOg ‘uIeJUNOW | gT ABW Pim” Sage cost oes cae oe OD gee lee OD sean Soe SS ee cea oojuOg ‘uUIBJUNOW | pl ABP Tee aes ae ae eneueg ‘ujejunoy | LT AB 29 19 *99 9g rg —~, 1917 *£10}0U90 Bou [eM UvBISOTe polJUBUISIG. 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WoIWBAcjeo ‘JeuITEYQUON | [PG PUTT mere en nnn ayIsopuy Lan) *sIOJOUL OGE*T UOly yy -BAQ]2 fasNoy 4S8ed JO SB “UI SS T ynoqe Suiids ‘yeueyyuoN | PIT | ayisepue oyAyoeay, Q *s10JOUl S 00ZT UOIZBAD[O ‘sdulids *19]Ue0 Snos.Ivd :s euljes Burpioq wor ejdureg | [iu -[89 pus snolel[is fezisepuy A, SPOT OME OOGMUOM BAG] ON GOB)) 9) | pete nits cnaaon naa eeeemn cans = “solos B JO SSulids July Cora aeglaaah Bc. oad oe “yny Aq pezuour & Fp, AR a s60d: eam are oe “sou -99 9}BIOWIO[Su0d snooeusyT “aot X “SyIBWoy aa e “UOLPBULIOZ DIDO[OI4) “ela UINIpey Vor) ra ‘ponuryu0jn—suajnm aumddywyg fo hpayonoippy—y] a1aVv.L 157 Waters ippine al Ph Wright and Heise XII, A, 3 ‘od *MO| A[QBqodd Si4[nsed soUuDY ‘Zuiddip Aq peainses sjduieg *Aulids [Boo] B A[quqorig Ta pre eign a he cil a a eee ei ezei[d “‘1To" uBIsoyIy yuRq AOA ‘JOM uBISEITy ee La RE cc ae | aes YoInyd Bou [eM UBISOILY “Tell PP “H “W 8D ‘e4 uelseqry “elouap -1sead JO }S9M siojOUI QOT Suradg PEneSs cree ares onbeuvieg ‘[eziy | 6T oun | 16 | Pe ORS arto ies ae Geer e OD een i> OD ans |/06 RS igs ae ea oR OD irean|: ORF =55-4|/.68 5 ig CE uesdnseq ‘ueuisesueg | 6Z ABI | 88 peprury, ‘ureyunoyy | gt “oad | 18 158! The Philippine Journal of Science 1917 Radium content of Philippine waters.—Samples of twenty typical waters, from which the emanation had been removed, were acidified, sealed up in proper containers, and allowed to stand at least one month. They were then tested for radium content, by the method previously outlined. In no case was there any indication of radioactivity. ; In addition, 15 liters of Batangas water (No. 1), 15 liters of Los Banos water (No. 12), and 5 liters of Sibul Springs water (Nos. 4 and 5) were evaporated to small bulk and similarly tested. The first two showed no emanation, and the third showed a trace. The radioactivity of the waters studied was, therefore, primarily due to emanation derived from the materials in the ground with which the water had been in contact and not to dissolved radium salts. DISCUSSION The work has not proceeded sufficiently to justify many con- clusions. The typical Philippine water supplies studied possess no abnormal features so far as their radioactivity is concerned. Though some of them are moderately high in radium-emanation content, none show an excessive amount, compared with waters from other countries reported in the literature.’° Since hot water is a poorer solvent of gases than cold water, it is to be expected that the radioactivity of hot springs should, in general, be low. With the exception of the Los Banos water (No. 12), most of the thermal waters studied in the course of this work showed little or no activity." , In general, the average activity of igneous rocks is greater than that of the sedimentary,’ and it is to be expected that water from the former material should show higher emanation content. Thus Sahlbom ** found that the water from sedimentary deposits was much lower in activity than that from primary rocks; further, that wells bored in the acid rocks showed the highest activity. In the Philippines the relatively small number of de- © Cf. Schlundt, H., Bull. U. S. Geol. Surv. (1909), No. 395, 31; Journ. Phys. Chem. (1914), 18, 662. Isitani, D., Proc. Tokyo Math. Physic. Soc. (1912), and following years. “The average temperature of ground waters in the lowlands of Luzon is about 28° C. ~ Cf. Clarke, F. W., Data of geochemistry, Bull. U. S. Geol. Surv. (1916), No. 616, 122. * Sahlbom, N., Arkiv Kemi, Min. Geol. (1915), 6, No. 3, 1-52; through Chem. Abst. (1916), 10, 1134. XII, A,3 Wright and Heise: Philippine Water's 159 terminations made and the frequent difficulty of determining the actual water-bearing stratum, since this is frequently not the same as the geological formation exposed at the place where the water emerges, make generalizations at this time inadvisable. In some cases, at least, the radioactive material from which the water derived its activity must have been confined to a rather limited area. Thus it was pointed out" that Olla Springs (No. 18) were in reality only seepage water derived from a river about a hundred meters distant.’ The “spring” water must, therefore, have acquired its activity in the course of a short journey underground. So far as the available analytical data at hand are concerned, there is no apparent general relation between the chemical quality of the water and its radioactivity. According to Schlundt 1° there is, in general, no detectible difference in activity between acid and alkaline waters. Practically all of the waters tested at the source in the course of this work were acid to phenolph- thalein and alkaline to methyl orange. We have been equally unable to make generalizations concerning other factors. This is not surprising, since the emanation content appears to be due not to dissolved radium but to contact with radioactive materials, sometimes within a very restricted area. For the sake of completeness, the available analyses of the waters under investigation, as compiled from the data in the Bureau of Science, are included in Table II. There was no sharply defined rainy season’’ during 1916 in the places visited. With the exception of the determinations made in April and December, the tests for radioactivity were conducted during months of considerable rain. Though no systematic study of the relation between the radio- activity and the variation of flowing wells and springs has been made,'® it may be of interest to point out that Sibul Springs (Nos. 4 and 5) was tested on two different occasions—once in the middle of the dry season, that is, after two or three prac- “By V. E. Lednicky, chief, division of mines, Bureau of Science. * A bacteriological test made in the course of a field survey of water supplies confirmed this view. * Schlundt, H., Bull. U. S. Geol. Surv. (1909), No. 395, 30. “For the distribution of rainfall in the Philippines according to locality and season, see Cox, A. J., This Journal, Sec. A (1911), 6, 287-296. *“ Many spring's and deep wells whose flow varies greatly with the tide show no appreciable variation in chemical quality. See Heise, G. W., Note on the tidal variation of springs and deep wells in the Philippine Islands, This Journal, Sec. A (1916), 11, 125-127. 1495174 ; 1917 LENCE Journal of Se ippine al The Ph 160 so, O01) FL Oe ae Pll hf) ack GPE ee Nike XO9cia | somenaans comes “ 000) ehieaas ans es ee op---- L ore N Coane ae: Meee INGE | CSP cae AT | OP OUTS tie eee ee CER posse iL-N ost N eee Si amo OS) see. |hic eee eee ae rad C2 ale. ca aaa PEt fil fee a Ne a ager ayoeg ‘eunsey "9 USDOL A 9T €L N (TSS | (aaa eet ded Pit Ga Oe ee ea = 9 AT 2 ROY .{|SSSgo Sereee are e318] ueg ‘ugpieosenN ‘“eundsey “os01q. 9t O9T N {bees ae See OO ee Oise | ae Sars |e 7F #9 OSES See Sees oB1B] usg ‘uBpiuoseN ‘eunsey ur 08 N Higa pean = GL tO"ae ae cae OO): silicestObaed|o eee opens eae esavy |-- oequuls ‘AvlAele ‘eunsey L OL N Le al) et ETE GG: Oe | mkt 3 at ee a 81 CY onl alate tata ciara a OSACT oleae ara Avlkeleyy ‘eunsey 08 OLZ N 00s ST OP |81°0 026 OPP ‘T} 8ST O2oie Sues ei es oe ItIN OGe es |e een souvg soy ‘eunsey L oat N fal Tee ae | is Sm TOs soe [aa ee rE cee | sige ad cian Raean ee al | ae ooyey UB ‘Oly ‘eunseT 9% LLG N O90 Pee * Slee S850 lcs cee | ae cb GiGi [PSS Saar oe | Risser | fae cr ese araeiea Seas op----- LE 992 or 09% | 9°6E | 68 A, gst 0g8 ao OU aera ers esiey |-~-- josuvg ‘equiepeg ‘eunsey ve 44 N GS Sitcaee a) 2 eed TOM | de Sele see + OGloul trace? sag Se ee CRIM eens ]eo0g ‘equir[eg ‘eunsey N O9L N 08 bs &6 |§8°0 98 O%L | 8&8 ORD: slreracee ee ODSasas seam Sale (Blouepiserg) Avg ‘eunsey | “(peoy. ap a o9g¢ | N oP 2 | 98 1970 | 08 ony | 18 02S) | ameagenetenme 230155: | eseaiaaeiiges | BS OME tTE SCT) ee Sue essa eS ei N 9°S9P N a) & I 8hr | ST ogg a (i: ce an eee TE Nig |e 28008] | ee meee a [nqig ‘uvoving pot | LI9t | 98 o°LT (8 SLO) Qi6Go” |e Nia |GSeorm Peres hae at onan OBABl cyl Rega e wer aa oRllaByy ‘UeoR[Ng yo [pe=snecs|P-->---- Or ol (cy eal RB 89 OSG sete | ee ne es ee ke eae sesuvjyeg ‘sesuvjegq *S4aqVT = = = = = — E 2 — a iw Ped Bel & |e Rre\ea5) Bee eee é oS 8 5 = ® a 5 i iy | & | & 3 ey ¢ g Z a eae. a gs | g. Bee eee pe |e | et glace | Sse] oer ee g 8 | B | § Bi | tee alee a = eae Geel ; aera. o & 8 a 3 a . i) = g IS I0[0D 3 o1req ‘UMO}7Z ‘adULAOIg D oO es i) ~ : = ® Se Ae aah oe Bole 2 | 8 d a a eS ® 3 3 fe) ; : | & it & e ® []9A utIsojIy usfuesseg ‘eunsey |- Suladg uesunqung Buradg ~ Bulidg o}ue01A uBg ~~~ BSulidg o#a1q ueg ae Bulidg oeqeuig Si yveeery Sulads B10 suds jo Bundg eee aa Sutids plop Bulids joy Buradg [944 uBisojly 7a ee ssulIdg *e01n0g [uorim ted syivd se passerdxe s}[nser [eorzseuy ‘2081 = L ‘Wews=g FIU—N ‘Mop =“ ‘9139 = T] ‘fgayovorpps sof paqsa, suaynm fo sashynun JoovueyQ—T]] Fav L 161 Waters ippine il Ph Wright and Heise XII, A, 3 *(®O*7vV+%o%aq7) Seprxo wmMurunre pur uoJy , 0&8& C6P 09 +8 \(Z) 861 (2) 821 OL O1Z OFS 21P 0s |Fr°0 | 98 |82°0 aga N-L al N a0 ISN Vee Sig aged Bases N Page N a L pe a ona N 6 v0 Te ea fe N-L ie 110 Iz |L0°0 rE” 92°0 Fe N S12 | 10 pL | oL0'T] N | 022 op | oos‘t| 9 00% ES ae [ceria N | 062 ee ae N | 9¥2 02 982 | N | 00r GOV yi se eee apc (OA) | ges ae los ae saa a ee oe + | ort See gal gs + |. seas |: en + | 8 ae ees + | 19 Fee | Ee ae + {8 Goal eee ge eS oe zz | Ont] N_ | oz ee eMac Se aie oe 002 Cease oe wy | 69 org aaa: S | 8 ort ge aT | 6I oat niger ols gaa N | aut og |g'or | N | var Paihia as Saeet TENG | ieee ciate oot ~ AOTIPA APY SNS 026 “ysl “uMOIG ATFYSIYS 09S See See eel oS1B] ceo haa =e ee Se od1e] ee ee ee a EE SC aB1R] SS eae are oe ae [Tews et SERS LA oe, ese] as sa ee sca ae ase] pa a re TENG eee (2 es Sema aaa s IIN | e31e] Be ape oe ae [ews Baa ie IIN | e81e] iia See OSCE aB1e] Pe Si a ee 02 Ragas or ea enbeueieg ‘(BZ *(QuOoIf TAIT) ‘uBeulIsesuvqd *(qox1eUL) ‘uBuUIsBsUBg *(peoy ovise[Eep) ‘uBulsesued uevdnseq uednseq uednseq . Sai = ieee ulpnsey, ‘UleyUNO;L "OXID YQensueg ‘ulByUNO, JIULe “ULreJUNO|y —omseg Yjensueg ‘urezUnoj;[ ‘ABy uyor ‘ule UNO; pie) bs duej ‘omseq Ress ake os ~ onseg ‘ulBjyUunOpT *(peoy wey -MBYOT) OINseg ‘ule UNOTAL a as olnseg “ulezyUNoOy *(Teq1dsoHy Jetsuey suiddyiyd) Bruel eae SBUIOT, OJUBG ‘UOIUQ BT pao opueuise gy ues ‘UolU_ BT ~--josueg ‘ojqeg ueg ‘vunseT “pnsunqey ‘olqed ueg ‘sunse'y ae ae a [bled ‘vunseyT PoaSaer etal uefuesseg ‘eunseT “uIne[ney ‘uefuesseg ‘eunseT fe ae =e ae OT! aeay=SS 119 uviseqry “> Sulads ex1puo[ yy Bul1ds JOP eee sulids [epyed duro ArBqIUuBS pe Ss Bulids Az19 *SuLIds JayueD JUSUTUATBAOD . 162 The Philippine Journal of Science 1917 tically rainless months, and once during a period of frequent rains. The results of the two determinations, which are prac- tically identical, indicate that deep-seated springs, such as Sibul Springs, may show surprisingly small seasonal variations in radioactivity. It should be pointed out that Sibul Springs shows a comparatively slight variation in flow throughout the year, so that the inference from the two isolated determinations just discussed is not considered to be at variance with the find- ings of other investigators. Thus Ramsey found a greater emanation content in certain springs during periods of wet weather and great flow, and Steichen *? observed an increase in activity in certain Bombay hot springs during the dry season, while the flow of water was considerably reduced. As pointed out by the latter writer, local conditions may well account for the differences noted. For the sake of completeness we have noted in our data (Table I) all sources of water supply which are popularly considered to have special medicinal virtues. Hither popular opinion is a poor guide to the medicinal value of a water, or else the medicinal properties of water are not to any great extent due to radium- emanation content. The waters with perhaps the greatest reputa- tion, namely, Los Banos (12) and Sibul Springs (4 and 5), have relatively high radium-emanation contents, yet many others regarded as highly, such as Marilao (3), Pansol (9 and 10), Santo Tomas (386) and Klondike (72), contain little or no ema- nation. Moreover many waters high in activity, such as Batan- gas (1), Kiangan (66-71), Pagsanjan (19 and 21), and in general, the spring waters near Mount Banajao (13-17), are regarded with entire indifference. Although emanation taken into the stomach is probably dif- ferent in effect from that taken into the lungs, the following comparison may be of interest: Assuming that in ordinary respiration the average human being breathes 7 liters of air per minute, or 10.1 cubic meter per day, the emanation content thus brought in contact with the human system is 77010 curies, if the normal emanation content of the air in the Philippines ”! be taken as a basis for calculation. Therefore a person would have to drink about three-fourths liter of Sibul Springs water. * Ramsey, R. R., The variation of the emanation content of certain springs, Phil. Mag. (1915), 30, 815-818. ** Steichen, A., The variation. of the radioactivity of the hot springs at Tuwa, ibid. (1916), 31, 401-403. * Wright, J. R., and Smith, O. F., loc. cit. XII, A, 8 Wright and Heise: Philippine Waters 163 or one and one-half liters of Los Banos water, in order to take as much emanation into his system as he ordinarily secures by ordinary daily respiration alone. SUMMARY The radioactivity of about ninety different Philippine waters, chiefly from springs and flowing wells, has been studied. The highest radium-emanation content encountered in a deep-well water was equivalent to 210010-" grams of radium; the highest in a spring water was equivalent to 130010"? grams of radium. ; A test for the actual radium content of about twenty typical sources showed that the radioactivity encountered was due to emanation absorbed from materials with which the ground water had been in contact and was not due to dissolved radium salts. One sample of water showed a scarcely detectible trace of activity due to radium salts in solution; all the others tested gave negative results. yal Dt Alerce ag fabio sedi va ol Vt eevee ST hie at eee devotee ° . Per Chaise aeelaths: Dat an ME OM to ae oe stone el et Sena yaaa 7 w)Siivn eringagtt telat gerey™ oa bo Fi peel Hike ata Bait: fertile . 7 = jhoweQabieyyG iaay> oon apelin one thn eet inanwing woe . Tite. ee COVE SRE phe? Pe cio vinag BRE eight CRAY EO Or ee OP > Seek ay rh Pe hit are gi dowd yierdn jo Wierd a eae cb Blew Sentai ioc tent 2 ee tapathes ig? dene HAR aA bind se Sac Rea Petre Rea. Wei, iter. eaw bo toads dt aah bata vost) “ene eh eh noe pain Dane. ae ae isms a ae pie enceler sinh ‘rick yes Si en Hunter as aie be OSE Stein Some, Va eS eee aaa anaes *: eouh giaithe tet te meoelietees) we eapcall ks Pris saat nie pees 1 PE OP SADIE, 00 es Oe Tae a 3 ay goss event ie 5 ee atte > Siethent, Te WAR ee ich Sees tee 2k Masi mbar uu 1 ROR, Leotk R: CR I RS ae Pr ie i@ 4 rOyeT Te SRR ee ol ae eee eee Peed te Rice Bee en ae: Mitts aka eS S94 ii £ inh Soin ets REE apd at Te) Reais a: uve ‘itn Wika? gritty ate ihe: te PoC ae, PAE HORT De Se ats Tae andl eee 7, Tle Se eee he ks Fane ee, ae PENS SAT eR Tree ae eerie 5) ea to at, uf ee ape PEAS Osta Rs ta eee yet ae ape Fata A ee i eae ant « Pear as a ‘tine. tytargeeae ats te OSE: S16 Deg DES ae ie gehen. ¥ oma ‘arin yg i MLD cheek geakek thee ey, ee Fatt eTAGE th cate? witty the nadie ee AE AL We. tee . tes crt Tey Iie ig pear au De Ones ere eS er eee Py Do. | Twenty grams of Lloyd’s reagent were insufficient to extract all the vitamine from a liter of yeast liquid; 40 grams left a small proportion remaining in the filtrate. After extraction with 50 grams of Lloyd’s reagent, the filtrate possessed only slightly pro- tective powers from polyneuritis when administered to pigeons. EXPERIMENTAL PART Because of the difficulty experienced in keeping the extract of rice polishings sterile, it was decided to investigate the possi- bility of extracting the hydrolyzed extract of rice polishings with infusorial earth. This infusorial earth was obtained from Japan. Its absorptive powers are less than those of Lloyd’s reagent. Under the conditions described by Lloyd for testing the efficiency of his reagent, Japanese infusorial earth reacted as follows: * Lloyd, John U., Journ. Am. Pharm. Assoc. (1916), 5, 381. * Seidell, Atherton, U. S. Pub. Health Rep. (1916), 31, 364. * Brewer’s yeast contains the highest percentage of any of the known sources of vitamine. As it is a waste product in the breweries, it is also a cheap source of vitamine. XII, A, 4 Brill: Infusorial Earth Eatract 201 TABLE II.—Absorptive power of Japanese infusorial earth for morphine bisulphate.* Quantity oa | Result with Mayer's reagent | earthen on the filtrate. | used. | 0.50 | Not opalescent. 0.40 | Slightly opalescent. 0.35 Do. 0.30 Do. 0.25 | Strongly opalescent. EE a 8 five cubic centimeters of a 1 per cent solution of morphine sulphate diluted to 80 cubic centimeters. Lloyd reports his reagent to have an absorptive power of 8 grams of earth to 1 gram of morphine bisulphate. This is nearly the same proportion given by the Japanese earth. The latter has an absorptive power of 10 grams of earth to 1 gram of morphine bisulphate. The alcoholic extract ® of rice polishings was hydrolyzed by heating with sulphuric acid in the manner described by Williams and Saleeby.* One 500 cubic centimeter portion of this hydro- lyzed extract was treated with 50 grams of the Japanese in- fusorial earth with shaking at intervals for a period of one hour. The mixture was allowed to subside, and the supernatant liquid was siphoned off. The infusorial earth was then placed on a suction funnel and washed with a 5 per cent sulphuric acid solution and finally dried. A second 500 cubic centimeters por- tion was treated with 25 grams of infusorial earth in a similar manner. The extracts, when dry, were placed in capsules for administration. The 50-gram sample, hereafter referred to as D, weighed 95 grams and filled 174 capsules, or each capsule represented the extract from 2.9 cubic centimeters of solution. The 25-gram sample, hereafter referred to as ELE, weighed 49 grams and was placed in 135 capsules, or each capsule represented the extract from 3.7 cubic centimeters of solution. The filtrate from D was bottled, subjected to fractional steriliza- tion, and marked B;; the filtrate from EF’ was bottled, subjected to fractional sterilization, and marked C. The original hydrolyzed °This extract is made by treating 25 kilograms of rice polishings with 5 demijohns of 25 per cent alcohol and later pressing this. The extract is evaporated at a low temperature, the fat is separated, and alcohol is added to precipitate the albuminous and other matter, and again the extract is evaporated. The solution is concentrated, so that 1 cubic centimeter of extract is equivalent to 15 grams of rice polishings. "Williams, R. R., and Saleeby, N. M., This Journal, Sec. B (1915), 10, 106. : 202 The Philippine Journal of Science 1917 extract of rice polishings is designated as A throughout this article. Two methods are applicable for the determination of activity in these extracts, namely, their protective property from the onset of polyneuritis in chickens fed on polished rice and their curative property when administered to chickens suffering from polyneuritis. Both methods were used for testing these extracts. Twelve chickens were placed on an exclusive diet of white rice and treated in the manner hereafter described. Two chickens had no treatment, but served as controls on the rice used. When polyneuritis became evident, they were treated with some one of the extracts, A, B, C, D, or EH. Two chickens were given 3 cubic centimeters of A three times a week; two received 3 cubic centi- meters of B three times a week; two received 3 cubic centimeters of C three times a week; two received one capsule of D three times a week; while two received one capsule of # three times a week. The experiments extended over a total period of one hundred eighty-six days. Table III gives the history of the chickens fed on polished rice. These chickens had no treatment until polyneu- ritis had set in. They were then treated as described in the table until their condition improved, when the treatment was dis- continued. TABLE III.—History of control chickens. ae ion ; ~ erore |jnumber um- ene onset of| of days Treatment. ber of ie - Results and remarks. en. poly- | on pol- treat- weight. neu- | ished ments. ritis. rice, Pact. 1 23 28) | (None 22seucs- slosh 2ebe es none 27 | Died at end of twenty-eight days. 2 (i ee ee 3 ec. of A on alternate Oy ae2 See Improved; treatment discon- | days. tinued. 2 | 69 1860222 CO soe ent REL See 2 36 | Improved; treatment discon- | tinued. Living at end of experiment. 3 Sbaj-esseees 1 capsule of D on alter- A ete Improved; gained weight af- nate days. ter treatment. Treat- ment discontinued. 3 | 18 | 1S0v Cs (ayer ee pe ees eee kee 3 28 | Improved; living at end of | NG experiment. ie Vou The weight of the chickens recorded in Table III decreased when polyneuritis set in. When treated, their weight increased at once. This increase amounted to as much as 20 per cent in some cases. XIL, A, 4 Brill: Infusorial Earth Extract 203 In order that a check might be kept on the activity of the original extract of rice polishings, two chickens were treated with 3 cubic centimeters of A on alternate days. TABLE IV.—History of chickens treated with 3 cubic centimeters of A on alternate days (three times weekly). | | pes | zor | N | efore number um- ae weertie pe kno Treatment. her at oe Results and remarks. | | neu- | ished ments, |Weight. ritis. rice. Pict. 1 87 | 92 | No extra treatment -__--_- reg- 50 | Died after refusing to eat | ular. for several days. 2) Se hd 2 ee Gove tosses seeks reg- 20 | Died without any symptoms | ular. of polyneuritis. U3" | ees ' WOilwcoce dG. Scop eo reg- 13 | Living at end of experiment ular. in good health. 4 ings. Sth 2 cc. of A daily ______.--_- Ol as Improved. 4 12 Ponds leew GU) Sere Seo oe ea SB) |e ee Do. 4 oh eee seco (iG) Seekeetoet sebeee ese (| Petes Do. 4 7 [igs ae CG be jp acta eet Sa chal 10 45 | Living at end of experiment, but in enfeebled condition. Three cubic centimeters of extract of rice polishings on alter- nate days were insufficient to prevent the onset of polyneuritis in chickens 1 and 4, but the extract prolonged the period of good health. Two cubic centimeters of A given daily for several days improved the condition of the chickens to such as extent that they could be again placed on the original treatment. To determine if 50 grams of infusorial earth would extract all the active substance from 500 cubic centimeters of hydrolyzed extract of rice polishings, the experiments recorded in Tables V and VII were planned. TABLE V.—History of chickens treated with 3 cubic centimeters of B on alternate days (three times weekly). Days | Total fe before ‘number Num- Total chick- pages of ot dave Treatment. ber of | jogs in Results and remarks. 3 poly- | on pol- ESE weight.) neu- | ished ments. zi ritis. rice. | PACt. 3 101 104 | 1 capsule of D on alter- 2 46 | Was in seriouscondition nate days. before it was reported. Died at end of one hun- dred four days. 2 25 BG) eee i (i eee es es 5 34 | Improved; living at end of | , experiment. : ft (secs el 186: |, None: sss222 Sane eee none 34 | Living at end of experiment. 1 204 The Philippine Journal of Science 1917 Of the three chickens treated one showed signs of polyneuritis at the end of one hundred one days, the second at the end of twenty-five days, while the third was still healthy at the end of one hundred eighty-six days. The vitamine has not been entirely extracted, as B still has protective properties. In the comparison made on morphine bisulphate, the Japanese infusorial earth compared favorably in absorptive powers with Lloyd’s reagent, but Seidell found that 50 grams of Lloyd’s re- agent extracted all the vitamine from 1 liter of autolyzed yeast liquid, while in the above experiment 50 grams of infusorial earth have not extracted all the vitamine from 500 cubic centi- meters of extract. The difference in the absorption must be due to the difference in the character of the two solutions. Hydro- lyzed extract of rice polishings is a thick, syruplike liquid, which undoubtedly collects on the infusorial earth and renders it in- capable of completely extracting the vitamine from the extract, while the yeast extract is no more viscous than water. When 500 cubic centimeters of extract of rice polishings are treated with 25 grams of Japanese infusorial earth, the filtrate, C, still has protective properties similar to those possessed by B. TABLE VI.—History of chickens treated with 3 cubic centimeters of C on alternate days (three times weekly). = | | Days | Total < before number um- No. of | i Total chick- Iga eae ae | Treatment. be r of loss in Results and remarks. St neu- | ished ments. weight ritis. rice. | eck 1 63 186 | 1 capsule of FE on alter- 3 13 | Alive at end of experiment. nate days. 2 63 GSE 00.5 eee 1 41 | Improved, but died four days later. k Sillessnese | 116’) Noneisuns-s =< ae none 16 | In healthy condition at end of experiment. | . i The infusorial earth extracts D and EF possess antineuritic properties. The chickens, No. 1, of Table V, and Nos. 1 and 2, of Table VII, were benefited by the administration of D when they had contracted polyneuritis. Chickens 1 and 2, of Table VI, and 1, of Table VIII, were benefited by treatment with EF. To test the activity of the infusorial earth extracts, the ex- periments described in Tables VII and VIII were performed. XII, A, 4 Brill: Infusorial Earth Extract 205 TABLE VII.—History of chickens treated with one capsule of D on alternate days (three times weekly). “Days Total %s | efore jnumber, um- eritke paect of pidare Treatment. bor ct ae Results and remarks. | ae neu- | ished ments. weight. ritis. | rice. } Pict: 1 155 | 186 | 1 capsule of D daily __---- 20 81 | Living at end of experi- | | ments. 2 70 BB) 2-508 Gop: taste. 4 >. Seeses 2 19 | Improved, but died fifteen days later. 3 | eS | SOMMNone)-.-eeeens see eee none 6 | In healthy condition at end | | | of experiments. TABLE VIII.—History of chickens treated with one capsule of E' on alternate days (three times weekly). i” eee total Ss ayia efore number um- elated pusetot gente Treatment. her of fosain Results and remarks. ns neu- | ished ments. weight. ritis. rice. TEA Gyre 1 105 122 | 1 capsule of E daily -_--_-- 3 23 | Improved, but died ten days later. 2A" (eae ee SShim None et 4: aur, nee See none | 26 | Aliveatend of experiments. 3 81 t3 eee G (SS Ses 2 eS See none 46 | Died without any extra treatment. 4 aa 100 ESS (> (6 nee enue, Seas wre aa aa none 23 | Aliveat end of experiments. DISCUSSION The results obtained show that the curative principle is ex- tracted from the hydrolyzed extract of rice polishings by means of infusorial earth, although not by as small a proportion of the earth as was found by Seidell when he used Lloyd’s reagent with autolyzed yeast liquor. This partial extraction is undoubtedly due to the character of the extract. Extract A, given on alternate days in doses of 3 cubic centi- meters, did not protect the chickens from polyneuritis for the entire period of one hundred eighty-six days. Chicken 1 con- tracted polyneuritis on the eighty-seventh day, chicken 2 died - on the seventy-third, while 4 became sick on the fifteenth day of its confinement or the one hundred thirty-first day of the experi- ment. An administration of 3 cubic centimeters of A on alter- nate days should be sufficient to protect these chickens. It is 206 The Philippine Journal of Science possible that this extract no longer possesses its full curative properties when it ages. Treatment of chicken 4 was begun- on the one hundred sixteenth day of the experiment; consequently the extract used had been made for some time. Wiiliams® has recently shown that hydroxy pyridines have antineuritic proper- ties, but these curative effects are lost after a solution stands for some time or more quickly when warmed. Evidence that the antineuritic’ compounds in autolyzed yeast undergo a change probably due to dynamic isomerism has been presented by Wil- liams and Seidell. A preparation from cardiac muscle loses its ameliorative power in a few days.’® A similar change may be the cause of the apparent lessened activity with age of the hydrolyzed extract used in these experiments. The method of extraction with infusorial earth appears in- applicable, due to the inability of small quantities of infusorial earth to absorb the total vitamine content of the hydrolyzed extract of rice polishings. SUMMARY A study of the antineuritic properties of infusorial earth ex- tracts of the hydrolyzed extract of rice polishings is reported. Only a part of the vitamine content of the extract was ex- tracted by the proportions of infusorial earth used. There appears to be a loss of antineuritic power in the extract as it ages. * Williams, R. R., Journ. Biol. Chem. (1916), 25, 437. | * Williams, R. R., and Seidell, Atherton, ibid. (1916), 26, 481. * Cooper, Evelyn A., Biochem. Journ. (1914), 8, 347. THE USE OF CHAULMOOGRA OIL AS A SPECIFIC FOR LEPROSY * By Harvey C. BRILL and ROBERT R. WILLIAMS (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) Regarding the cure of leprosy by means of chaulmoogra oil, considerable differences of opinion exist. Thompson,’ of New South Wales,.was unable to effect any cures by its use. The Philippine Health Service released twenty-three cases from Cu- lion leper colony about a year ago that had been treated with chaulmoogra oil. No positive claims that it brought about these cures are made by the more judicial members of the Health Service staff, nor can these patients be considered permanently cured until they have been under observation for a longer period of time. However, chaulmoogra oil appears to be the most pro- mising remedy for the treatment of leprosy at present known. The administration of chaulmoogra oil is accompanied by con- siderable difficulties. When administered by mouth, nausea and digestive disturbances follow. Given subcutaneously, it is ab- sorbed slowly, since it is a heavy oil; consequently its adminis- tration in this manner is painful, due to the pressure on the nerves and the sores that result from the slow absorption. Then not all cases react to the treatment. The nonuniformity of the results that follow its administration may be due to a difference in the quality of the oil or to a variation in the disease itself in dif- ferent localities. : Crude chaulmoogra oil is usually recommended for use.* The recommendations of those engaged in its administration are strongly in favor of the crude oil, but these opinions may partly be a matter of prejudice. These practicioners undoubt- edly have been previously disposed in its favor by their reading, and as observations of leprosy treatment are not very general nor very decisive, and as recovery in any case is slow, decisions as to its efficiency are difficult to form. We must conclude that eases of positive cures by means of chaulmoogra oil are not de- finitely proved. * Received for publication January 29, 1917. * Report of the Board of Health on Leprosy in New South Wales (1908). *United States Dispensatory. 18th ed. (1899), 1678. 207 208 The Philippine Journal of Science 1917 EFFECTIVENESS OF CHAULMOOGRA OIL Again, standards for determining whether an oil is crude or refined are rather arbitrary, and when applied to an oil such as chaulmoogra, where the previous history of the oil is not known, the difficulty of deciding is still more difficult. An expressed oil would carry with it other substances.. For example, when the oil from bitter almonds is expressed, a small amount of the amyg- dalin of the nuts is carried with the oil. Power and Lees* have shown that the chaulmoogra seeds and the hydnocarpus seeds all contain small quantities of a cyanogenetic glucoside that they found to be identical with gynocardin, the glucoside present in Gynocardia odorata. When the oil of these nuts is expressed, minute amounts of the glucoside doubtless accompany the oil; therefore the effective- ness of the crude oil may possibly be due to the presence of the cyanogenetic glucoside. The small amount of the glucoside . present would account for the slowness of the action of the oil. The small amount of glucoside that may possibly be present in the oils is shown by the nitrogen content of some chaulmoogra oils in Table I. These data illustrate the maximum possible amount that could be present. TABLE I.—Nitrogen content of various chaulmoogra oils. Calculated as No. of sample. ® \Nitrogen. (ate +1.5H20). Per cent. vee cent. fp [eeneeeeernne inion Bes apie iy eh ee ee eh be Ree ee Se at eS 0. 01863 0.350 Been De ceeneeB eeeeee on e et rs e 0.00438 0.113 Bos nct Reet ee ea Bee poe re Re ee Pe Ee 0.01880 0.355 Bee oe ee we Ss IS ese eT ee eee 0.01415 0.364 Bae rpc ie es A a ne eR eS ap Os a ee etree 0. 01257 0. 323 GLEEE 2 EE ee Sie eT a OE Eee. SS SE ee ee 0. 00670 0.172 Neacen Be oc os scene ek aene dese teen Be pe oa oe See ee eee 0. 01503 0. 386 Sc foo ee a ee ee eee LE eines Rn ee 0. 02209 0. 568 8 For description of samples see Table III. CONSTITUTION OF THE OIL The acids of the oils of this family of seeds, Taratogenos kur- 2ui,> Hydnocarpus wighttiana, H. anthelmintica,® H. venenata,' * Journ. Chem Soc. London (1905), 87, 349. * Power and Gornall, Journ. Chem. Soc. London (1904), 85, 838. ° Power and Barrowceliff, ibid. (1905), 87, 884. "Brill, This Journal, Sec. A, (1916), 11, 75. XII, A, 4 Brill and Williams: A Specific for Leprosy 209 H. alcalae, and Pangium edule,’ are peculiar in that they are monobasic unsaturated acids with a ring structure.’ Chaulmoo- gric acid is isomeric with linoleic acid (C,H,.0.), but differs from the latter in that it combines with but two bromine or iodine atoms and contains but one ethylenic linking and a closed chain. It is very stable toward alkalies. Heating to 300° C. with alkalies does not decompose it. It is optically active, rotating the plane of polarized light to the right. These properties make it dis- tinct from all other known acids, and one would expect its phys- iological properties to be different from those of other acids. Hydnocarpic, the other peculiar acid found in the oil of these seeds, is a lower member of this same series. Chattopadhyay has taken exception to the conclusions of Power and his coworkers regarding the presence of acids of the nature of chaulmoogric and hydnocarpic in chaulmoogra oil, but his results are not complete enough to substantiate his contention. The results by one of us (Brill) on H. venenata are in agree- ment with those of Power et al., and unless Chattopadhyay can produce results which really contradict those of Power, the results of the latter will continue to be accepted. That the effectiveness of chaulmoogra oil may be due to the presence of free acids has received further confirmation recently by the experiments of Leonard Rogers,'? who administered the free acids themselves and these in the form of their sodium salts. However, the com- pound known as antileprol, which is the mixture of the ethyl esters of chaulmoogric and hydnocarpic acids, was without effect when used by the Philippine health authorities. We should ex- pect the ethyl esters to have an effect as powerful as that of the free acids, since they would be readily hydrolyzed in the system. Indeed it is hardly to be expected that the free acids should be so radically different in activity from the glyceryl] esters, the neutral oil itself, since the oil when absorbed would be undoubtedly hydrolyzed to some extent in the system. The use of the soluble alkali salts would appear to be more promising on account of their solubility and more ready absorption, and as Rogers obtains promising reactions when a solution of these salts is administered intravenously, they deserve to be tested thoroughly by the va- rious scientists interested in the treatment of leprosy. The work described in this article was undertaken in the hope SBrill; ibid (lo17))) 2; Now. * Barrowcliff and Power, Journ. Chem. Soc. London (1907), 91, 557. * Chattopadhyay, P. C., Am. Journ. Pharm, (1915), 87, 473. =~ LOC. aCit. % Lancet (1916), 190, 288; Indian Med. Gaz. (1916), 51, 195 and 437. 210 The Philippine Journal of Science 1917 that some light might be thrown on the constituent in chaulmoo- gra oil that is specific for leprosy; that it might be isolated and that its isolation would simplify the administration of the oil; and that the more concentrated form of the physiologically active substance would bring about speedier improvements in the con- dition of the patients. While the results have not been entirely successful in this endeavor, yet in the hope that they may give an inspiration to other investigators, and because of the infor- mation they give concerning chaulmoogra oil itself, they are presented here. The administration of the preparations was kindly performed by the Philippine health authorities at the Culion leper colony. Circumstances were such that in some cases the treatment was not continued over a sufficiently prolonged period, nor were the administrations frequent enough. Denney ** has described the difficulties of persuading lepers to continue a treatment for any length of time. For this reason some of the fractions hereafter described might show more satisfactory results under more favorable circumstances. The treatment at Culion is entirely voluntary. The leper voluntarily presents himself for treat- ment, and the treatment is continued only as long as the patient is in the humor for taking it. No coercion can be applied; con- sequently the health officer is handicapped in his desire for a systematic study of the treatment of leprosy. TABLE II.—Constants of various chaulmoogra oils examined by the Bureau of Science. Specific Ve att ie Specific in chloro-| Tue ce. |Sepenif Index of | qogine at 30° C. . Y value. tion. value. “| sodium base. light. Ne rs eee a eee eee eee 0.9585 | +62.23 5. 28 196. 6 1. 4755 99.3 JER ERES Was 5! MEAS DE he ae See 0.9464 | +52.12 2.69 189.1 1.4768 | 101.1 Be ele ee eget 5 og ee 0.9492 | +45. 69 7.19 191.6 1.4766 | 102.6 ys Se eS ee aoe ea 0. 9492 +57. 45 9.38 196.8 1. 4730 79.6 Deen rete an See ae eer 0.9429 | +48.95 21.48 196.3 1.4720 | 100.1 GPE LSE ECOEE RES 0 SE ee? 0.9487 | + 58.20 5.63 196.2 1.4732 | 102.1 Y ee See Oe ee eS eee Se Sem 0.9484 | +.48.73 1.55 210.5 1.4755 | 110.4 tw testay Rey ae Sig SCE a Se pe A RS 0.9467 | +46.26 6.36 210.5 1.4750 | 104.6 Que ie 2s aoe 2 oe eee ae ee 0. 9470 +51. 60 2.80 215.0 1.4774 107.5 RE SE ee BS ES ie Ly ee see bk ea | 0.9454 +47. 30 5. 56 203.3 1.4762 99.5 Maximumies sbi scans essen ees 0.9535 | +58. 20 21.48 210.5 1.4774 | 110.4 Minimum Averipe =~ 2S ee ne ee ee *® Denney, Oswald E., This Journal, Sec. B (1915), 10, 357. XII. A, 4 Brill and Williams: A Specific for Leprosy P11 For comparative purposes the constants of chaulmoogra oil used in this experimental work and of other samples of chaul- moogra oil that have been examined in the Bureau of Science are inserted. DESCRIPTION OF SAMPLES OF CHAULMOOGRA OIL Sample 1.—This oil was obtained from the Philippine Health Service from the stock used by them in the treatment of the lepers at Culion. It was a greenish yellow limpid oil (30°C.) with a characteristic odor. Sample 2.—This oil was extracted from seeds by means of petroleum ether. The oil was liquid (30° C.) ; it was somewhat lighter in color than sample 1, but had the same odor. The seeds were obtained from H. G. Carter, economic botanist to the Botanical Survey of India, Calcutta, India, and were labeled “chaulmoogra seed—Taraktogenos kurz.” Sample 3.—This is an oil purchased from the German Dis- pensary, Manila. The oil was of the same color and odor as sample 1, but differed from the preceding in that it had a small quantity of solid particles deposited, about two parts per hundred. Sample 4.—This is a sample of oil purchased from the Botica de Santa Cruz, Manila, and marked “Aceite de Chaulmugra.”’ The sample was practically identical with sample 1 in appearance and other properties. Sample 5.—This sample was purchased from the Botica de Santa Cruz. It bore the following on its label: “Chaulmoogra oil.” The fixed oil expressed from the seeds of Gynocardia odorata R. Brown natural order Bixacez. Should the oil become solidified from cold, it may be readily liquified by placing the container in warm water. Dose 10 to 20 minims (0.6 to 1.3 cc.). Guaranteed under the Food and Drugs Act, June 30, 1906, guaranty No. 6. This oil was so nearly solidified at the ordinary temperature (30° C.), that-it would not readily pour. Sample 6.—This oil was submitted by the Philippine Health Service for test to determine its purity. The sample was liquid and possessed the odor and color of sample 1. Sample 7.—This oil was expressed from seeds purchased through the Department of Agriculture, Assam, Seed Depot Gauhati. They were marked “gynocardia odorata,’ but were sold to the Bureau of Science in response to a request for chaul- moogra seeds. The oil was a heavy, limpid oil, darker in color than sample 1, but with the same characteristic odor. Sample 8.—This oil was submitted by the Philippine Health 212 The Philippine Journal of Science 1917 Service for testing as to purity. It was marked: “Finest oil of Chaulmoogra, Stanistreet Brand.” It is very similar in prop- erties to sample 7. Sample 9.—This oil is identical in all respects with sample 7, being obtained by expression from seeds from Assam, marked “Gynocardia odorata.” Sample 10.—This oil was submitted by the Philippine Bureau of Supply for testing as to purity. It was marked: “Crude Chaulmoogra Oil. A. S. Watson, Hongkong China.” The oil was very similar to sample 1. A survey of the constants of the oils described above shows that they are different from the constants given by Power and Barrowcliff '* for the oil from Gynocardia odorata and that the name Gynocardia odorata used for some of the oils examined by us is incorrect, but that they are in substantial agreement with their results for the chaulmoogra and the hydnocarpus oils. CHEMICAL EXAMINATION OF CHAULMOOGRA OIL A more thorough chemical examination of chaulmoogra oil was made for the purpose of substantiating the results of either Power or those who disagree with him. For this examination samples 2 and 5 were chosen. They were saponified with alco- holic potash, and the free acids were obtained by acidification and extraction with ether. Table III gives the properties of the free acids. TABLE III.—Properties of the free acids of chaulmoogra oil. Sample No.— | 2 | 5 = a BC i aEY j | : Specific rotation in chloroform for sodium light at 80°C -__________. --__-- +54. 00 +47. 40 Todinevaltie 2 45— 2 = 5 eT SRE oe, in Rage EE eee ae 101. 38° | 99. 7° ACG Values. 4. concen scnanons eee ei ot es acon ancee eer Ce. ose 235.31 | 234,95 Melting points. i seccsc2n toss oe ee ee eee eee SIGH 38-39 | 3S-40 "0.1 N base. These acids were treated in the manner adopted by Power for the separation of chaulmoogric and hydnocarpic acids. Not much difficulty was experienced in obtaining a body from No. 5 that melted at 67° to 68°C. when recrystallized from al- cohol, but considerable difficulty was experienced in purifying the fraction from No. 2 sufficiently to raise its melting point to * Journ. Chem. Soc. London (1905), 87, 887. XII, A, 4 Brill and Williams: A Specific for Leprosy 213 67° to 68° C. The properties of these acids are tabulated in Table IV. When the residue of acids after the separation by means of crystallization from alcohol was treated with barium acetate, four fractions were obtained. These had the melting points noted in Table IV. = TABLE I1V.—Melting point of acids obtained by treatment with barium acetate. | Sample No.— 2 5 IG: Chor Meltnpi nomiorfrachOn 2-6 oon6 Sea ee see oe ete no ease nnn eeeasaosee 36-37 47-48 Merion OG frACtlON aio cn = seen na ee eee eee ere ne ap eet sae 40-41 38-39 REI nNP DOIN b Ol raC HON Gane ase = eee nce Gees on etc ean anaaseseense 39-40 | 39-40 Mebimp none Of crac won 4. 02252 G8 ee rE ge 2 ee 37-38 34-35 ee oot Nots.—Fractions 2 and 3 were in both cases united, and the combined portions were recrystallized from alcohol, discarding the portion first erystallizing out. They were then again converted into the barium salts, the acids set free, and again crystallized from alcohol. The melting points correspond to the melting point of hydnocarpic acid, 59° to 60° C. TABLE V.—Saponification values of acids isolated from chaulmoogra oil. 0.1 N base required | Saponi- Sample. Quantity.| for neu-| fication traliza- | value.4 tion. 9g. ce. PECTS MOOR RIC ACE see sere on a5 ee ee Se 1.1454 | 40. 92 200.5 brorrehanlmoopricacid’ 2.0.2 = oped! ooh Ses ols ay eo | 1.0587| 38.13! 202.4 EEO ON OCAMPIC ACO = ee ie nee ae ee, ee 1. 9205 76.21 222.7 LOM MvaNncdcarpiciacid..9s.. Seis Stas Bee hie Se ae ae a ee 2. 8560 110. 82 218.2 ® Theoretical saponification value for chaulmoogrie acid, C;;Hs;COOH=200.5; for hydno- cearpic acid, C;; He; COOH= 222.7. TABLE VI.—Specific rotation in chloroform at 30°. C/D of fees isolated from chaulmoogra oil. Sample. ‘in 25 ce. Bey Specific | | enone tube, | rotation. Gia aca g. Degrees.| Degrees. NIRS Se Sag tok OO SR = Se eS Ore ea oe pe RPE AS PS 1. 8120 +2.14 +59. 05 Bee ee eres sees SL SE ee meena at ay eGo. oad ee Na 1.4416 | +1.68 +58. 10 Hydnocarpic acid Gites ask &. Shoe | Se eee bee ete ee ees ee ee sc AL 2.6740 | +7. 24 +67. 70 BS otk Soe eso ess ee Saeko} So go See ae as = ae |} 1.5545 +4. 20 +67. 60 i 8 Found by Power for chaulmoogric acid, 58.6°; for hydnocarpic acid, 68.1°. 214 The Philippine Journal of Science 1917 TABLE VII.—Jodine value of acids isolated from chaulmoogra oil. 0.1N Iodine iodine value Sample. Quantity-| olution | (Han- used, us).a gn TONE rece: Chaulmoogric acid: eaters BASE UE ye ee ns eee sn eee 0. 1806 12.73 89.5 Bocun abn tee dee eee t eG! PA a eee eae Se 0.1558 11.13 90.7 Hydnocarpic acid: DOES ee oo hn saan beat owe uk wanaeonee Coe see aonecu ae Ssiassece 0. 2250 17.71 100.2 | BSSeE SoCeeE ae See SR Bone cee ees enee eaten 0. 1625 12.73 99.9 8 Theoretical iodine value for the addition of two atoms of iodine to chaulmoogrie acid, Cy7H3,COOH = 90.6; for the addition of two atoms of iodine to hydnocarpic acid, C;;Hs;COOH =100.6 : Preparation and description of samples—A sample of chaul- moogra oil was washed with three separate portions of alcohol. The alcohol took on the color of the chaulmoogra oil, and a par- tial solution of the two took place. The separation was effected by adding water to the mixture, when the alcohol and oil formed separate layers. The alcohol-washed oil had the properties noted in Table VIII. TABLE VIII.—Properties of chaulmoogra oil after washing with alcohol Specific gravity 0.9530 Specific rotation in chloroform for sodium light +652.11 Acid value ce. 0.1 N base 2.46 Saponification value : 196.3 Index of refraction 1.4735 The alcohol extract after extraction with petroleum ether was distilled under lowered pressure until all the water and alcohol were removed and only a small residue remained; it was then dried over sulphuric acid in a vacuum desiccator. The residue is a golden yellow, viscous, almost odorless, noncrystallizable mass. It constitutes about 0.06 per cent of the original oil. It was insoluble in olive oil, but was suspended in 50 cubic centi- meters of this oil, marked No. 1, and submitted to the authorities at Culion with the following directions: Directions: 1 cubic centimeter=80 cubic centimeters chaulmoogra oil; initial dose 0.10 cubic centimeter increasing to 0.50 cubic centimeter; shake before using. The sample used in this manner at no time caused a reaction, that is, it appeared to be physiologically inactive when given in the above doses. The petroleum ether extract of the alcohol extract was placed on the steam bath for the removal of the pe- troleum ether and finally dried in a vacuum desiccator. This oil, XII, A, 4 Brill and Williams: A Specific for Leprosy 215 marked No. 2, is darker than No. 3 (described later) ; it is solid at ordinary temperature (30° C.). It constituted about 26.2 per cent of the original oil. Directions: Dose same as chaulmoogra. The alcohol-washed oil was then placed in a cold room (tem- perature, 17° to 19°C.) for four days, where it hardened to a viscous mass. When placed in cheesecloth and hung, only a very small portion separated. It was then placed in a hand press and subjected to pressure. The fractions resulting were again subjected to fractionation by means of the press, and the hard fractions were mixed, and the soft samples that resulted were mixed. The soft oil fraction, known as No. 4, was the darkest of the three samples. It is soft at 17° C. and constitutes about 20.7 per cent of the original oil. The hard oil fraction, submitted to Culion as No. 3, is darker than No. 2, but not so dark as No. 4. -It is hard at 17° C. and constitutes about 53 per cent of the original oil. The directions for Nos. 3 and 4 were identical with the directions for No. 2. The chemical constants of these three fractions are tabulated in Table IX. TABLE IX.—Constants of fractions Nos. 1, 2, and 3. | | Specific z | * | | 1 Specific Oso Acid va- Saponifi- | Index of | ae Ieee ah | [Sample No.| gravity | Fo eotere. es cation | refrac- | lodine Original | Remarks. CRARLIS COM [AAO Se value. tion. Wee Oar | sodium | base. | light. pce | | | | | P. cent. | (Aas ae 0.9440 | +52.35 | 17.08 190.2 1. 4699 98.7 26.2 | Solid at 30° C. |p CaS eee 0. 6522 17 ES Os | ee gy 7 ty eee 100. 2 538.0 | Solid at 17° C. (Np ee 0. 9537 4584 oo 191.3 1, 4764 103.4 20.7 | Liquid at 17°'C: | | None of the fractions showed any greater activity than the orig- inal chaulmoogra oil, that is, no more marked reactions were ob- ‘served than are caused by the administration of chaulmoogra oil. Sample 2, Table II, which was obtained by petroleum ether extraction of seeds received from Madras from H. G. Carter, economic botanist to the Botanical Survey of India, and listed as seeds of chaulmoogra, was forwarded as No. 5. Its proper- ties place it with chaulmoogra oil. Directions: Dose same as chaulmoogra oil. The sample gave no reaction, differing in in- tensity from that of ordinary chaulmoogra oil when it was ad- ministered. It seemed no less active than many commercial samples used by the Public Health Service. 150276——4 216 The Philippine Journal of Science 1917 TABLE X.—Daita on seeds of chaulmoogra. Grams. Per cent. | BiB a} Cov V1 A >: ene me poy Se ye SE Se ea a a eae ee IR BE i 10, 366 | PR = Koerniel gino aa nea se ee a ee ee 6, 372 61. 47 | |." Shella. css tose ea enn a ee 3,994, 38,53 | Ie Dry ernelacses 2 eee corer cae ae ee eres 5,959 BT. 48 | Oil extracted with patroleuiti BuWer oe Po os hn do ee ee ee ees 3, 160 |----------- Qs based ontwihtole mnt on nee een ee eee / 30. 48 Onli based toner ern elem a cae | Mee ae ae | 58.08 PAT CONGHCIOR DUC tse mn es a ec ee ee 810 Alcoholic extract based on whole nut -_-.-----.-------- iivsbecceh sn deaeekee |----222== 3.57 Alcoholic extract based on dry kernel-_-___.----.-------------------- nanan n--=- | wea sseeuee | 6.20 VALOR Or ere ae ee ee ~ 2 enn oe nana nnn = === | 350 |---.2e eee ! Water extract bused'on whole: mut ---=.—-"-22 50-20-34 ne es ee peesceco=- / 3.37 Water extract based ondry ‘kernel. 23. +_.-.-..3-t222 cee eee eee ee bikes Sees 5.87 eee | The ground petroleum ether extracted nuts were then extracted . with hot absolute alcohol, and the alcohol extract was evaporated to small bulk. A large quantity of sugar (glucose) separated from the mother liquor. After the separation of the free glucose the extract was evaporated to dryness, and the residue was dis- solved in water and extracted with chloroform. The chloroform was evaporated, and the residue was dissolved in water and evaporated very slowly over sulphuric acid. No crystalline prod- uct was obtained. The sample had a somewhat bitter taste. It was dissolved in a mixture of alcohol and olive oil and for- warded to Culion as No. 6. Directions: Contents, 100 cubie centimeters; initial dose 1 cubic centimeter, to be increased later if advisable; shake before using. In one case this sample gave a decided reaction, Be no repeti- tions of this reaction were obtained. One half of the material after having been extracted with chloroform was dissolved in 200 cubic centimeters of 15 per cent alcohol and forwarded as No. 7. Directions: Initial dose 1 cubic centimeter to be increased later if advisable; shake before using. No noticeable reaction was obtained with this fraction. An attempt was made to isolate a crystalline product from the remaining half of the extract. A small amount of sugar only was obtained. Apparently the glucoside, originally pres- ent, has been hydrolyzed by the enzymes and moisture. One half of the water extract obtained by treatment of the ground seeds after the alcohol treatment was dissolved in 500 cubic centimeters of 15 per cent alcohol and submitted as No. 8. XII, A, 4 Brill and Williams: A Specific for Leprosy P17 The remainder was examined for crystalline bodies without any success. Directions: Initial dose 5 cubic centimeters, to be increased later if ad- visable; shake before using. No reaction was observed when No. 8 was administered. The ethyl esters of the acids present in chaulmoogra oil were prepared by esterification of a mixture of alcohol and chaul- moogra oil, using hydrochloric acid gas as the dehydrating agent. The excess acid was neutralized by adding dry sodium carbonate. This sample was submitted as No. 9. No observed reactions attended its administration. Because of the reputed superiority of the crude oil over the refined oil, the two remaining samples were prepared. To de- termine if the greater effectiveness of the crude oil might be due to the presence of free acids, No. 10 was prepared. Two hun- dred grams of chaulmoogra oil were saponified, and the free acids were dissolved in a portion of the original oil. This pre- paration had an acid value of 11.47 cubic centimeters 0.1 N base. Directions: Dose same as chaulmoogra oil. The reactions observed were reported as no more marked than the reactions caused by chaulmoogra oil itself. EXPERIMENTS WITH AMYGDALIN The other speculation, regarding the cause of the greater effectiveness of the crude oil, that it might be due to the pre- sence of small amounts of the cyanogenetic glucoside, induced us to investigate the effect of amygdalin on leprosy. Amyg- dalin ** is hydrolyzed by emulsin, crab juice, and acids, giving glucose, benzaldehyde, and hydrocyanic acid. Wchler and Fre- richs '° state that amygdalin in small quantities is not poisonous ' to dogs, but when given in quantities of from 4 to 5 grams it causes sickness, and when accompanied by emulsin it is extremely poisonous, since it is hydrolyzed by the enzyme giving free hydro- cyanic acid. To determine the rapidity with which it is eliminated from the blood stream, 0.25 gram was dissolved in 1 cubic centimeter of water, and this solution was injected into the vein of the right ear of a rabbit. Four rabbits were so treated. At the end of two, ten, and twenty-four hours 0.5 cubic centimeter quantities of blood were drawn from the left ears of the rabbits, and this * Abderhalden, Emil, Biochemisches Handlexikon. Julius Springer, Ber- lin=(1911), 2, 707. * Annal. d. Chem. & Pharm. (1848), 65, 337. 218 The Philippine Journal. of Science 1917 blood was tested for the presence of amygdalin by hydrolysis with hydrochloric acid and was tested for hydrocyanic acid by distilling into alkali and using ferrous sulphate paper, with the results noted in Table XI. TABLE XI.—Elimination of amygdalin from blood stream of rabbits. Results. Rabbit. 2hours. | 10 hours. | 24 hours. We aoc cas Ja BRE eas & RC Re ee clas (a) — } eee ea See oes oe iee me Leese aye ES. aRar (2) = Blk eshte oe TI ORs eae, Eee RL Pee ae ey Cee ee oe eee ++ (a) - Ma ON re a na ee ee ee ++ (a) = ++, fair test for hydrocyanice acid; —, negative for hydrocyanic acid. ® Questionable. The results indicate that the amygdalin no longer exists in the blood stream after ten hours. Tests were made with blood and blood serum from lepers and with blood from apparently healthy people by incubating the samples with a standard amygdalin solution to determine if any difference exists in their hydrolytic powers on amygdalin. TABLE XII.—Quantity of hydrocyanic acid liberated by the action of blood on amygdalin. Quantity of amyg- |Quantityof} Hydro- dalin solu- |0.1.N silverjecyanic acid) Hydrocy- Kind of blood. tion (1 nitrate liberated | anic acid gram in solution jin per cent! liberated. 150 cc. of used. of original. water). cc. cc. Teper fos in- feta eer c we eet ee cone tem enaeer 25 1.10 3.68 | 0.000860 Blood serum from leper --_-----------.------------- 25 1.63 5.50 | 0.000540 Healthy:: 2236054285) 20 eB a Re See 25 0. 22 0.60 | 0.000059 WDWOrs cee tee ee ee Se ee ee 25 0.22 0.60 | 0.000059 DOS ree eee ena seen eee Oe cec are eon eee 25 0.38 1.05 | 0.000103 ee REN eae i ee ee Soe en 25 0.38 1.05 | 0.000103 Doesnt Ses ke Soe oes Rhea ae eee ee 25 0.36 0.98 | 0.000097 DO oon stare ocr ents oe hn ear 25 0. 28 0.77 | 0.000076 DOS nose res SA Sa ae ee 25 0. 47 1.30 | 0.000128 YD [a eee cae en eR eae ee a ee a ee eee oi 25 0.49 1.33 | 0.000182 I D Ya ae eerie in AE Lope ag Bs Le US Soe 25 0.34 0.94 | 0.000092 Dor setae Sle ee ee ee eee eee none. 0.38 1.05 | 0.000103 None 222se ode a eee RE ee ok i os 26 0. 40 1.10 | 0.000108 While the absolute results may not be of extreme accuracy, they are comparable and indicate that leper blood may have greater hydrolytic power on amygdalin than does normal blood. XII, A, 4 Brill and Williams: A Specifie for Leprosy 219 It is to be regretted that we were unable to procure more leper blood in order that this study might have been extended. To determine the action of amygdalin on lepers, tablets weigh- ing approximately 0.05 gram were made and submitted as No. At. Directions: One tablet every other day gradually increasing the size and frequency of the dose. The Culion authorities reported no marked reactions with amygdalin, but the trial was not over a long period. It might give more favorable results under improved conditions. HYDNOCARPUS ANTHELMINTICA For the purpose of further confirming the results of Power and others on their work on chaulmoogra and hydnocarpus oils, the constants of the oil from the seeds of Hydnocarpus anthelmintica obtained from Madras, through the kindness of H. G. Carter, and examined in the Bureau of Science, are added. TABLE XIII.—Constants of oils from Hydnocarpus anthelmintica seeds. Results. NDECIIC Craviby at 300 Gr soe ee be oo een enka seuss ese od 0. 9487 a0. 9520 Specific rotation in chloroform for sodium light -____---._...--.------.--- +49. 50 51.0 Acidhyalnetces OS/NiDAEe ene eae oie ae PM, 0.6 8.1 Pa TIO TINO TION RLU C sorrel ee tr a oe ee ES 206. 2 208.0 MIdexiOn YeLraction=|~- 25, .ssoe == <2 suai Sooo eed eee eben ascend 4725) Peo o22 222.2 Nadine value= sso +o -o8 sso n os oe ene a one ea eee ee Se beck 90.8 82.5 | 8 At 25°C. Results of Power and Barrowcliff, loc. cit. The results are close enough to prove the identity of the seeds furnishing the two oils. DISCUSSION As has been previously stated, the medicinal administration of chaulmoogra oil should be accompanied by the chemical control of the samples used. It seems plausible to think that the slow- ness of the changes caused by the use of chaulmoogra oil in the treatment of leprosy may be due to the small quantity of the active constituent present in the oil. If this constituent could be isolated and administered in concentrated form, more rapid cures should result, and the treament would undoubtedly be less painful. ; The results of Rogers?" with the free acids and the sodium " Loe. cit. 220) The Philippine Journal of Science salts make the use of these appear as promising remedies. But Rogers cautions against the assumption of a too optimistic at- titude, as he regards the problem as still unsolved. On the other hand, it seems likely that antileprol and the neutral oil should be more effective than they have been found to be, if cures result from the use of the free acids and of the sodium salts. Consequently the inactivity of antileprol and of many of the commercial chaulmoogra oils should make practitioners cau- tious about accepting a remedy as specific for leprosy until it is proved to be such. SUMMARY The constants of ten samples of chaulmoogra oil are given. A chemical examination of chaulmoogra oil is included. The use of various fractions of chaulmoogra in the treatment of leprosy is discussed, and the desirability of chemical investigation accom- panying the medicinal administration is pointed out. ‘and En centre i §.- a Ns ; (REED; py fah lan ae ) Bre. ; Got - ERS and Rar eas aye} alee, 1 se b, 0 dere tet te Y i ry a *STeiportant at a nae t a 215 and. effort in. Bg govess 2 2 oa Hi at the |. THE PHILIPPINE JOURNAL OF SCIENCE A. CHEMICAL AND GEOLOGICAL SCIENCES AND THE INDUSTRIES VoL. XII SEPTEMBER, 1917 No. 5 THE COMPOSITION AND MOISTURE CONTENT OF THE SOILS IN THE TYPES OF VEGETATION AT DIFFERENT ELEVATIONS ON MOUNT MAQUILING? By WILLIAM H. BRown and ANGEL S. ARGUELLES (From the College of Liberal Arts, University of the Philippines, and the Bureau of Science, Manila) THREE PLATES AND ONE TEXT FIGURE In the Philippines, as in other moist tropical countries, there are frequently decided changes both in the composition and in the physical character of the vegetation even in very limited areas. One of the most remarkable examples of this is the frequency with which vegetation becomes dwarfed at compara- tively low elevation. On Mount Maquiling a lofty forest occurs at elevations up to 600 meters, while at an altitude of 1,000 meters the ground is covered by elfin wood. The object of the work here reported was to determine whether or not the types of vegetation on the eastern and southeastern slopes of Mount Maquiling could be correlated with the composition and water content of the soils. : The soil of the Philippines is largely of volcanic origin. Cox? has published the results of a large number of analyses of soil from different parts of the Archipelago. He concluded that both the chemical and physical analyses indicated that the soil of the Islands was on the whole fertile. Cox also shows that the distri- bution of cultivated crops appears to be determined largely by the Received for publication June, 1917. ? Cox, Alvin J., Philippine soils and some of the factors which influence them, This Journal, Sec. A (1911), 6, 279-330, Pls. I-XI. 150586 221 222 The Philippine Journal of Science 1917 character of the rainfall, certain plants being grown more ex- tensively where there is a distinct dry season and others where the rain is more evenly distributed throughout the year. A more intensive study of the soils of Luzon has been published by Cox and Argiielles.® Brown and Matthews * have shown that in the Philippines the present distribution of forest and grassland is due to the activity of man combined with climatic influences. Grasslands only occur where the forests have been removed. They are produced and maintained by frequent fires and so are most extensive where there is a pronounced dry season. MOUNT MAQUILING Mount Maquiling is an isolated volcanic cone, situated on Luzon, midway between the eastern and western coasts, about 64 kilometers southeast of Manila, in latitude 14° 10’ east of Greenwich. It reaches an altitude of approximately 1,100 me- ters. The geology of the mountain, particularly of the lower slopes, has been described in considerable detail by Abella.® The main crater of the volcano has apparently been extinct for a long period. The rim has been eroded until it has become a series of peaks which, except on very steep slopes, are covered with deep soil. Volcanic activity has, however, not entirely ceased, as numerous fumeroles and hot springs occur around the base and on the lower slopes. On the eastern and southeastern sides the mountain grades into the surrounding plain at an elevation of approximately 50 meters. On the lower slopes there are layers of soft volcanic tuff. At elevations of from 50 to 100 meters these layers of tuff, which are mixed with layers of soil, may be many feet thick and are frequently near the surface. The layers near the surface are, however, usually thin, soft, and very much broken. Such a layer, about 30 centimeters thick, is frequently found about 30 centimeters below the surface, and traces of such a layer occur at elevations as great as 300 meters or more. West and Cox ®* give *Cox, A. J., and Argiielles, A. S., The soils of the Island of Luzon, ibid., Sec. A (1914), 9, 1-50. ‘Brown, W. H., and Matthews, D. M., Philippine dipterocarp forests, ibid., Sec. A (1914), 9, 418-561, Pls. I-XIIT. * Abella y Casariego, D. E., El Monte Maquilin (Filipinas) y sus ac- tuales unanaciones voleanicas. Imprenta y Fundacién de M. Tullo, Madrid (1885), 1-28, Pls. 1-2. ‘West, A. P., and Cox, A. J., Burning tests of Philippine Portland cement raw materials, This Journal, Sec. A (1914), 9, 79. xu,a,5 Brown and Argiielles: Soils on Mount Maquiling 923 analyses of a number of samples of similar tuff. These analyses indicate that the tuff should disintegrate into a fertile soil. Where the surface layers of the tuff are shallow and much broken, they appear to have little if any effect in determining the character of the vegetation. We have seen thick surface layers only around the base, where the original vegetation has been almost entirely removed. The climate of Mount Maquiling may be classified as mon- soonal; that is, the rains depend upon rain-bearing winds, which shift their direction twice a year. This results in distinct wet and dry seasons. The northeastern monsoon strikes Luzon on its eastern coast and deposits a large part of its moisture in passing over the divide between the Pacific Ocean and Laguna de Bay; when it reaches Mount Maquiling, it is a drying wind. This monsoon results in a decided dry season from January to April. The most pronounced rainy season is from July to Sep- tember during the southwest monsoon, when a large part of the rains are the result of cyclonic disturbances (typhoons). Around the base and on the lower slopes of Mount Maquiling there is a mixture of grassland and second-growth forest. Above this there are three distinct types of original forest, which occur at successively higher levels. GRASS AREA The mixture of grassland and second-growth forest at the base has been described by Brown and Matthews.’ This region appears to have been originally covered with a tall dipterocarp forest, which is the type occurring at the next higher elevations. The original forest was removed, and the land was cultivated. In the area under consideration cultivation was abandoned, and much of the ground became covered by tall grasses, chiefly Sac- charum spontaneum (talahib) and Imperata exaltata (cogon). These grasses are very inflammable when dry. They were burned at frequent intervals, the last fire occurring in 1911. The grass fires kill nearly all tree seedlings, but appear to do little if any damage to the rhizomes of the grasses. Saccharum spontaneum (Plate 1, fig. 1) and Imperata exaltata both form dense stands, the former frequently reaching a height of over 3 meters, while the latter is shorter, being rarely more than 1.5 meters in height. Mixed with the grass are areas of second-growth forest, and since 1911 much of the grassland has changed to 7 Op. cit. 294 The Philippine Journal of Science 1917 forest, as quick-growing trees readily invade the grass areas when there are no fires. The trees have a very rapid rate of growth and are small, usually reaching a height of only 10 meters or less. Our soil samples from this altitude were taken in a grass area at an elevation of approximately 100 meters. DIPTEROCARP FOREST At altitudes between 200 and 600 meters the ground is covered by a tall, dense dipterocarp forest. This is composed of three distinct stories of trees, the tallest of which reaches a height of from 35 to 40 meters (Plate I, fig. 2). The most prominent tree in it is Parashorea plicata, which is frequently more than a meter in diameter. The second, or middle story, is composed of medium-sized trees, which spread their leaves under the branches of those of the top story. The second story reaches a height of about 18 or 20 meters. The most prominent species is Diplodiscus paniculatus (balobo), which is represented by many more trees than any other species in the forest and is probably about four times as numerous as any other second-story species. The third story is composed of small trees that reach a height of about 10 meters. The presence of the different stories is not evident on casual observation, as the specific composition of the stories is very complex and few of the trees present any striking peculiarities, while smaller trees of a higher story always occur in a lower story and between the different stories. In addition to the above stories of trees there is a ground cover composed largely of seed- lings of tree species and climbing palms (rattans), but also con- taining numerous herbs and shrubs. The foliage is so dense that when one walks through the forest most of the large trees are completely hidden from view. Plate II, fig. 1, shows an area from which the undergrowth and small trees have been removed. It will be seen that large trees are much more numerous than would be suspected from an examina- tion of Plate I, fig. 2, which shows a virgin area where there are probably as many trees as in the area shown in Plate I], fig. 1. For a fuller discussion of this forest, see an article by Brown and Matthews.® The soil samples in the dipterocarp forest were obtained near the top of a ridge at an altitude of about 300 meters. ° Op. cit. xra,5 Brown and Argiielles: Soils on Mount Maquiling 995 MIDMOUNTAIN FOREST The forest occurring above the dipterocarp forest is much smaller than the latter and is composed of only two stories of trees (Plate II, fig. 2). This forest extends upward to an elevation of approximately 900 meters. The soil samples con- sidered in this paper were obtained on the top of a broad ridge at an elevation of about 730 meters. In this locality the trees of the top story reach a height of about 18 meters. The forest is much more open than the dipterocarp forest (Plate III, fig. 1). The most prominent large tree in it is Quercus solariana (cata- ban), while Cratoxylon celebicum (guyong guyong), which is somewhat smaller, is more numerous. The average height of the second story is about 6 or 8 meters. The most numerous species are Oreocnide trinervis (malatuba), Neolitsia villosa, and Sauraunia barnsti. The ground cover consists largely of ferns and other herbs, of which species of Hlatostema are the most prominent. The herbs in this region require much moister conditions than those in the dipterocarp forest. MOSSY FOREST The top of the mountain is in the cloud belt and is covered with an elfin wood or mossy forest. This type is composed of only one story and is characterized by having the trunks of the trees thickly covered by mosses, mosslike plants, and other epi- phytes. The ground cover is composed almost entirely of herbs, among which Strobilanthus plurifomis, ferns, and species of Selaginella are the most prominent. The most striking peculiar- ity of the trees is a tendency to produce a large number of aérial roots, which grow to such a size as to form, as far as function goes, secondary trunks (Plate III, fig. 1). The soil samples from this forest were taken within a few meters of the top of the mountain. From the above description it will be seen that the chief changes caused by increased altitude, which might conceivably be connected with soil conditions, are a dwarfing of the vegetation as higher elevations are reached and the occurrence in the ground cover of plants requiring moister conditions at high than at low altitudes. In order to see whether or not these changes could be connected with soil conditions, we have made a chemical and physical analysis of soil samples taken at a depth of 20 centimeters in the four different types of vegetation and have determined the water content of the soils, for different weeks 226 The Philippine Journal of Science 1917 of the year, in the same locations at depths of 10, 20, and 30 centimeters. CHEMICAL COMPOSITION In Table I are given chemical analyses of the soils from the different altitudes. TABLE I.—Chemical analyses of soils from Mount Maquiling, Laguna Province, Luzon. [Water-free basis, numbers give percentages.] Source of soil. Grass- Diptero a ae ‘| Mossy lan eee tain forest. forest TORS ON ISTICION See ee ree eee ee ne see ee 10.32 10. 08 13.56 29. 97 Nitrogen (Ne) Meo5... SARE ee SEP a see 0. 150 0. 187 0.199 0. 644 Phosphoricianhbydride (Por) ease a. eee ee 0.278 0. 106 0.104 | 0,112 Hime: (CaO) 22s. .ce Se etree ee eee ee lel OLR 1.01 0.31 0.52 Mapnesia' (MgO) \i2 = velar Oe ane ee ee ee 0. 62 0.61 0.49 0.79 Potashh(Ks@)) 2 2) etl ek eee ES ahs ees 0. 294 0. 241 0. 189 0.170 Sada (Na2O) oh eee ee Se eee 0.37 0. 44 0. 53 0.34 Hume sh 328682558 S ee eee ae ee eee 1.36 1.06 1.71 8. 06 Soil acidity (CaCOs equivalent) ____.____________--_--_-- 0.0069! 0.0100 | 0.0094} 0.0082 It will be seen that none of the soils are strikingly deficient in any important element and none can be considered as acid. The amount of nitrogen and humus is greatest in the mossy forest, where the vegetation is most dwarfed. It is to be noted that the smallest amount of nitrogen and humus is shown by the sample from the tall dipterocarp forest. The chemical analyses of the soil, as shown in Table I, do not indicate that there is any connection between the chemical composition of the soil and the dwarfing of the vegetation as higher elevations are reached. PHYSICAL COMPOSITION The physical analyses of the soils from the different types of vegetation are given in Table II. There is nothing in these analyses to indicate that all of the soils should not produce a luxuriant type of vegetation. If any distinction can be made, it seems that the soil of the mossy forest should be the best, as this is a fine sandy loam, while the soil of the dipterocarp forest and grassland is a loamy clay. xu,4,5 Brown and Argiielles: Soils on Mount Maquiling 227 TABLE II.—Mechanical analyses of soils from Mount Maquiling, Laguna Province, Luzon. (Water-free basis, numbers give percentages.] Classifieation of soil. Source of soil. Diameter of particles. Dip- Mid- Grass-| ter- | moun-| Mossy land. | ocarp tain | forest. , forest. | forest. mm. QV er 2esseed wot estes ewes nil nil nil nil 2to Ves ees sea 2 ee 0.9 0.5 0.7 nil oes AO tOONG ee eseeee ea ea eee 2.2 1.3 0.9 5.9 ae Osbito Ol 2b neeean ee naaaeete 5.4 | 4.5 4.1] 23.3 Se Os cur LO) On lObseee sone oe 12.5 9.8 8.8 | 31.4 Bee TOs Oita Os Ubarmeneene cena seen 10.8 | 7.8 12.3 | 13.2 Seah ONObito OXON ae tone eee ee oe 13.6 13.5 4.9) 11.2 Bes OxOUtel0s O02 en as Soo eo Es 36.5 | 41.7 39.4 9.4 wea |ess) thamOs0022-2sces- acces 5.6 19.0 | 21.4 | 29.6 MOISTURE CONTENT In Tables III to VI is shown the percentage of moisture in the soil at the different altitudes. TABLE IIJ.—Percentage of soil moisture in grassland (altitude 100 meters) at base of Mount Maquiling, Laguna Province, Luzon. = Depth in centi- Depth in centi- meters. meters. Date. Date. 10. | 20. | 30. 10 |» 30. 1912. 1918—Cont. December 6 -----.---------- 30.3 | 34.5 | 38.6 || May CRE A eae 27.6 | 27.5 | 27.8 1S ee eae Ne 34.1 | 34.7 | 35.5 Siem aA a 27.0 | 26.8 | 27.1 20 eet eee ks 35.6 | 34.6 | 35.3 1 Geers oer 33.8 | 28.7 | 30.3 (| ee ee 36.9 | 35.7 | 35.6 opin Maen se 34.3 | 34.8! 32.8 (a9: SD arene A 33.3 | 32.7 | 38.1 June Gees eee ley sch de 30.8 | 30.3 | 31.9 Fanuary So osee 38.5 | 39.4 | 39.1 an eioiltsesultoaig 10 ---------------- 38.7 | 36.5 | 37.6 || yay fora eetiaraa 1) 40.9 | 38.9 | 35.1 Agee ener ans 34.1 | 38.1 | 39.8 op as ailanalian G 24 ---------------- 87.6 | 36.4 | 87.6 || auoust 1.-.____...____! 35.8 | 34.8 | 35.7 Bier suet hl med 34.2 | 33.4 | 38.3 pelacie Bebruary) Veo tee 30.3 | 30.4 | 31.5 abe se 1a te eR 0) 33.2 | 34.6 | 35.5 35.1 eis Dips $)_Pie) the 35.8 | 33.6 | 33.0 86.8 ae SRL aa | 35.6 | 34.6 | 33.6 MWA a March eaten aig 8S | 35.6 | $4.8 | 38.5 35.8 ane B2sAN 88-81 October’); Bee 36.6 | 37.8 | 36.9 25.6 | 28.3 DAMN ery a 35.1 | 34.8 | 98.4 23.8 | 28.8 || November’ 7.---.---------- 33,6 | 32.7 | 31.7 April 29.3 | 28.6 14 81.8 |'85.4 |/94.3 Kare 27.7 Cy Ae les 41.3 | 88.7 | 42.6 26.5 | 27.1 Taw oo 39.1 | 37.1 | 38.1 30.6 | 33.4 | 223 The Philippine Journal of Science 1917 One of the most striking peculiarities about these tables is the similarity in the amount of moisture in any given soil at different depths. This is apparently due to the fact that the dense covering of the vegetation prevents the surface soil from drying out at a much more rapid rate than the deeper layers. The average percentage by months of the moisture in the soil at a depth of 20 centimeters, at elevations of 90, 350, and 725 meters, is shown graphically in fig. 1. Mov. Dec. Jon. ‘feb Mor Apr May June July Aug. Sept Oct. Nov. Dec vf Mid 4 °) \Altitudel 129 (egal a | ; aa + = ° 2 i 2 » | 2 / iat ee s / Ae . ety ‘ed ° leo g 56} Gm Ice 4 8 at forest_ ff & 8 ™ ae 350 5 AY a & 40 ah aI & $ ee f i < | ye as Ba | OP meters] | 4s | 0 : nn oes — 36 aa rar Fic. 1. Average percentage, by months, of moisture in the soil at a depth of 20 centi- meters at different elevations on Mount Maquiling. The lowest moisture content is shown by the grassland at the base of Mount Maquiling (Table III). Here, however, the growth of trees is much more rapid than at any of the higher elevations. This is very probably not due at all to soil con- ditions, but to the greater illumination of the individual trees and the rapid rate of growth characteristic of the second-growth species. At a depth of 10 centimeters the greatest variation of water content is from 41.3 per cent on November 21 to 24.1 per cent on April 11. The soil samples taken in different places in a very limited area on the same day would, of course, show varia- xu,4,5 Brown and Argiielles: Soils on Mount Maquiling 229 tions in water content. Some of the variations seen in Table III are undoubtedly due to the selection of individual samples and are not connected with any change in the water content of the soil as a whole. It is probable that this source of error is responsible for the extreme variations noted in the water con- tent given in Table III. The soil at a depth of 10 centimeters gives an average water content for November of 38 per cent and for April of 27 per cent. These figures would probably represent the extreme variations for the region as a whole more accurately than the highest and lowest figure shown in Table III. The figures for April show that even in the dry season the soil contains considerable moisture. The lower moisture content combined with the dry atmospheric conditions at this season are, however, sufficient to affect the plants very adversely. Many of the second-growth tree species loose their leaves completely for longer or shorter periods, and all of them show a much lower rate of growth during the dry season than at other times of the year. TABLE IV.—Percentage of moisture in soil in dipterocarp forest (altitude 800 meters) on Mount Maquiling, Laguna Province. | { Depth incenti- | | Depth in centi- ] meters. meters. Date. Date. A ti 10. | 20. | 30. 10. | 20. | 30. | din 1912. 1913—Cont. i November 162252. ese 57.4 | 57.1 | 56.6 || May PEED Ld eNaie elles 44.2 | 46.2 | 48.1 Dee Se ost! 57.2 | 59.5 | 66.5 GUS an sete 45.1 | 42.9 | 42.4 DOME geal 57.2 | 57.8 | 58.6 Ge OT | 50.7 | 49.4 | 51.0 December 6 ___...---------- 55.2 | 57.8 | 56.5 30 Meena | 51.4 | 50.8 | 55.4 Tie, hae e 53.1 | 54.4 | 52.3 || June Gueteei nen 46.1 | 45.4 | 46.6 BO ease oe, 54.2 | 52.4 | 56.2 || 1B 23 bene pea 42.0 | 43.5 | 44.7 CH fe pte ere ee 60.4 | 54.6 | 54.5 ZO Re ede be) 64.8 | 51.7 | 54.4 1913 i July 1 ee eC ee 53.2 59.8 if 57.9 | Ce a asa em 56.1 | 57.3 | 59.4 January ae oe oe 65.5 | 54.7 | 57.0 | August iLL eee eS 52.4 | 52.9 | 50.0 10 wt en ne nnn 53. 8 52. 2 54. 2 | 8 eee eee ey 54, 8 56. 2 65. 1 aaa 51:2)| 41.2) ) 64-9) ya aad and oa 53.0 | 57.8 | 60.0 24 ---_-.------_--- 53.6 | 57.4 | 60.0 | Some ny ane 58.1 | 57.2 | 55.8 31 ---------.------ 54.6 | 54.4 | 56.3 | Cy WS wah ema 64.5 | 61.2 | 58.8 February 7 ---------------- 47.1 | 45.8 | 51.7 i September qb. 25-25) eee 55.4 | 53.9 | 51.2 14 wwe wn one eK - 47. 6 50. 5 53. 5 | 12 Rt EB ah ee 54. 8 53. 8 55. 1 21 -------------_-- 55.6 | 52.5 | 48.0 | Agee edu. ka 57.0 | 61.2 | 59.4 28 ------.--------- Bas Ae La ATW ctohen, Slee ee 55.4 | 57.7 | 56.1 March Ue ee 47.5 | 62.4 | 51.5 DA el | 56.1 | 54.8 | 54.4 14 _--------------- A OW AGH WAC Sin ovember (Tne) | 55.2 | 51.2 | 52.1 IS nes ed 39.0 | 45.0 | 50.3 | aL Apes tekcaal Vaca lea cl ee.6 : foeeceedbaaaes seas 40.6 | 44.1 | 48.8 | Be gee Ae 58.4 | 52.0 | 47.6 tee ee 42.4 | 41.4 | 44.5 || Bees. St 55.2 | 65.3 | 55.1 | TE ee geen aE ae el December 2.) 0 3 57.2 | 55.4 | 54.3 18 ----------_--_-- 52,1) 49.4 | 49.8 |) Ges eva eae 59.1 | 59.1 | 59.4 2 ---.------------ 42.1 | 47.6 | 44.8 | Die Gem sis Se | 51.2 | 48.1 | 50.8 230 The Philippine Journal of Science 1917 The soil of the dipterocarp forest contains considerably more water than that of the grassland. The greatest variation in moisture content at a depth of 10 centimeters is from 59.1 per cent on December 19 to 39 per cent on March 21. The latter figure appears to be high for a minimum water content at this depth, but during the dry season the effects of drought on the dipterocarp forest are very evident. The foliage is much less dense than at other seasons, while Parastaca plicata (bagtican lauan), the dominant tree, shows a greatly diminished rate of growth.’ The effect of drought in the dipterocarp forest is, however, not so marked as in the grassland. The percentages of moisture shown in Table V for the mid- mountain forest are considerably greater than those for the dipterocarp forest, and the variation is relatively less. TABLE V.—Percentage of moisture in soil in midmountain forest (altitude 730 meters) on Mount Maquiling, Laguna Province, Luzon. | | Depth in centi- | Depth in centi- meters. meters, Date. eneee es RGeueeee | PEE! Date. Nd oe so 10. | 20. | 30. 10. | 20. | 30. 1912. 1913—Cont. | November 162 a =- ee ae eeeee 82.9 | 73.7 76.8 May Bete. Fad 59.1 | 58.8 ; 62.0 a eee, Oe SA 68.2 | 71.2 | 70.3 10 e se mee 61.7 | 63.1 | 62.9 SO ee eho 73.5 | 72.3 | 77.7 ene SRN ye 59.2 | 67.8 | 65.2 December 7.-.--.---------s 75.0 | 78.1 | 77.8 i) eae at en i #8 62.9 | 55.2 aia ae Be rE 78.0 | 76.2 | 74.5 || June fe AL aS 2 3 ....| 64.9 | 68.6 | 65-7 Py ee Se 72.7 | 74.5 | 73.5 DE a aie Bee 58.9 | 60.6 | 62.0 Pere ios Went 79.0 | 78.1 | 76.8 Pye Mae, 69.1 | 68.3 | 70.1 aye | July 1g Nee en org) | eee 80.1 Pah emanate 70.7 | 71.0 | 78.7 January 11------.---------- 77.2 | 80.1 |------ Wiaprnkei aaa oa 71.9 | 74.5 | 73.4 18_-----.---.------]------ | 15.6 | 77.5 ORE Ny esr 70.8 | 77.6 | 70.5 25 ---------------- 76.8 |------ 86.2 So 67.8 | 72.7 | 71.7 BPebraarys da ree eee 70.2 | 73.6 | 74.7 Septem berion cee eel | eae 74.6 | 69.3 8.---------------- 69.1 | 72.8 | 73.5 | Powe mui. ie, a 68.2! 74.9 | 71.3 SY aca te ae Ay 70.5 | 74.7 | 76.4 | a ae haa aii = [Pot rad Briere ec L i 22. --- ~~~. ------ 73.7 | 69.7 | 72.01 October 4_-------------- 74.9 | 71.8 | 72.6 March iE Ae ae oe 74.6 73.1 | 75.6 Spee. Soe) 65.8 | 71.4 | 78.1 8. ---------------- 70.1 | 70.7 | 74.5 || November 1--------------- 64.3 | 64.6 | 66.9 11 aes cee 51.2 | 65.1 | 66.4 || Op Siar Terres 62.4 | 65.9 | 68.8 || April ice oS Sie 57.8 | 55.2 | 60.1 Eh MANE ey Bl Se 66.2 | 66.5 Gt te havea 64.4 | 68.8 | 69.5 In this region there were no marked effects of droughts during the dry season except on the epiphitic vegetation. The percent- age of moisture in the soil is very high, being between 70 and 80 ° Brown and Matthews, op. cit. xua.s Brown and Argiielles: Soils on Mount Maquiling 931 per cent for a large portion of the year. There is, however, no indication that this amount is excessive, as the soil is well drained. TABLE VI.— Percentage of moisture in soil in mossy forest (altitude 1,070 meters) at top of Mount Maquiling, Laguna Province, Luzon. | lbepthin centimeters. Depth in centimeters:| Date. = a ar as aa Date. aa | | Osun 20! el pS: 10. | 20. 30. | eed i | 1912. 1913—Cont. November 16___.-_.------ 258.1 | 190.5 | 246.7 || May TOS es ts 226.4 | 136.8 | 122.0 Deeds i G4 ot 251.5 | 167.5 | 121.1 | tics aide ag! 308.9 | 214.5 | 173.6 Owes Al igh! 305.0 | 312.4 | 129.5 || DA Wea We 224.8 | 185.4 | 173.6 December 7_.----------- 275.9 | 258.2 | 123.2 || 3 (Een ade ote 260.2 | 246.7 | 251.8 14____...-_---.] 291.0 | 188.1 | 180.5 || June Vine UseaEe 159.4 | 161.7 | 162.4 | Digs Stree | 284.5 | 852.8 | 232.0 of ee ne on ae 209.8 | 226.0 | 206.0 | 191%, Piece ae | bel staal ee | July 1 ete A ei aS i 137.2 | 255.0 | sanuary willy. o3.4-.1.-0 | 245.0 268.2 , 273.0 | August oleh a aby 237.7 | 211.8 | 231.8 if ee 178.6 | 149.5 | 362.3 |! pial iene 1 073.8 | 207.6 |........ Rebruary | esse -- = 130.5 | 234.3 | 305.8 fax beta oaee 104.2 | 197.7 ses ee Os Bie | 211.1 | 225.2 | 289.0 | it. WEP Sool qa. sl idsie Ap. -- 22-22 -2-=- 250.5 | 188.0 | 206.0 || soreset bea 218.3 | 199.7’) 142.8 Rieti Secs a j-------| 820.2 | 819.9 |) September 27.-.-..------ 238.0 | 257.1 |-------- March eet oe: eee | 281.8 ['256:0"| 255.51 October 4... Fea ie | 378.4 | space eee 257.2 | 198.8 | 198.6 fh eet REA 148.1 | 164.2 | 256.2 jee oan ee 221.2 | 264.9 | 232.1 || pig? obesity’ 159.9 | 806.5 | 247.9 eae ae ee | 257.2 || November 8---.-------- 185.7 | 186.1 | 302.0 | 29_----------- 306.3 | 114.6 |-_---.- tee 154.2 | 263.2 | 801.2 April AGES. HESS 167.4 88. 2 75.1 | FG pe ras Sees 247.3 | 203.6 | 256.5 | iow sezssccsbse 176.6 | 162.0 | 389.2 1) December) 62.4.-25.2--2 165.3 | 204.8 | 272.1 | | 1 Kee err er TEELG || Php The moisture content of the soil in the mossy forest (Table V1) is extremely high. There is only one week when the determina- tions show less than 100 per cent of moisture, and on this occasion this is true of only two of the three depths. Equally as striking as the high moisture content is the variation from week to week and at different depths on the same week. The different depths frequently show a variation of more than 100 per cent on the same day. The high moisture content is apparently connected with the large amount of organic matter found in this soil. The amount of organic matter apparently varies greatly in different situations, and the variations in the water content, shown in Table VI, are probably due more to the places in which the samples were taken than to any weekly change in the moisture content of the soil as a whole. The high moisture content shown by the soil in the mossy and the midmountain forests undoubtedly accounts for the fact 232 The Philippine Journal of Science that the ground covering is composed of plants requiring more moisture than those found in the dipterocarp forest. It does not seem probable, however, that the dwarfing of the vegetation is connected with this high water content. The great amount of water in the soil of the mossy forest is not due to heavy rains that would cause the soil to become leached out, as the rainfall here is about the same as it is in the place where the soil samples were taken in the dipterocarp forest and is con- siderably less than in the midmountain forest and in a large pro- portion of the dipterocarp forest. ‘The soil of the mossy forest is, moreover, well drained, so that it must be well aérated, and it has a springy consistency. The figures in Table I show less acidity in the soil of the mossy forest than in that of the dip- terocarp forest. There seems, therefore, to be no reason for considering the high moisture content of the soil as harmful. The moisture content of the soil of the midmountain forest would certainly not seem to be high enough to be deleterious to the vegetation. The fact that the trees in this situation are much smaller than those in the dipterocarp forest is probably due to the same factors that have resulted in the stunted vegetation on the top of the mountain, the difference being that these factors are more pronounced at the top. The above discussion indicates that the moisture contents of the soil should be as favorable at high as at low altitudes and so cannot be connected with the dwarfing of the vegetation as higher altitudes are reached. SUMMARY The natural vegetation of Mount Maquiling becomes more and more dwarfed as higher elevations are reached. There does not appear to be anything in the physical or mechanical composition of the soil or its moisture content which would account for this fact. The character of the plants in the ground cover varies accord- ing to the amount of moisture in the soil at different altitudes. ILLUSTRATIONS PLATE I Fic. 1. Growth of Saccharum spontaneusn, at an altitude of about 90 meters on Mount Maguiling. Photograph by Brown. 2. View in dipterocarp forest, Mount Maquiling, at an elevation of about 500 meters. The large tree in the center is an individual of Parashorea plicata in the first story, the smaller trees on the right are in the second story, while still smaller third-story species are scattered throughout the picture. The feathery leaves of the climbing palms (rattans) are the most conspicuous elements in the undergrowth. The density of the vegetation is very evident, the foliage of the undergrowth and lower stories being so dense that most of the large trees are completely hidden. Photograph by Brown. PLATE II Fic. 1. View in dipterocarp forest, Mount Maquiling, altitude about 300 meters. The undergrowth and all small trees have been removed. The clearing was done by the College of Agriculture for the purpose of planting coffee, and some of the trees removed were as much as a meter in diameter. In the forest shown in Plate I, fig. 2, there are probably as many trees as in the one shown in this picture, the difference in the number of trees seen in the pictures being due to the fact that in the former case the trees are hidden by the foliage, while in the latter they are in plainer view. Photograph by Brown. 2. View along a trail in the midmountain forest, Mount Maquiling, at an altitude of 740 meters. The vines that are prominent, particularly in the left of the picture, are species of Freycinetia. Fruits can be seen growing on the trunk of the large Ficus to the right. A comparison of this view with Plate I, fig. 2, will show that the midmountain forest is much more open than the dipterocarp forest. Photograph by Brown. PLATE III Fic. 1. View in midmountain forest, Mount Maquiling, altitude about 730 meters. This view shows the undergrowth and the open charac- ter of the midmountain forest even better than Plate II, fig. 2. Photograph by Brown. 2. Large aérial roots of a tree in the mossy forest on Mount Maquiling. Photograph by Brown. TEXT FIGURE Fic. 1. Average percentage, by months, of moisture in the soil at a depth of 20 centimeters at different elevations on Mount Maquiling. 233 ie eigen ae \2) aod sah oh" ot Pra het. ', ics tiie stan ‘a _ ‘ a) i) OE ; = t . es | es Ns yee Pia} vats cl Le ae £ Jey ad} me nade wal } ry . hil gy, pheihla | adlf hoade ) bien i, ee? ee paige ut’ Sages: aw f a>) yer Ile £NR Has ee Wa al. SR Lely es giv Cen dh Yeates ay ut ANE. Phalg yP Feu CNS) yA: ror vat At ee Brn. we T he suidl ein & i eeuent Preith, Skok Gd. SE A ateeaaier a tt a aA Lone Ohi? a RHE Maen ee atari, te went 2 ae oben "i 4 . “ Ree? 84) Ou Una) vay Seis sane ‘up f ttl Lerel s LI weygoiter an So ‘miguel fot wei feniton j i reag-viaghs PRE, eel ap aid Set Get coh . a lid? weeh Pe Lect eae: Ce ERS af Pe ba ST bey wid + ae? Ww i Ra. Witees ‘ a itd 7 he OA oie ag se, 4 ' itaase We iw = oes ht 2a CE a ‘thy ia | ooig tlt slgthewosiy Bananas aa Suan a Gulbis tent ot) (Wieden Phantasy seihts Bie San OTM et yagi ay a Sie, eleva v aetugt aor na wed sintht” ye fiml oAT Ae etter, Gh) “az +a ue abt tastak et : sath ely rit] val’ Save A aa Wp eet sw ks ey rita dad aarti nt fs) Kutiies ew ae tae wate SaeP ek eee at! ents t Pe ve rte we) Ta Pte ni! yi 4 roe it by ews pall ae Sitivhry., come id Awe 1: SE SU Ae Far tote DR aereys 2 Sitar att vcr ha piit Hing Yh bers ayaee (y) eA alpen b SP RAD ie tae agai § Ch GAR Alero bes Lites prod Ealn yl RR bart Deir eit sladnletie ig} aT hs e198 Pravyindiiny gil aalts erect abl” » nat ie , H"B) ued? eee: ve g¥ yok gee: ale els) | + Ope me Sy Fit Sa } 6 Sieh ay Tae i Si ha odie att y Ard 1) apa per 2 wv pags ce TAFT GER whP ii dave tans hy Ase tepaes Vd witb Serves 0, A Pe BOO Neda I da epatartrs | = BROWN AND ARGUELLES: SOILS ON MOUNT MAQUILING.] (Pum. Journ. Sctr., XII, A, No. 5. Fig. 1. Saccharum spontaneum on Mount Maquiling; altitude, 90 meters. Fig. 2. Dipterocarp forest, Mount Maquiling; elevation, 500 meters. , ; PLATE I, uN if ss AY a*s Wee se] ae es . «sat rE ee eel Mesore upsets LSTA y ay mene OA Gi sek A eS eee Scr., XII, A, No. (Pum. JourRN. Sorts ON Mount MAQUILING.] BROWN AND ARGUELLES: er eer See Mount Maquiling; Fig. 1. Dipterocarp forest with undergrowth and small trees removed , 300 meters. elevation , 740 meters. elevation Mount Maquiling; Trail in midmountain forest, Fig. 2. FLATE II rc (Puiu. Journ. Sci., XII, A, No. Sorts oN Mount MAQUILING.] BROWN AND ARGUELLES: 730 meters. , Mount Magquiling; elevation Midmountain forest Fig. 1. Mount Maquiling. , Fig. 2. Aérial roots of a tree in the mossy forest PLATE Ill A COMPARISON OF LINSEED OIL AND LUMBANG OILS AS PAINT VEHICLES ? By R. H. AGUILAR (From the Laboratory of General, Inorganic, and Physical Chemistry, Bureau of Science, Manila) ONE PLATE AND ONE TEXT FIGURE Because of its general adaptability to different kinds of paints, linseed oil has not been supplanted? on a commercial scale by any other oil. The lumbang oils are possible substitutes for linseed oil, and they have been much studied,’ but little has been reported concerning their behavior with different pigments or the quality of the resulting paints. It is, therefore, hoped that the following preliminary series of comparative tests on the proper- ties of linseed, lumbang bato, and lumbang banucalag oils may be of interest. Lumbang bato (Aleurites moluccana), a large tree belonging to the family Euphorbiacez, is common and widely distributed in the Philippines, occurring in most islands and provinces. It occurs both as a native and as a semicultivated tree and is locally abundant. The species is one of very wide geographic distribu- tion, extending from India through Malaya to Polynesia. It is commonly known as the candlenut tree, but has numerous local names in the various countries where it occurs. In Hawaii it is known as kukuwi. According to Richmond and Rosario‘ the seed yields from 60 to 65 per cent oil by extraction with carbon bisulphide, ether, or chloroform and 55 per cent by hydraulic expression at 500 kilo- grams per square centimeter. In the present work the yield of oil was 44 per cent (calculated on the weight of the kernels) by hydraulic expression at 310 kilograms per square centimeter. * Received for publication July, 1917. * Gardner, H. A., Paint Technology and Tests. McGraw-Hill Book Co., New York (1911), 2. “ * Wilcox, E. V., and Thomson, A. R., Bull. Hawaii Agr. Exp. Sta. (1918), 39. Brill, H. C., and Agcaoili, F., This Journal, Sec. A (1915), 10, 105-119. *Richmond, C. F., and Rosario, M. V., ibid., Sec. A (1907), 2, 441. 235 236 The Philippine Journal of Science 1917 Lumbang banucalag (Aleurites trisperma) is confined to the Philippine Islands. Though of wide geographic distribution in the Archipelago, extending from central Luzon to Mindanao, it is less common and much more local than is lumbang bato. The oil is darker colored and more viscous than lumbang bato oil. It is commonly supposed to cause skin eruptions on contact, but I have seen no foundation for this belief. I have handled the oil constantly in this work, but have suffered no inconvenience. The yield, calculated on the kernel weight, is about 43 per cent by hydraulic expression at 310 kilograms per square centimeter. Brill and Agcaoili ° found that the lumbang oils are comparable with linseed oil in drying quality of film and percentage change in weight when drying; also that they can be used as substitutes for tung, or Chinese wood, oil, the product of allied species of the same genus, Aleurites fordti and Aleurites cordata. EXPERIMENTAL PART The oils used in this series of tests have the constants noted in Table I. TABLE I.—Oil constants." Fresh lumbang. Raw lin- seed oil. Bato. | Banucalag. Specie gravity at Ibo CoS k. 22 ee eS ee 0.9345 0. 9252 0. 9368 Saponification; value .¢f-.. ts no Pa oe oe coe ee 189. 40 192. 95 197.74 | Todizre: value sae oa nae reper gee 183. 96 150. 36 145. 25 Acid value ce: O:IoN KOM tise nena seen eece= pe ene eee 0. 50 1.05 8.70 ® Analyzed by F. Agcaoili, chemist, Bureau of Science. All the tests included in this preliminary work have been carried on under ordinary Philippine laboratory conditions, that is to say, in diffused daylight, at a temperature of from 28° to 30° C., and at a. relative humidity of about 75 per cent. Drying test—The drying tests were made in the usual way by spreading a small amount of oil to uniform thickness on glass plates, each 6.35 by 8.89 centimeters (2.5 by 3.5 inches) in size. The oil films were placed in a glass case and were exposed to a dry atmosphere obtained by passing a slow current of air through sulphuric acid. The changes in weight and ap- pearance are shown in Table II and in fig. 1. "Op. cit. XII, A, 5 Aguilar: Linseed and Lumbang Oils Sw TABLE II.—Comparative drying tests with linseed and lumbang oils." | Day | when Maxi- maxi- . mum in- | mum in- ra Oils used. REEAtGnCreRSetin Condition of film. weight. | weight was attained. Per cent. 1 | Linseed, boiled commercial sam- 13. 85 1 | Perfectly dry, clear, and firm in ple. one day. 2 | Linseed, raw, of the best quality_ 12.18 4|Dry, clear, and firm between the fourth and the fifth day. 8; Lumbang bato, bottled six 11.20 2 | Dry, clear, and firm between the months. second and the third day, tacky at the end of twenty days. 4 | Lumbang bato, fresh__--.--_--_-- 11.03 4| Dry between the fourth and the sixth day. 5 | Lumbang banucalag, boiled ___-__- 8.30 2 | Dry and firm in two days. 6 | Lumbang banucalag, fresh ----- 8.92 4| Dry in four days, but slightly opaque. ® Average weight of oil taken was 0.1415 gram. The oil films were dry and firm about the time the maximum increase in weights was attained. Fig. 1 shows the similarity in the behavior of the three oils. The boiled and the aged oils dry much more rapidly than the fresh oils, and the curves of weight increase are almost straight lines from the origin to the maximum point. On the other hand, the fresh oils dry very slowly the first day, then more rapidly, until the maximum increase in weight is attained. Redman and others ® give 11.7 per cent as the maximum in- crease in weight for linseed oil at the end of the sixth day and 10.5 per cent for tung oil between the eighth and the ninth day. Lippert” gives 12.4 per cent as the maximum increase in weight for linseed oil. The lumbang oils are, therefore, similar in this respect to linseed and Chinese tung oil. Paint films.—The following methods for the preparation of paint films have been tested in the laboratory: 1. The mercury method consists in allowing a paint to spread on top of mercury and later removing the dried paint film by lifting it off the liquid metal. Films obtained in this manner °Redman, L. V., Weith, A. J., Brock, F. P., Journ. Ind. & Eng. Chem. (1913), 5, 630. ‘Lippert, W., Zeitschr. f. angew. Chem. (1898), 412. 150586——2 238 The Philippine Journal of Science 1917 are not uniform; they become thicker in the center than at the edges because of surface tension. 2. The amalgam method consists in painting over a piece of tin plate. After the paint is dry, it is scratched at a few points and drops of mercury are placed on the scratches. The mercury amalgamates with the tin, and the paint film can be lifted off the semiliquid amalgam. The quantity of tin and mer- cury needed, the necessity for using only unrusted tin plate, and the time required to remove the film from the tin militate against the usefulness of this method. Time in days. —— Tinseed oil boiled. -——— — Lumbang bato oi), 6 months old. —~-——— Lumbang banucalag oil boiled. | —------ Linseed oil, fresh. | eee —.Lumbang bato oil, fresh. se — Lumbong banucalog oil, fresh a as ca ee i Percentage gain in weight. Fic. 1. Comparative drying tests for linseed, lumbang bato, and lumbang banucalag oils. 3. Lipowitz or Wood’s metal can be also used. The metal is coated with the paint under examination. After the paint is dry, the metal is put on a smooth plate and gently warmed. At a temperature below its melting point (60°C.) the metal softens sufficiently to allow the stripping of the paint. Satisfactory paint films can be made in this way. This process is not well adapted to laboratory work because of the large amount of ex- pensive alloy required and the care necessary in removing a film. *Emsmann, D. H., in Brannt, W. T., Varnishes, Lacquers, Printing Inks and Sealing Waxes. H. C. Baird Co., Phila. (1893), 321. XII, A, 5 Aguilar: Linseed and Lumbang Oils 239 The most satisfactory results, however, were obtained by paint- ing over paper of fair quality, sized with some inert substance from which paint could readily be removed by soaking in warm water. Among the substances tried were library paste, agar- agar, sugar sirup, and glue. Of these, the use of paste or agar resulted in a shriveled film of low tensile strength. The use of sugar sirup ° was satisfactory, but since the glue method, as described by Gardner, '® was simpler and gave more uniform results, the latter was adopted for this work. The method of procedure was as follows: The paint was applied to the sized paper and allowed to dry. It was then removed by immersion in water at 40°C., washed off with fresh water to remove the glue, hung on a glass rod to dry, and placed in a suitable con- tainer to prevent the accumulation of dust and insects. Tensile strength and elasticity.—In testing the paint films, a modified Gardner-de Horvath?! film-testing machine was em- ployed. The apparatus is shown on Plate I. The pressure was measured by means of a mercury manom- eter. This was made self-registering by placing inside the manometer tube an indicator, which remained at the highest point reached by the mercury column. The stretch was recorded by means of an aluminium rod resting on the center of the film. This rod was in turn fastened to the short arm of a lever and so delicately counterpoised that it exerted no appreciable pressure, yet rose and fell with any movement of the film. As the long, or pointer, arm of the lever was ten times as long as the short arm, it is obvious that any movement of the film was transmitted tenfold to the pointer arm and could thus be estimated with a certain degree of accuracy. To study the behavior of oil films,’* precipitated silica passing through a 200-mesh sieve was incorporated with the oil in the proportion of 15 per cent silica by weight. The films were made of three coats of 2.5 grams of paint each, applied to 400 square centimeters of sized paper. Table III shows the effect of age upon the strength of films made from mixtures of linseed oil with lumbang bato oil in different proportions. * Labordere, P., and Anstett, F., Chem Eng. (1913), 17, 1. ~ Op, clita npewiile “ Gardner, op. cit., p. 79. “ Gardner, op. cit., p. 31. PAD The Philippine Journal of Science 1917 TABLE III.—Fffect of age upon the strength of oil-silica films. | Breaking strength of oil- | silica films in \Stretches in centi- terms of centi- | meters, after— meters of mer- Oil in mixture. cury, after— T days. | 60 days.| 7days. | 60 days. Linseed eRe een s/n DAE epee a 100} 20.0/ 126) 0.23) 0.89 DO aaa gee ace aa acaes (aa aaa ie i 16.4| 8.9] 0.25] 0.45 Gumbane tae esas. ea ee Og Jee ee 2 25 | | Linseed .----.-----.--------------.-------------------- 50 | 11.8 6.3| 0.26] 0.56 TRiimbanie ss tS eee ae ee ie lle ee ea 50 Linseed -----.-------------~----~-------. -------------- 25 | 10.0 4.2 ae 0.54 ([umbarigssteise ssl oee eee eS ag ORR 15 |} | Dose ee ee Bid oe pl 100 9.4 2.5] 0.22 | 0.66 The films after sixty days were tacky and soft and of greatly reduced tensile strength. To study the effect of age upon the strength of paint films prepared from active pigments, red lead was employed. The paints were prepared by incorporating 40 grams of red lead with 25 grams of oil, and the films were the same in weight as the oil- silica films previously described. Table IV shows the relation between the increase of strength and the age of the paint films. TABLE 1V.—Tensile strength of red lead paint films. moose pa A Breaking strength in terms of, : P eEntinictenslonimercrias | Stretches in centimeters. | P Per 5 a | Oils used. ‘cent. | Age of film in days. Age of film in days. | | Nie ee a | fie 40. 60. 90. | 120. as 40. | 60. | 90. | 120. | Hl = = ero) ee ! | Tingeed.o 2. = 2c ei eee | 100 | 18.9 | 32.4 | 35.4 | 37.5 | 34.5 | 0.25 | 0.24 | 0.22 | 0.18 | 0.18 | | | BMS soca cees snes aot: Bp je.1 | 23.6 | 27.2 | 28.6 | 27.1) 0.24 | 0.23 | 0.20 | 0.19 | 0.22 Lumbang bato -_.___.------ 50 | | | | Doves es sees 100 | 10.7 | 16.8 | 18.3 22.0 | 20.9 | 0.27 0.26 | 0.24 | 0.26 | 0.24 a Table IV shows that the paint films attained their maximum strength between the third and the fourth month and that then a gradual decrease followed. Further tests were conducted to compare the paint properties of lumbang banucalag with those of linseed oil and lumbang bato oil. Twenty-five grams of lumbang banucalag oil were mixed with 40 grams of red lead; the mixture became thick and pasty in fifteen minutes, a property by means of which it can be differen- tiated from lumbang bato, because the latter, very much like XII, A, 5 Aguilar: Linseed and Lumbang Oils 241 linseed oil, does not show this phenomenon. The paint made with lumbang banucalag oil and red lead, painted on a smooth surface, did not dry in twelve days, probably because a very thin layer of the exposed surface dried in a very short time, thus preventing the action of the atmosphere upon the underlying paint. This property makes banucalag undesirable as a paint vehicle when used alone. However, by mixing 1 part of lum- bang banucalag with from 1 to 3 parts of lumbang bato, a quick- drying and altogether satisfactory paint is obtained. Table V shows the variation in the tensile strength of paint films made from mixtures of lumbang oils. TABLE V.—Tensile strength of red lead paint films. rag avr wil Breaking strength in terms Stretches in centi-| of centimeters of | meters, after— No. Oilatased: meee mercury, after— General remarks. 10 30 60 10 30 60 days.| days.| days.| days. days.| days. bere = : poe | an eanseed o5) 2245222 2 100 | 26.3 | 34.0 | 38.0 | 0.27 | 0.26 | 0.29| Film was dry in 36 hours. Appearance | good. 2 | Lumbang bato--_-_--__- 100 | 10.8 | 17.4 | 20.5 | 0.25 | 0.28 | 0.29 | Film was dry in 48 hours. Appearance i | | | good. 3 woo. peer 90 fli0.2 | 15.7 | 15.5 | 0.25 | 0.24/ 0.24] Do. | Lumbang banucalag _ 10 || 4 eae bate“ pe |12.4 17.6 | 17.1 | 0.32 | 0.31 | 0.26 | Film was dry in 24 Lumbang banucalag _| 25 | | \fuhoure’ A Dpeatnte i | good. ; ae Date ree ao |r2.4 | 18.0 | 18.4 | 0.30 | 0.35| 0.88) Do. Lumbang banucalag _ 50 | I | | 6 feats bato----.--- 25 |l16.1 | 20.2 | 21.2 | 0.25 | 0.22 | 0.21 | Film was not dry in 6 Lumbang banucalag _| 75 || davsuunhetmcnee | rete was dull. Paint ; | dried into a paste in | | | the container in a | short time. 7 Seer bato.--.---- | 10 l14,2 | 22.3 | 22.4 |'0.24 | 0.27 | 0.25 | Film was not dry in 9 | Lumbang banucalag _| 90 | | desce, Wie Smee | | | wasalsodull. Paint | dried into a paste in | the container in a | “| short time. The above results indicate that the mixtures of lumbang oils attain their maximum strength more quickly than either linseed or lumbang bato. Judging from the general behavior and ap- pearance of the paints, mixtures 4 and 5, that is, mixtures with lumbang banucalag containing 50 to 75 per cent lumbang bato, 942 The Philippine Journal of Science 1917 will be the most desirable for a red lead paint. With these mixtures, the resulting paint does not set as in the case of lin- seed ** or lumbang bato oils; it does not dry into a paste in the container as in the case of mixtures 6 and 7; and a better paint is obtained than can be secured with linseed or lumbang bato oils alone. Movwsture-excluding property.—To determine the moisture- excluding property of films, pieces of suitable size and shape were fastened with Canada balsam over the mouths of 200 cubic centimeter bottles containing drying agents. One set of bottles was half filled with concentrated sulphuric acid, another set with calcium chloride. The test pieces were cut from the same films as those whose tensile strength was recorded in Table IV. The moisture-excluding property of linseed and lumbang oils as determined by the increase in weight of the bottles of drying agent is shown in Table VI. TABLE VI.—Moisture experiment. [Numbers express percentage gain in weight. The calculations were based on the original weights of concentrated sulphuric acid and calcium chloride.] Number of days. | Oils used. Res Absorbent. ae 5 10. 40. hinseed wi- 8-26 4 oo ee | 100 | Concentracted H2SO4 _________- 0.24 0.45 | 1.67 Diese Fae a2 os eecbe= sts BOH bs adoi. ate om tee ecseecnes 0.37| 0.69! 2.58 Lombang ie 22 4 eee 50 || Dos lk ee eee AON esses GO scored A Ie 0.42} 0.81] 3.03 | hinseedt 22.22). = ee 100}; CaG@loe ? f 4 ! . a ieaaaitt! : eas t a iy a y Af pe? i% ] tae ; 44h) 44 % a a - : nw / ‘ te ; ‘ a C Bate permet Sa ¢ 1 44 en bat peg oe ry ite SERS ar ft ut 9 ce | Neat avodE: 3 hpab asi wet MEN PMR A Ts bear ih hee 4 We fiat a opty oy Bet Wiesel we vd Sha eg he 4 ‘Whi b > ¢ say ee ae — _ * ILLUSTRATIONS LA TE I. Modified Gardner-de Horvath apparatus used in testing paint’ of TEXT FIGURE ; ia . Drying rate of linseed and lumbang oils. 245 <= wy , ae a i] s~ Were / ‘ous ‘i oa ae oe ey Raat Pine 4, Fl e | f us Madea Oe pee ih | : Baceel ty Te : hy ren vot floc. telbiwtee! AGUILAR, R. H., LINSEED AND LUMBANG OILS.] (Pum. Journ. Scr., XII, A, No. 5 PLATE I, MODIFIED GARDNER-DE HORVATH APPARATUS. THE CRATER LAKE OF TAAL VOLCANO! By GEORGE W. HEISE (From the Laboratory of General, Inorganic, and Physical Chemistry, Bureau of Science, Manila) ONE PLATE AND ONE TEXT FIGURE Previous to 1911 Taal was an active volcano, which had erupt- ed frequently during historic times. The last and, as far as known, the greatest eruption occurred in January, 1911. An area of approximately 230 square kilometers was affected with de- vastating violence,(7) and over 1,800 people were killed. Since that time the volcano has been practically inactive. The following description of the volcano was published by Adams(1) about a year before the eruption: Taal volcano is situated on an island in Taal or Bombon Lake. The island, on which are found a number of extinct cinder cones and the active crater, has been built near the center of the lake by late volcanic activity. * * * The main crater which is situated near the center is usually referred to as Taal voleano. It is approximately circular in form. The southwestern border of the crater rim rises to an elevation of 320 meters, which is the highest point on the island. The lowest points on the rim are about 130 to 150 meters in elevation. The lowest points on the floor of the crater are about on a level with the water of Taal ake Ft * Two lakes lie within this crater. They are usually called the yellow lake and the green lake. During the rainy season there is a third tem- porary red lake. The yellow lake receives the natural drainage of the crater. It appears to be shallow and is hot, but does not boil. The green lake gives off steam from its surface and near its southern border boils violently as if over a vent. A circular crater is located to the south of the green lake. On its floor there are several boiling mud spots from which but little vapor rises. On the south border of the yellow lake there is a cone, called the red cone, because of the color of its crater. It is broken down on the south side and drains around its eastern base into the yellow lake. A vent from which steam issues with great force occurs on its northern outer base. The yellow lake now extends to this vent but formerly was separated from it by a narrow isthmus. There is a remnant of an older, large crater rim which forms a crescentic ridge rising southeast of the yellow lake and curving around to the south of the green lake, passing between the green lake and the crater with the mud spots. Plate I, fig. 1, is from a photograph of the crater that was taken before the 1911 eruption. 1 Received for publication June 9, 1917. 247 YAR The Philippine Journal of Science 1917 A peculiar feature of Taal Volcano is the fact that the main floor of the crater before the eruption was very nearly at sea level and that, owing to the ejection of much material during the eruption, the crater floor is now much lower. The volcano was little altered in outward appearance in the eruption of 1911, but the crater proper was greatly changed. According to the description by Pratt(7)— The absence of vegetation and the smooth drifted surface of the ash covering which is almost white in the sunlight, give the island an appear- ance of a vast snow heap. The crater rim is unbroken and save for minor fissures and cracks is intact. * * * The interior of the crater has been transformed. * * * The well- known Green Lake and Yellow Lake, which were small bodies of water, one of which (Yellow Lake) was quite shallow, referred to in descriptions of Taal since earliest historic times, are gone. In the position of the former Green Lake there is a new one, the water of which appears milky- white, due to suspended solid matter. The level of this lake was on February 17 approximately 70 meters below that of the sea. Green Lake had stood 5 meters above sea level. Two streams of hot water, the combined flow of which was estimated at 100 to 150 cubic meters per minute, were pouring into the lake. These streams came out of the crater walls about 50 meters above the lake level, seeping from just over a layer of fine-grained, impervious, bedded tuff. On the west shore of the lake a conical rock 50 to 70 meters in diameter rose to a height of 115 meters above the lake level. The upper 50 meters of this natural obelisk appeared to be bedded tuff, but the lower portion is massive basalt. A week later, the streams pouring into the crater lake had increased both in volume and in number, and the lake itself had risen apparently about 5 meters. * * * : Although hot and heavily mineralized, the water which is flowing into the new crater probably is seepage from Lake Bombon through the crater walls. Since Lake Bombon stands a few meters above sea level, the new crater lake will probably rise in time to about sea level. A comparison of the old and new craters is shown in fig. 1. As predicted, the water entering the crater formed a single ~ new lake, leaving no trace of the small lakes previously present (Plate I, fig. 2). This new lake, which is over a kilometer in width and at least 70 meters deep, has no visible inlet nor outlet. The following description was written by Gates,(6) in 1914: It [the crater] is about 2.3 kilometers long and 1.7 kilometers wide at the top. More than half of the bottom is occupied by a lake, whose elevation is about 2.5 meters above sea level, the same as that of the surrounding Lake Bombon. The water of the crater lake is clear, although dark colored, and salty. Its temperature decreased from about 37° C. in October, 1913, to about 32° in April, 1914. Swimming in it, although much like salt water bathing, was of course more exciting. Very little steam, if any, arose from the lake in either October or December, 1913, but in April, 1914, some steam was noticed arising from a few places along the shore of the lake, as well as from small vents in the north crater wall, both 249 Crater Lake of Taal Heise XI, A, 5 “uoIZdNIe [IG 94} 19}Je pue o1OJoq 19}B10 JO SUOL}JIBS SSOID posodulliadng “{[ “Oly WGI LI 924 2407 214M JOA2] DS -~-"3y907 MO/J/OA~ ~~~ ~~~ /2A07 b2S =e ee ‘wOte Siz $201 0 ‘A212°W SO a\e0S YOO/f J2JOID MBU SMOYS BUI/ PI/OS JOO/f J2}JO4D pjO SMOYS d2UI/ P2}30C7 ONWIDIOA IWVL 40 V3LvVYD 3HL 4O NOILD3S SSOUd LS 3IMHLNOS-1SWASHLYON 950 The Philippine Journal of Science 1917 inside and outside the crater. From certain points on the crater rim sulphurous odors are noticeable, but none were detected in the bottom of the crater. Steep precipitous walls formed the boundary of the crater on all sides. At the foot of the walls, especially on the east side, large quantities of ash and mud have been washed down and have accumulated. The crater rim is highest on the south and north sides with altitudes of 304 and 230 meters, respectively. Nearly all of the west side is low, the minimum elevation being about 95 meters. There are other low points on the east side. The above description holds very well for the conditions in the crater at the present time. There is a faint “sulphurous” smell at various points, due to mineral decomposition, and there are a number of small steam vents, principally on the north crater wall and at the west shore of the lake. Most of these vents were not readily accessible at the time the crater was visited, but on the northwest shore there were some very small openings, from which faint wisps of steam issued, and places where the sand, under water, was hot to the touch. As evidence of the insignificance of the present activity, it may be mentioned that the temperature of the lake was about 30° C., which is only a few degrees above that of ordinary surface waters in the Luzon lowlands. There are also a few steam vents at various points on the outer slope of the volcano,-and there is at least one under water, on the northern shore of the island. These, too, are insignificant. The presence of steam vents under water has given rise to the belief that there are hot springs at various points. So far as could be determined, there is no foundation for this belief. Crystals of calcium sulphate, of iron salts, and of sulphur are found on the walls and floor of the crater, the first being abun- dant, the last very rare. Calcium sulphate is very plentiful, especially near the shore of the crater lake, where it has ap- parently been deposited from the water in large sheets a half centimeter in thickness. Analyses of the waters of the crater previous to the 1911 eruption have been published by Centeno, in 1885,(4) and by Bacon, in 1906(2) and 1907.(3) The analysis of a sample of water from the stream flowing into the crater soon after the eruption was published by Cox. (5) Bacon(4) made qualitative tests for radioactivity in the waters and their sediments and found that the water and sedi- ment from the old “green lake’ were very feebly active, the other waters and sediments showing no activity. Wright and Heise(8) were unable to detect the presence of radium in the water of the present crater lake. XII, A, 5 Heise: Crater Lake of Taal 251 The results of the most recent analyses of samples taken by me in February and April, 1917, are given in Table I, coupled, for comparison, with the older analyses. The analysis of the water from Lake Bombon is also shown. A comparison of the above analyses shows that the crater waters became progressively more salty before the eruption; that immediately after the eruption, as might be expected, the water entering the crater was much less highly mineralized; and that the salt concentration has greatly increased since that time. The crater lake is at approximately the same level as Lake Bombon, that is, a few meters above sea level, and must be over 70 meters deep. There are no indications of any springs, or of ingress of water other than that which would normally occur in an excavation extending below the water table. The crater is, in effect, a huge basin exposed to insolation. There is, however, a large volume of water added to the lake through the rainfall, which, in this region, averages about 1,900 millimeters (75 inches) per year. The rainwater, running down the inner slope of the crater and into the lake, leaches the soluble salts from the volcanic ejecta forming the crater walls, increasing the amount of salts in the water; the intense tropical sunlight stimulates evaporation. Thus the lake water becomes more concentrated. This alternate addition of salt and evaporation of water is sufficient to account for the increasing concentration of the lake water. The quantity of soluble salts in the soil of the volcano may be inferred from the fact that large areas on the outer slopes are still practically unvegetated, except for occasional tufts of coarse grass, and that the inside of the crater is barren, except in isolated places. On the outer slope of the volcano, the soil, 5 to 20 centimeters below the surface, still shows, six years after the eruption, large quantities of soluble matter. Analyses of the water-soluble constituents of two soil samples—one from a typical unvegetated area on the west slope of the volcano and one from a typical grass area from the west shore of the island— are given in Table II. For comparison, two analyses(5) of the water-soluble material in fine ash and ejecta, collected soon after the eruption, are shown. 252 The Philippine Journal of Science 1917 TABLE I.—Analyses of [Results expressed as grams per Year. ‘ 1885 1885 1906 1906 Authority 2255533 4-2 ee eee oe Centeno™) ___| Centeno'4) ___| Bacon®) _____ Bacon) _____ Source scc825oi ee ae oe Se ae Yellow Lake4| Green Lake#_| Green Lake. | Yellow Lake_ Color: 225 eet 8s fa ea ee nie Green-__-_----- Yellow_---_-- | Specific gravity at 15° C_________.___- Se OLE em eee ee | T3062. A> ile TO Tose Acidity: 22 <2 cee sae ee | ae 2 gee eee | ae ee 1d28 Na2e-- 2:08 1Nesseee Acidity calculated as HeSO4.________- ONIGIDSS 2 esate eee ee GS14ib sese24 10.286... =222 Acidity calculated as-HCl___...-.._--|_--.-------___- 05894 ees AIGHD = Eseccs TSU co: eee Total :solids;filterediwater--)s2- ote |e en ee | ea eee 15. 8678_.-_-.- 25. 7235. ------ Total solids, unfiltered water_________ 2h698R ce se 4-2 G,0022 bese ceus Lbs 9812 sees 80. 8175. ..--.- Sediment (by difference) _______ Waa Eee a he Sa Sake hee 0. 0634______- 4. 5940__--_- Silica (SiO2)te 22220: es ie ete 0.0640_______- OK0740--2 sees o)sus2. ope bea cade ee ee eee Iron‘and aluminiumjoxides (WeoOsd: he 22 se eee ee ee ee ee Al20s). fron(Be) (total) ates ee ee Iron (ferrous) ___ Magnesium (Mg) Sodium (Na) Potassium. (Ki)! 12 325 eee A Hsi2 a a On1S21e as 0504182 220552) \ON0b14Ese= See Chloridés(C)) 22226 ee ee AORTA eee ee 3.4596_______- (Soba 112760222228 Bromides (Br) 2: 2.o-¢- 3) 23225 See A Se I es he ahem | Todides. (U)i22 ne ese eee | em ld eae ce | en | Sulphatesi(S Os) Mes eee eee OF41225e2-2 OFA1862 S22 222 4. 18038__....- 5. 6768_------ Phosphates (POs) eae caee- ee ee 050896222553 (QXOb1 bee eae (OX027BSeeeeee O}O89122_5522 Logs on‘evaporating; toitotalsolids).(2))| ce seo oe ea ree ee ene | ee Lithium iBorates!:(BO2)- 22 ere ee ee Arsenates (AsO«) ® Analytical results are given as recalculated by Bacon. (*) > Per cent. ¢ Analyzed by J. Gonzalez Nunez, chemist, Bureau of Science. 4 Normal carbonate (as NasCQ3), 24; bicarbonates (as HCO3), 150. XI, A, 5 Heise: Crater Lake of Taal waters from Taal Volcano. 100 cubic centimeters except as noted.] | Year. 1907 1907 1907 1911 Bacon® __._____ Bacon® _______. Bacon'®) ______| Cox) meee nennn Boiling crater | Green pool, | Green Lake_-_| Streum ------- lake. north of boil- | ing lake. Light grayish | Green --..------ Green ____---- Millegee ee 90 0. 7622 b 0.2813 | 0.0318» 0.7419b 0.0125» 4.7512 b 1917 0.9210 0. 8367 b 0. 0843 b 0. 8978 b 0. 2082 b 0. 4343 b 0. 7192 b 0. 0048 b 1.34466 1.19605 0. 1486 b 2.0927 b 0.1328 b 0.1514b 2.3246 b 0.0104 b 10. 9312 b © Determined turbidimetrically. t Determined by evaporation with hydrofluoric acid. £ Loss on ignition. 150586——3 253 1917 Lake Bom- bon (parts per mil- lion).4 Nil. Nil. 0. 14. 0. 95. 64. 50. * 580. 254 The Philippine Journal of Science TABLE I].—Analyses of water-soluble constituents of Taal ejecta and soils. [Numbers give percentaare by bho a of air-dried sample.] oe Je = a: a = 1911 1917 | | Soil from Ash.'4) |Ejecta. «s) | tated ae area. SUSE Silica (SiQ) Be acc eect eee wae eee cane ee eee ene 0. 82 0.95 0.12 0.03 | Iron and aluminium oxides (R2Os) ----------------------- 0.01 | trace 0.03 nil ime (CaO) 2222222 = Sosa cocks assan nemo peecanesesassemnes 0.16 0.32 8.81 0. 04 Maonesia:(MeO)) 255262. 6 2 sn he eee Soe esae none none trace trace Soda (NaeO) aa0 22 252 oe aso coe oe eccem een osensence 1.51 2.08 |.---2---=-)..-25eeee Potash’ (B2O)) 228 Se. seen so a cee ea sees 1.34 1 ener ee Manganereloxide (Mns04): -.- 5225s. se enone ome oe trace trace’ .|...-.2<-=- fees Sulphuric anhydride (SOs) ..-_-_-.-.--------------.------ 0.30 0. 60 4.33 0.11 Phosphoric anhydride (P20s) -----.---------. ------------ none none .|_-=~=--5=-/becebeneee Chiorme((G)) \s3 ee cate een cee eee 0.74 0.95 0.03 0. 02 Acidity: (intermpiot CaCOs)! =: 5... 57 epee ee seen cee |Eetee eee se Se eee 0.16 0.04 Totalisoluble:material <4 -. 2-2 5-0- Senne ede eee meee leeccarcca 8.75 0.88 Apparently the two sets of analyses are not strictly com- . parable because of the length of time between them and because of the probability that somewhat different materials were tested. It is significant, however, that the amounts of chlorides, that is, of the more soluble substances, are present in much smaller quantities in the 1917 samples than in those of 1911, indicating the extent to which leaching has taken place. Sodium and potas- sium, though not quantitatively determined in the later analyses, could not have been present as more than traces. The difference between the two 1917 analyses is of interest and furnishes at least a partial explanation for the differences in vegetation on different portions of the island. The acidity and the high soluble salt content, over six years after the eruption, indicate that a still greater salt concentration in the crater lake may be expected. REFERENCES . ADAMS, G. I. Geologic reconnaissance of southwestern Luzon, Phil. Journ. Sci., Sec. A (1910), 5, 57-116. . Bacon, R. F. The waters of the crater lakes of Taal Voleano, with a note on some phenomena of radioactivity, ibid. (1906), 1, 483-437. . IpbEM. The crater lakes of Taal Volcano, ibid., Sec. A (1907), 2, 115-127. . CENTENO, J. Estudio geologico del voleéan de Taal. Madrid (1885). . Cox, A. J. The composition of the fine ejecta and a few other inorganic factors of Taal Volcano, Phil. Journ. Sci., Sec. A (1911), 6, 93-97. . GATEes, F. C. The pioneer vegetation of Taal Volcano, ibid., Sec. C (1914), 9, 391-434, . Pratt, W. EK. The eruption of Taal Volcano, ibid., Sec. A (1911), 6 63-86. . WRIGHT, J. R., and HeIse, G.W. The radioactivity of ge waters, ibid., Sec. A (1917), 12), 145; ILLUSTRATIONS PLATE I Fic. 1. Crater of Taal Volcano from the southeast, March, 1907. Photo- graph by Bacon. 2. Panoramic view from the south rim-of the crater of Taal Volcano. Photograph by Cortez. TEXT FIGURE Fic. 1. Superimposed cross sections of crater before and after the 1911 eruption. : 255 te Me. oe. ar —— HEISE: THE CRATER LAKE OF TAAL VOL 3 (Puiu. Journ. Scr., XII, A, No. 5. Hetsh: THE CRATER LAKE or TAAL VoLcANo.] (Prin. Journ. Scr. XII, A, No. 5. Fig. 1. Crater of Taal Vcleano from the southeast, March, 1907. Fig. 2. Panoramic view from the south rim of the crater of Taal Volcano. PLATE I. i COMPOSITION OF BRICK AND MORTAR IN THE GREAT WALL OF CHINA * By J. C. Witt (From the Laboratory of General, Inorganic, and Physical Chemistry, Bureau of Science, Manila) ONE PLATE During a recent trip to northern China I visited the Great Wall at Shanhaikwan. At this point the wall is largely com- posed of gray brick laid with lime mortar. The bricks have a porous structure, somewhat resembling pumice, and are much larger than ordinary building bricks. They are so weak that pieces may be easily broken off with the fingers. The mortar is pure white, under the exposed surface, and is much stronger than the brick. The materials were of special interest to me because of recent research in ceramics and lime-burning at the Bureau of Science. A sample of each was taken and analyzed in this laboratory. The construction of the wall began in the third century before Christ, but was repaired eighteen centuries later. Therefore there was no means of knowing the age of the materials sampled, but apparently they were a part of the original structure. The general condition of the wall at this point is very good, as can be seen from Plate I, though near the top a number of the bricks are missing. Table I shows the analytical results. TABLE I.—Analysis of brick and mortar." | Determination. Brick. | Mortar. Pacts PaCE | | LL SET Orn Te UO ae es ceo ace ce Sener ee eee Sete a Seer mene n eee 0.10 43.88 | | SGD (GHG) pee ae a Sa re eee ee 73. 02 PAs be) Iron and aluminium oxides (Fe203,Al2Os)-_----------------------------------- 18. 96 0. 44 | Pilcinmioxide.(CaQ) hans aa nao are et ae See ee ae Re eee | 1.29 48.83 | MISPTIeRI MO XIGeu( MEO) = 22 eas e- = een eae eee ee oe J Pee Po 1.05 4.03 | | Sodium and potassium oxides (Na20, K20) -_---__----.----------------------- | 5.73 0.85 | a Analyzed by F. D. Reyes, inorganic chemist, Bureau of Science. The brick is said to have been dried in the sun only. This was confirmed in the laboratory tests, because on ignition the material becomes dark red. If it had been originally burned in a kiln, the appearance of the wall would have been consid- erably different, and the strength and durability would doubt- less have been much greater. Both the general appearance and the analysis of the mortar indicate that no sand was mixed with the lime. It is apparent also that the stone from which the lime was made was of good quality. * Received for publication May 16, 1917. LIA ey Meet “T iAtanaine k : 4 iS - AVE ~ AO vr Prey a it ya * Ly ’ warnqgay bien shangey wk Tors iteth ber eet ated ue (alr soeseey ay pani Voth She, ueiene . Age hay: ; _ ; t att Teidiaies TD acd D crite iss diaest wy % ; » viewisl dt thew edi-iciog ahi? 2A” wpyedineicade, ie a " 2 , “ aE 2 a eae 48) 700t : m i" Ye low Dea solana ailing jadwenmios. 2 rttorise - . . ted cdevwocor etg sod) avoivd> Reba viaditeas niiht * eH {ever { .»segad of! diiw Tk pastoud liste sch Yar ten 3 st Pine 4i bua sontice boeeges off tabs oie am oS ahd adits 4 it 6 sareeed ont id Jeeasiot Taiseas Tto Sau elaist ang ‘i int }o Yatra ant de gerieciet-arail Sae-sohrurros mt as b J ei : . "ss val “ “ ot y Iatoom aid &] pesviane DE Gioia? axa i5e5 Ta olf ea . : 4 £4 te , ae y : Z : i OT MIISO: DURF AT 11 Tee a liner ot 4 j OAS DEES AS, ; % 477 : . ay tal sapien od tsclaceh hattrass: wa sud wioMmse wl i Jar att to spa ati f ynlwound ¥5 2M oe ont aie 7] wihurite lartalio ad? to faints yoo yout chbaets ; aes iim en boon yee al trio atcit te flaw ond te oibaes ic - doitd of} to tdi ¢ dod edt teed dpuodt ener mort ; : atiuvet falivlage edt awodte I sidaT “acl a a ; “om yon live aie * vin Weel F RAT ; Zz ere At t sa a : , ; : “2 ~pa Gertie aie Py ~~ ~ OR “ a ee ee A hats are a NR ey i? ; : SAE veoten, pom : OE palo “ al? + tee Ors ‘shes fe, Se oe nee iw ; me . 3 a Bred A >" j ii Dare ; og 4 ea 2 ine ai hoe) : aval xteol, “Rideredal wal gt hind - ; : L «linia aaa bead a) YEO et ts ay aonabasel: lebih ) yen Big i ie Te iaetaan beyit nlf” it yay i ic Agence al han pis Gk as ; erg one aed TYE enue T Mt Jag) sain sate ott ge th tay oiechaea, rn) sfote off jad? oele Geesagwe ab ie sit ed is CHlowp. boon to aaw abamt deg, ites (itary swt bata wel i ILLUSTRATIONS PLATE I Fic. 1. The Great Wall of China, showing location near top of wall at which samples were taken, January 4, 1917. 2. View at base of wall. 3. The wall extends over mountains and across valleys. 259 ay RP Bears Deh, <0 Ti ¥ a righ %) a P Bae et ‘aes wend ale i Ai, ss ait Cit) Nes a Pst We el ; ¥ us i) ; , vai, J ' et hee © ato me: - aes za taw to qos teay naktesol yale rh ae ks Wa > AiOl & vrewnel ,polel ota : cTTay eee bee Bales wave eae t * ’ i : 7 A j Wirt, J. C.: BRICK AND Mortar oF GREAT WALL. ] (Pum. Journ. Sci., XII, A, No. 5. Fig. 1. The Great Wall of China, showing location near top of wall at which samples were taken, January 4, 1917. Fig. 2. View at base of wall. Fig. 3. The wall extends over mountains and across valleys. PLATE I. : “ SOME LIMITATIONS OF THE KJELDAHL METHOD ' By Harvey C. BRILL and FRANCISCO AGCAOILI (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) It is an interesting fact that the various chemistry textbooks dealing with analytical methods? in describing the Kjeldahl method for the determination of the nitrogen of nitrogenous organic compounds cite only hyrazine, nitro, and similar nitrogen and nitro-oxygen groups as the exceptions, which require special treatment before their total nitrogen can be obtained by this process. Recent investigations have shown that compounds other than those enumerated in the above references are resistant to decom- position when subjected to treatment according to the Kjeldahl method or some of its modifications. Pyridine sulphonic acids are prepared by heating pyridine with sulphuric acid. The yield is increased by the addition of certain metallic sulphates. This increase results from the raising of the temperature of the sulphuric acid solution due to the presence of the sulphate and possibly from the catalytic action of the latter. But more of the sulphonic acid derivative is synthesized in the presence of the sulphate at the higher temperature than in its absence. * Received for publication March, 1917. 7In Bull. U. S. Dept. Agr. (1912), 107, 5, is the following in regard to applicability of the Kjeldahl and the Gunning methods: “Not applicable in the presence of nitrates.” Sudborough, J. J., and James, T. C., in Practical Organic Chemistry, Van Nostrand Company, New York (1908), 61, write: “It should be remembered the following groups of compounds - do not yield quantitative results unless subjected to a preliminary treat- ment: Nitro, nitroso azo, hydrazo, diazonium compounds and probably cyanogen derivatives and platinichlorides of bases.” Leach, A. E., Food Inspection and Analysis, John Wiley & Sons, New York (1914), 69, in discussing the use of the Kjeldahl and the Gunning methods, warns the analyst that: “Neither method in its simplest form is applicable in the presence of nitrates; if these are present, a modification must be used. The Gunning Arnold method is employed for the determination of the nitrogen in pepper, as the piperin is not completely decomposed by the usual processes.” * Wiedell and Wurman, Monatsh. f. Chem. (1895), 16, 749. Meyer and Ritter, ibid. (1914), 35, 765. 261 2962 The Philippine Journal of Science 1911 Funk,‘ in his study of the vitamine bodies in rice polishings, found that he obtained smaller yields of nitrogen from these compounds when the Kjeldahl method was used than when the Dumas or absolute method was used. TABLE I.—Nitrogen determination by means of the Kjeldahl method. Nitrogen. a ek ee SN trogen Compound. liberated. Theory. | Found. | Per cent. | Per cent. | Per cent. 11. 92 99.73 Benzylcyanide =. -- 225-2 ac en anae eee ener tel oasis & | 11. 96 11.99 | 100. 00 |] 11.75} 98.25 | 11.79 98.59 Phenyleyanate: . 2.295. 2.3 3 on ooo sano cs enema een eee 11.76 | 11. 62 98.80 11.69 99. 40 Pyrrole=-----25 Ae Lote dns con bees tawetee aw ouene meee aeee eee 20. 90 17. 20 82.30 16.61 79.47 12.18 68. 72 Pyridine -(2.2-V ei 6 se BOS eee SS 17. 72 | 12.19 | 68. 73 12.34 69. 64 { 11.30 68. 63 Piperidine: --..200--- sccn en eas one cednaee as SaaS een at See eee 16.47 9.50 57.69 | 12.70 77.12 8.41 77.50 Quinoline sits. eee seat eee eee ee ee ee ee 10. 85 | 8.79 81.00 8.58 79. 07 Jsoquinoline sc! 2) a: eRe 82 ee ee SB ee 10.85 8.48) 76.37 : 6. 28 65. 90 Oxyqutinoline) 22 ooo 3 ree ence ee ra ee ee ee eee 9.58 6.14 64.43 Piperazine 223 se foe ote ee ee ee ee ee 32.54 82.44 99. 66 | 10.12 | 100.00 Oxynicotinic:acid 222229 eee ee LE eee eee 10. 00 9.90 99. 00 16. 93 97.67 Nicotine 220i obese ees oes eke cee ee ae ne ee eee Se ene 17.34 16. 85 97.19 r 15.89 | 91.63 if 22.25 | 100.00 | Methyluracy i: 28822 Bee 6-2 hoot hoa Et ee | 22.23 | 22.55 100. 00 i[ 84.95} 98.60 ) LAUER yi) Sooo obs soe os cece rs Soece aes Sos hee Soe 2 eee de nsscs | 35. 44 34.99 98. 73 | Uxiewncid! 2.02 ee eet 8 adc b ce ae ee ee See 33. 34 33.39 | 100.00 28, 35 | 28.02 | 98.82 Williams, > who was investigating this subject of compounds with antineuritic properties, at once saw the possibility of making use of this property of resisting decomposition to determine the chemical character of these compounds. As a preliminary step in the solution of this problem we undertook a determination of ‘Funk, C., Journ. Physiol. (1913), 46, 177. Drummond, J. C., and Funk, C., Biochem. Journ. (1914), 8, 598. 5 Williams, R. R., This Journal, Sec. A (1916), 11, 49. XI, A, 5 Brill and Agceaoili: Kjeldahl Method 263 the nitrogen content of various classes of nitrocarbon com- pounds by means of the Kjeldahl method to determine what type of compounds yields only a part of its nitrogen by this process. A sample of approximately 0.2 gram of the pure compound was heated with concentrated sulphuric acid (20 to 30 cubic centi- meters), potassium sulphate (5 grams), and copper sulphate (0.5 gram) for two and one-half to four hours or for one-half hour after the solution had become clear, at the boiling point of the solution. The results of this examination are given in Table I. Benzylcyanide and phenylcyanate were included in this inves- tigation, as it was at first thought that the low yields of nitrogen obtained might be due to the breaking down of the molecule with the liberation of hydrocyanic acid. However, it seems more plausible to attribute the low yields of nitrogen from pyrrole, pyridine, piperidine, quinoline, isoquinoline, and oxyquinoline to the formation of sulphonic acid derivatives and their subsequent resistance to decomposition by the sulphuric acid. The use of vanadium oxide ° has been recommended as a cataly- zery in the Kjeldahl method. The method was employed by us in the determination of the nitrogen of piperidine without satis- factory results. TABLE II.—WNitrogen determination of piperidine by use of the modified Kjeldahl method.* Nitrogen. | | Total ni- No, of analysis. Compound. ——| trogen | Theory. | Found. liberated. 4 | Per cent.| Per cent.) Per cent. | TS ot lS ee ee eet IGLOS | 16. 47 | 12. 23 74.26 CA a ee aera ee ne eee eee OOo ae ase ee eee eee a 16.47 12.15 73.77 pe eae ee ene | eoaee (> (pee ne re oe 16.47 12. 96 78.69 | *No 1 was prepared in the manner described by Wunder and Lascar; No. 2 had 0.5 gram of bismuth oxide substituted for the vanadium oxide; while No. 3 had the same amount of antimony oxide used as a substitute. The results obtained in the experiment using vanadium oxide are no better than where bismuth or antimony oxide was used. Dakin and Dudiey’ state that piperidine by prolonged heating with sulphuric acid in the presence of potassium sulphate and copper sulphate gives up all its nitrogen, but that pyridine gives less satisfactory results. In the determination of the nitrogen * Wunder, W., and Lascar, O., Journ. Pharm. et Chim. (1914), 19, 329. "Dakin, H. D., and Dudley, H. W., Journ. Biol. Chem. (1914), 17, 275. 964 The Philippine Journal of Science 1917 content of coal, Fieldner and Taylor * found that low results were always obtained when the digestion was stopped as soon as the solution became colorless. We have used piperidine with potassium sulphate and different amounts of mercuric oxide and with sodium sulphate and dif- ferent amounts of mercuric oxide without quantitative yields, even when the mixture was heated for a period of ten hours. TABLE III.—WNitrogen determination of piperidine by a modified Kjeldahl method. Nitrogen. i worse “ Sodium Monee Mercuric)| ine) ee ee aa o. of sample. sulphate oxide. | heated. cree 4 | | F, 4 sulphate. | Theory. | Found. Lvoe Grams. | Grams. | Grams. | Hours. | Per cent.' Per cent.| Per cent. p iid Sn eg a oe ce 0 8 | 0.3 | 10 16. 47 12.63 76.69 Oem ma ee eet 0 8; 0.7 10| 16.47| 13.22! 980.27 Eni los te Be cra 8 0 0.3 8| 16.47| 12,46 | 75. 65 The above methods were unsuccessful in giving quantitative yields. Finally the method known as the Gunning-Arnold method, which is recommended by Leach, ® for the determination of the nitrogen in black pepper, was employed. This method gives good results with pyridine when the heating is continued for a considerable period after the solution becomes clear. An attempt was made to substitute sodium sulphate for the potassium sul- phate in the Gunning-Arnold method, but the substitution was unsuccessful. TABLE IV.—Nitrogen determination of pyridine by the Gunning-Arnold method and by a modified Gunning-Arnold method. = ee a — —- Nitrogen. | Potassi- | a fe etetmmots | Ris eae (aa eae ‘| phate. | (Wiens. |) anadl liberated. st = yah a enc od lll wt la Grams. | Grams. | Hours. | Per cent.| Per cent. Per cent. quate te 1 Pak Me eabae eB 16 0! 4, |° “Ke he mae he RENEE Cae Ca Yr theta 16 0; 4 | 17.72) 12.0! 621 Qo ah aber eare, cl, cate ee ce 16 0| 4 YAN Rf OAM BRN e TERRE Le 16 0 | 4 | 17.72 15.8} 89.2 Bid ad Py os eee: sais 0 16 | 4 4 A y792)| 17.2 96.5 eee Sees BN se ee ee A ae 0 16 | ai vi2 17.6| 99 3 Tes PEPER 3 6 7 Coot WR 0 16 | 8h) 17.72 16.6] 93.6 BG SEERA AE 8 ei) Lees 0 16 | 3t | 17.72 16.3 : 92.0 * Fieldner, A. C., and Taylor, C. A., Journ. Ind. & Eng. Chem. (1915), 7, 106. * Loe. cit. XII, A, 5 Brill and Agcaotli: Kjeldahl Method 265 The results when sodium sulphate was used are in every case low. Digesting the pyridine for a longer time is conducive to more nearly theoretical yields. Where mercury is used, care must be taken to precipitate it as the sulphide. A loss in nitrogen is liable to arise from this source, because of the difficulty of decomposing the ammonio-mercurial compound.?° SUMMARY The Kjeldahl method gives low results for nitrogen with pyri- dine, piperidine, quinoline, isoquinoline, oxyquinoline, pyrrole, and in some cases with nicotine. The authors believe this arises from the formation of sulphonic acid derivatives and their resist- ance to decomposition. The Gunning-Arnold method gives more reliable results with pyridine when heated for a considerable period after the solution has become clear. Sodium sulphate is not conducive to good yields and cannot be substituted for potassium sulphate. * Justin-Mueller, Ed., Bull. Sct. Pharm., Paris (1916), 23, 167. Nolte, Otto, Zeitschr. f. anal. Chem. (1916), 55, 185. } tw oe Sate a CoRR Bret 4 | idan | m5. haga - fr js wort jap THE PHILIPPINE JOURNAL OF SCIENCE A. CHEMICAL AND GEOLOGICAL SCIENCES AND THE INDUSTRIES VoL. XII NOVEMBER, 1917 No. 6 ALCOHOL FROM DISCARD MOLASSES IN THE PHILIPPINE ISLANDS * By Harvey C. BRILL AND LEAVITT W. THURLOW (From the Laboratory of Organic Chemistry, Bureau of Science, Manila) The utilization of the discard molasses of the sugar mill is yearly becoming of more importance. Several uses suggest themselves. 1. Molasses has value as a cattle food. Its application to this use depends on local conditions of freight rates and whether it is to be transported long distances or consumed near where it is produced. At present very little is thus utilized in the Philip- pine Islands, although this use may have possibilities, for in the United States molasses for this purpose, inferior to the Philip- pine products, sells at a greater price even though it is shipped considerable distances. 2. Attempts have been and are being made to use it for fuel. In Honolulu it has been burned to recover the ash for fertilizer purposes. All the phosphates and potash, except a small vola- tilized portion, remain. Practically all the nitrogen is lost when molasses is burned. It is difficult to handle as a fuel, because of easily fusible constituents of the ash that form a glaze on the walls of the furnace. However, since fuel is scarce in many centrals, the use of extra grate bars, effort, and expense are justifiable in the utilization of molasses as fuel. 3. Its use as a binder in paving brick is still in the experi- mental stage, and its usefulness for this purpose cannot be predicted at this time. 4. It has been used as a binder in the manufacture of bri- quettes from coal dust. Only a portion of it could be utilized * Received for publication May, 1917. 151034 267 268 The Philippine Journal of Science 1917 in the manufacture of briquettes were the enterprise ever so successful, and as coal dust ? promises to be extensively used per se for fuel purposes, no great quantities of. molasses are likely to be used for the manufacture of briquettes from coal dust. 5. Molasses is valuable per se as a fertilizer, but in this use too much sugar is wasted and the effects of the sugar on the - soil are not altogether beneficial. The bacteria * that fix nitrogen in the soil independently of the host plant are stimulated by su- gar, especially glucose. One should expect to be able so to stimulate the bacteria by the use of molasses that the nitrogen fixation from this source would become important. All attempts to do this have been disappointing, since the sugar likewise stimulates the class of bacteria that breaks down the stored-up nitrogen compounds. ; 6. If the molasses were first fermented, it would yield a profit from the alcohol obtained and the lees would become a valuable source of fertilizer, because of their nitrogen, potash, and phos- phate content. The making of alcohol from molasses and the recovery of the fertilizing ingredients is the most profitable of the known uses for molasses. All the fertilizing ingredients ordinarily removed from the soil by the cane are concentrated in the molasses, so that when these are recovered and returned to the soil, together with the ash from the fiber or bagasse, the soil has suffered no loss and theoretically is as capable of producing a second crop as it was of producing the preceding one. The sugar industry is unique in that the sugar produced represents no constituent taken from the soil that must be returned in the form of fertilizer. Consequently, if the mineral ingredients found in the bagasse and in the molasses are returned to the soil, the soil is no more depleted than before the crop was harvested. Discard molasses in the Philippine Islands sells for about 6 centavos‘ a gallon (1.6 centavos a liter), or about 10 pesos a ton. Peck and Noel Deerr ° have estimated the value of the fertilizer ingredients in 1 ton of Hawaiian molasses at 14 pesos and the cost of the re- covery of these constituents at 6 pesos. ?The Chicago & North Western Railway Co. is successfully using coal dust in running one of its engines. It claims to obtain higher efficiency from coal dust than from lump coal. 2These are a different group from those existing in the nodules of legumes. “One peso Philippine currency equals 100 centavos, equals 50 cents United States currency. ; * Bull. Hawaiian Exp. Station, 26, through Sugar (1914), 16, No. 7, 38. XII, A, 6 Brill and Thurlow: Alcohol from Molasses 269 TABLE I.—Fertilizer constituents of Philippine and of Hawaiian molasses. | Philip. | Hawai- Constituent. | pine. | ian. aes -|_—_—— LT TR ates ie Bed ee eS en ee ee eee | PERTOND DOU eee eee ee eae el ere ae ee a nt Ee tok oe 0.38 | 0.21 | Pra MOreNas Se pe ee ol oe Pe ee at Sse Sea ees 0.21 | 0.64 The potash and nitrogen content are greater for Hawaiian _molasses than for Philippine molasses. The Hawaiian cane takes up more of these constituents, because the quantity availi- able is greater due to the general use of fertilizers in the Hawaiian Islands. In many cases no fertilizer is added to the sugar lands of the Philippine Islands and no attempt is made to return the fertilizer ingredients found in the ash of the bagasse and in the molasses. Thus it is only a question of years before fertilization must be practiced, or this land will become exhausted and the planters’ loss will be much larger than at present on account of the smaller crops resulting. Therefore it is expected that the fertilizer value will never be lower than now. In practice about 1 ton of molasses is produced for every 5 to 6 tons of centrifugal sugar. During 1915, 211,012,817 kilograms of. sugar were exported from the Philippine Islands. Were this exportation all centrifugal sugar, it would represent over 30,000,000 kilograms of molasses. If this molasses were con- verted into alcohol and the fertilizer ingredients were re- covered from the lees, they would be worth more than 125,000 ‘ pesos at the price quoted for the fertilizer ingredients in Hawaiian molasses,® while the alcohol would represent a value of, approximately, 1,750,000 pesos calculated at 17.2 centavos, the current (December 1, 1916) selling price per liter of 182 proof denatured alcohol. A considerable portion of the Philippine discard molasses is now being used for the manufacture of alcohol, and several con- cerns are planning to extend their activities so that the waste here is not greater than in many other sugar-growing countries. The methods of fermentation are crude and capable of much im- provement. For example, no well-directed effort is made to keep an accurate control of the percentage yields by deter- mining the sugar content of the molasses and by diluting the wort to a definite strength. Care is seldom taken to keep the vats and machinery clean or to sterilize the vats, and-even com- * Peck and Deerr, loc. cit. 270 The Philippine Journal of Science 1917 mon cleanliness is often strikingly lacking. Neither the inocula- tion of the wort with a culture of yeast in order that the yeast may have a start on the bacteria, nor the distillation of the fer- ment when the alcohol content is at a maximum, is always carried out. It is common practice to allow the wort to become inoculated with yeast from the air. From one to three days are required to bring about active fermentation, and as a consequence the ferment becomes infested with bacteria, which destroy much of the sugar before the yeast crowds them out. No attempt is made to use good water for diluting the molasses, and it is a- common practice to use dirty water, thus introducing large quantities of bacteria. Poor yields are obtained when poor methods are used. When the vats and solutions are sterilized, when pure cultures are used, and more care is taken, the cost of handling the solutions will increase, but the greater yield will more than compensate for this. Some figures presented by Owen? on the relation of profit to efficiency of fermentation are significant enough to be quoted here. TABLE Il.—Profits from the fermentation of molasses, under varying conditions of efficiency. Theoretical yield. Profit per gallon. Per cent. Cents.* 57 —5.5 60 0.1 66 1.43 69 2.0 75 3.3 80 4.3 85 5.4 90 6.5 94.7 7.4 ® United States currency. This estimate is based on a cost price for Cuban molasses (total sugar as glucose, 55.11 per cent) of 10 centavos a gallon and a selling price of alcohol of 76 centavos a gallon, 180 proof. Theoretically 51.1 per cent of the weight of the sugar is the weight of the resulting alcohol, but in practice this cannot be attained, since some of the sugar is consumed by the yeast and some of it is converted into glycerol, succinic acid, cellulose, etc., so that the highest percentage possible is 94.7 per cent of the theoretical. Table II shows that no profit results when a yield below 60 per cent is obtained from molasses under these conditions of cost and selling price. A profit of 2 centavos is not obtained until we reach an efficiency of 65 per cent. At 80 per cent, which is * Sugar (1914), 16, No. 7, 32. XII, A, 6 Brill and Thurlow: Alcohol from Molasses 271 considered good distillery practice, the profits increase to 8.6 centavos; while at 94.7 per cent of the theoretical, which is the highest possible yield obtainable, the profits have risen to 14.8 centavos a gallon, almost three times as great as the profits for a 75 per cent yield. This seemingly high increase in the profits is due to the increased yields more than compensating for the increased cost of production. In the Philippines, where the molasses * costs 6 centavos a gallon and 182 proof alcohol sells at 17.2 centavos a liter, the profits resulting are as given in Table III. TABLE III].—Projits from the fermentation of Philippine molasses under varying conditions of efficiency. f Sap. } | | Profit per gallonof | molasses. Theoretical Based on ! yield. Calculated | the estima-| on the basis} ted cost of of Table /alcohol pro- Il. duction in the P. I.a Per cent. | Centavos. | Centavos. 57 5.8 4.5 60 7.0 | 5.7 65 | 8.9 7.6 | 1 | 10.8 9.5 | 15 | 12.7 11.4 80 | 14.6 18.3 | 85 16.6 15.3 | 90 | 18.5 | 17.2 94.7 | 20.3 19.0 L — 8 Calculated on the basis of a cost of 17.3 centavos for converting 1 gallon of molasses into aleohol. The cost of converting 1 gallon of molasses in the United States into 90 per cent alcohol is 16 centavos. The estimate as deduced from certain data collected in the Philippine Islands makes the cost 17.3 centavos, only slightly greater than the above, and leaves a good margin of profit for the manufacturer. The larger profit for alcohol produced in the Philippine Islands is due to the smaller price paid for the molasses and its higher sugar content. A yield of 80 per cent of the theoretical gives a profit on the molasses of 13.3 centavos per gallon, while a 60 per cent yield allows a profit less than half as great. Any im- provement in the methods of fermentation and distillation of molasses would mean an increase of revenue to the Islands and larger profits to the manufacturers. No alarm need be felt in * Average total sugar as glucose for 10 samples, 62.6 per cent. 272 The Philippine Journal of Science 1917 regard to a possible overproduction of alcohol® in the future. It is certain to have an increased sale for power purposes with the rise in the price of gasoline. Special carburetors are sure to be invented which will be adapted for alcohol or gasoline interchangeably as a fuel. The data in Table IV are suggestive of what will take place on a large scale at no distant date. TABLE I1V.—Data obtained in Germany with various fuels and mixtures on a model 1914 Mercedes car, ordinary carburetor.* : | Distance Fuel. see com ae of fuel. = = eee | Parts. Miles. | Miles. 1 benzol ‘to: l alcohol). -2=3-5- | ¥9°8 G8 13°9 08°L 689 | P8°S 9°89 80 90°0 : 0°18 9F°9 OP's €2°9 82 °8 9P°9 69°8 6°LE éL'9 8P°L 97'S 9L°§ QoL él 'T euou 0°18 9F'9 99°8 £6 °9 9L°8 9F°9 63 °8 8°62 ST9 98°8 66°9 16°8 8°89 ¥8°0 90°0 6°68 69°9 | 58°8 &°9 08 °8 69 °9 68 °8 bat 97'S 268 6h P 16 °§ 0 a 90°T suou “pb | ? ES ee | ee ell ie a "a ee ie x Aiea “Se eee “ leae ao qussnon "Ayy | “yoyoo | *A3y | “Joyo | “A | oo 5 | Touo> | “431 | “Tou? | “0402 | .g5, | ‘louoD | “uoKntos qusdsed| lew | “PPV | “Iv |-PPV | -IV | -PPV AV | -PPY | IV | -IV “Iv | paepusys PIPLA | | goer ON 18804 | T 03 poppe = = —s => | a | 5 oe apiiony *JOyooly “sanoy 981 *sanoy ZIT “sanoy gg *sanoy F9 eee ‘sanoy 9T ates ‘aol odiu Buyuowsof mors paznjosr 87100 y8nah fo saunqjno aay ayy fo sz)nsax aarnn.mdwojg— IIA ATA, 1917 crence Journal of S lippine t The Ph 278 . aes a iis ee) ss Pe eS Pa = may Bete es as 5 LR a ; a SS ES 1°88 a) | 80°9 | £29 | 06 | 18°¢ | 99°P | W'S 823 0-19 | 18 0g LOO) eR oe ae oa ne eee 8 | S"OL veo | Wed} TOS | TOT 86° =| ‘Tre 0L°% PLT | 0°88 18°T 08 @ Me BUOUS » ngapsman a shoo ane seareShrnaeba cers L | 9°b8 62°9 | 60°9 | 629 b8 LL'g 9L°9 10°9 21's 8°99 OFT 08 ODES ie Sacre ae ee a 9 . ovsg | ze'9 19 ze "9 06 9P°g 99°F 88 19°% 0°19 89°T 08 LOMO). aCe “Sere aes ereess econ aere q vGL | 16°9 16S Te"¢ 0°6 98°F 16° 88°8 10°% 0°68 18 T 0g ZOO P el ges sma” sgek gar anne tases ae ore y | esa | arp Be iar sal fee sa geod (IH: 6F'S al'P §8°¢ 08 °% 2°28 16°0 98 ODO! ees ee aa aes re & Cibies NSatg ie Nersartca|oranraan a 8°6 | 82°8 9° 90°8 98°% 8 "Sh 6L°0 98 POLO Fem | ocbin ce s ce coca: Wogan 3 Oreeil Tage: veeserse=s pease eee: 0°OL 62% =| Ig"@ 93°% OFT 38h ~—s| Sh"0 98 | euom |---------===--2=--a-nnnnnn anne ie | | “Qo 6 | $$] J —_ d Oe Seabee eee weeees | “piers | | | Kren aaa Sa 93) LOMGOE YE | AIC HOORY TOHOlY | “SII | 1OUPTV | an. | “POPPE ‘Dierme | eee | -Raladwie} a cia ‘ON o[dureg | # i - | eB8I2AV | oury | *Oyooly *sInoy 09T|"Sinoy 9gT “sanoy ZIT “sanoy OF *s.moy 9T } | ‘sasspjowm fo Uounzuamtaf aYy2 UO aprsony wnuowun fo szunown burhana fo aouenfuj— ITA AAV, e . XII, A, 6 Brill and Thurlow: Alcohol from Molasses 279 were added, the maximum alcohol content was attained at the end of the fourth day. In Table Vi the maximum alcohol con- tent was not reached at the end of the fourth day in a single instance. No effort was made to accustom the yeast to the pres- ence of the fluoride by culture, antecedent to the experiment tabulated in Table VIII, and‘this partly accounts for the slow- ness of the fermentation. A study of the effect of adding various inorganic salts to the ferment was made. ‘The results of this experiment are recorded in Table IX. The standard solution used here was 200 grams of molasses made up to 1 liter, with the addition of 2 grams of sulphuric acid, and then heated to 70°C. After cooling, the samples were inoculated with pure yeast culture and the various salts were added. Table IX shows that magnesium sulphate, sodium chloride, sodium fluoride, potassium phosphate, and sea water do not stimulate the yeast as do ammonium sulphate and fluoride. Sam- ples 2, 3, and 4 gave the largest yields. Samples 3 and 4 had two equivalents of ammonium salts added to them, while 2 had but one. Samples 1, 5, and 9 had one equivalent of ammonium salts added; they excel the remainder of the samples that had no ammonium salts added. This is good evidence of the benefit of adding ammonium salts. Phosphates '* stimulate yeast, so that its initial activity is increased. They apparently initiate the fermentation, that is, if the materials used in fermentation could be made absolutely free from phosphates, no fermentation would occur. The apparent noneffect caused by the addition of the phosphate in samples 8 and 9 is due probably to the presence of sufficient quantities of phosphates in the original molasses solution to accelerate the fermentation, and the addition of further quantities has no apparent effect. The ammonium salts keep the ferment comparatively free from bacteria, because the growth of the yeast is stimulated and the bacteria are crowded out. Ammonium sulphate is as efficient for this purpose as is ammonium fluoride and is much cheaper. Sea water has a deleterious effect on the ferment.*7 The amount of alcohol produced in every case is less than where distilled water alone was used. Sample 7, Table VIII (distilled water used), gave a yield of 70.5 per cent of the theoretical, while ** Harden, Arthur, Alcoholic Fermentation. Longmans, Green, and Co., 839 Paternoster Row, London (1911), 50. * The influence of sea water was studied, since salt water from the esteros, on which many of the distilleries are located, is often used for diluting the molasses. 1917 tence Journal of Sc ippine il The Ph g°9g Cl hay Shige Ops) v0'8 al 'P 92°8 | Gh s tS) b0°% 3°29 AT a ll (ca Op ies 00°8 SEG 2 P88 als 68 | £9°% | ¥°89 IL’¥ | ee AQAIG | B6°L IL"? | 16°8 =| 6L°S | 64 Lg°% | oh | T8°s be ale UBT | CL'8 18S | 6L°b | $8°S | 68 90° | $°08 OO" Sie Fa Ophea” | 00°OT r 00°9 9L°9 &8 ay 14-09 06° i | . | PSL 9P°S ~~~" UBeID | $9°6 9p °S re P 9L°& | 88 86% ; 9 TL Le oe. ae oS UBT | 99°38 T8"9 | 6L' b8°s 8& La& | OL Rade | ae CS) Seas 02°8 go's | Fag SO && LO& E 9°08 COURSE” Sain ome SRE ae" v8 °L 009 «=| 66'S 98°F | 0S 86° 6°88 Oboe Sia uBalD | F2'6 yg “9 1959 199 OL 00°9 6°88 LON Os aE 37 ouly | 99°8 9F°9 19°9 19°9 GL 9T°S T 68 TOO te Sie es op” 00°L L1g°9 p9°9 8i'g OL 16 8 9°08 CPS Paleo uBalD | 206 S66 99° 98 °P 66 Tes "TBO} . } piers 4 . . . . -39.1094} . sainoy , jou ©) jou |. jou | Jo yue0 bor atl gg Jo pue AUPPV) -00/V¥ Seate -0d|V SID | -oary dod ‘pjarx ah NM 48 Bl18}0eq | jo ooueseid ni 0} passer mL foo Ul WOIZIpUuO: : : “Oyooly PUD | -sanoy ggt SBEE Tie caeriall. oEanOHES 9g zit «4/8 0010) Nassar co Saar J0JVM Bos YIBUEI}S [[N |---- ET 0s 19'T 198 29/0) eae age a Se 10}8M BOS Y}BU0I48 | |-~--ZT 89 oor | 92 CULO, le -eeeceeee fos gan os JoyBM vas YIBuII3s F |--- TT | *s]u9]e 89 10'S | 68 290 | -Ainbe gz ‘eyeyd[ns unisouseu werd gg‘) | -~~OL "yore jo yue[eAInbe [ ‘apliony winiuowure 28 PUT | SF 610 | OL 0 Sn{dozeydsoyd unissejod mers PE ‘0 |--~6 “quole SF TORCHe ALE 980 | -Amba | ‘eyeydsoyd wmnissejod wes3 pg 0 | ---8 £9 122 | 8 16°0 |-8yueTRAINbe ¢ ‘epl4ozyo uNtpos WEA gp "0 |-~~L 69 10’2 | 98 gg°0 | -“4ueleamnbe T ‘epyzony wnjpos urEIS ZT“ |-""9 “quale 69 6r% | 99 z6'0 | Amba 7 ‘eyeydins umiuowue wesd gro |g “squa[e OST 9u'P 19 6L'T -Ainbo Z ‘o}yeyd[ns winiuowMe wield ge°9 | --F *sjuo[e Olt Ths | 8b 66°0 | -Ammbe gz ‘epraony winjuowue wieIs 0Z°0 | ~~~8 LL 99° | SP QC10ME ager ae ae a Oe obs oe Gy) SA “quale 86 10% | 06 16°0 | -Ambe { ‘epitony wnuouwe wed QT ‘0 | ~T sa2g | J | aneg | 24 ‘uOI}N[Os pAepuLzs 0} pappe souBysqng | race | | “sinoy Op “sano0y oT if ‘sasspjow fo uonpjyuaemusef oY42 UO SsZvS snoipa fo aouenyfuJ—YX] AIaVL = XI, A, 6 Brill and Thurlow: Alcohol from Molasses 281 samples 11, 12, and 13, where sea water was used, gave 63.4, 62.5, and 55.5 per cent of alcohol, respectively. The percentage yields range inversely to the concentration of the sea water used and are the result of the influence of the impurities carried by this water. A sample of molasses was prepared as under Table VI and exposed to the air without inoculation. At the end of forty hours active fermentation had begun, due to inoculation by wild yeasts, and the sample showed an alcohol content of 1.40 per cent. The maximum alcohol content, 6.61 per cent, was shown after one hundred twenty hours had elapsed from the time of mixing. Much interest is taken in this and other laboratories in the properties of the compound occurring in tiqui-tiqui (the polish- ings from rice), brewer’s yeasts, wheat bran, etc., and which is known by the names vitamine, oryzanin, water soluble B, etc. Kurono '§ was led to investigate its effect on yeast in fermenta- tion. He made an alcohol extract of rice polishings and added small quantities of the dried extract to his ferment. The ex- tract accelerated the fermentation even more than does peptone or asparagine. The results obtained by Kurono led us to investigate the effect of adding rice polishings directly to the ferment. These results are tabulated in Table X. Because of the poor results obtained, another sample (No. 7) was inoculated, this time from sample 6, to determine if the yeast would be more active after having become accustomed to the tiqui-tiqui. TABLE X.—The effect of adding varying amounts of tiqui-tiqui (rice polish- ing) to fermenting molasses. Alcohol. 136 hours. Alcohol. Tiqui- : tiqui F Sample No. | added Yield, |} tol | 46 40 64 gg | 112 | Alco-| Acid-| Max-| per liter. | hours. | hours. | hours. | hours. | hours. | hol. ity. imum} cent yield. |of theo- retical. poe si> * | eee ee g- | 1 oe eee 5 0.38 1.50 2.50 3.05 3.99} 5.24 10. 86 5.24] 70.4 Deets ee saw a 10 0.38 1.50 2.64| 2.90 3.90 4,66 11.44) 4.66] 62.7 | C2 SS ee 20 0.38 1.60 2.64 4.13| 5.07} 5.70] 10.66| 6.70] 76.5 Ch Se ee Es a5 0.38 1.60} 2.50 3.13 4.05 5.14} 10.84 5.14] 69.4 | | (= eee al0 0.38 1.54, 2.84 3.55 4.04} 6.31) 9.81 5.381 | 71.3 Geek ae ee #20 0.38 | 1.60) 2.98 3.85 | 4.71 5. 24 11.08 5.24 | 70.3 (iterate ee 5| 0.35] 1.60 | 2.50.) 3.41! 3.97 | 4.12] 12.32] 4.12] 65.5 ® Cooked. * Journ. Coll. Agr., Imp. Univ. Tokyo (1915), 5, 305. 282 The Philippine Journal of Science (1917 A comparison of the results with the results obtained when the standard solution for Table VIII was fermented shows that the addition of tiqui-tiqui has no beneficial influence. One result, sample 3, only shows a real increase in alcohol content over the sample where no yeast food was added (see sample 7, Table VIII). The acidity in every one was high at the end of the sixth day, indicating that the addition of tiqui-tiqui contaminates the solution or makes the ferment more favorable for the growth of bacteria. To extract the tiqui-tiqui with alcohol as done by Kurono would be more expensive than using ammonium sulphate. Culturing the yeast in ferment to which tiqui-tiqui has been added did not stimulate its ability to grow in the presence of tiqui-tiqui. The use of ammonium salts'’® lowers the yield of the higher alcohols (fusel oils) and is, therefore, an advantage for this reason. Yeast can be invigorated by culture in a nourishing ferment, and such yeast acquires a vigor that induces rapid fermentation. It can be accustomed to conditions that would ordinarily inhibit its grow and that are unfavorable to the growth of bacteria and wild yeasts. Advantage has been taken of this property, in the method of fermentation known as the Molhant process, to increase the resistance of the yeast to more concentrated solu- tions of alcohol and to add to its ability to ferment higher concentrations of molasses. Mirior,2®° in using this method, proceeded as follows: Yeast was added to a small amount of molasses of 6° Baumé acidified with 3.5 cubic centimeters of hydrochloric acid per liter, and the whole was allowed to ferment. When fermentation was active, the ferment was pumped to a larger tank and more molasses of similar quality was added. This was permitted to ferment twenty-four hours and then put in a larger tank, where plain molasses of 14° Baumé was added until the whole mixture was about 12° Baumé. Fermentation was complete in from twenty-four to thirty hours, and a must of 9 to 9.5 per cent alcohol was obtained. The process gives 60.23 liters of alcohol per 100 kilograms of sugar, calculated as sucrose. He states that this is 1.5 liters per 100 kilograms more than is obtained by the old process. To determine if this process would increase the yields of alcohol with the yeast at hand, the following experiments re- * Ehriich, Paul, Ber. d. deutsch. chem Ges. (1906), 39, 4072; (1907), 40, 1027, * Bull. Assoc. Chim. de Sucr. et Dist. (1914), 31, 936. XII, A, 6 Brill and Thurlow: Alcohol fron. Molasses 923 corded were planned and performed; solutions were made up as described under a, b, and c: a. Two hundred fifty cubic centimeters of 20 per cent molasses solution, plus 0.25 cubic centimeter concentrated sulphuric, plus 1 equivalent of ammonium sulphate were sterilized once by heating and inoculated with yeast. Four of these solutions were prepared and allowed to ferment. 6. Twenty-four hours later 250 cubic centimeters of solutions identical with a were added to each of the above four solutions. c. Twenty-four hours later 500 cubic centimeters of quantities of solu- _tions of the strength given below were added to the respective samples: 1. One hundred twenty grams of molasses in 500 cubic centimeters of solution plus the usual proportion of acid and ammonium sulphate. 2. One hundred thirty grams of molasses in 500 cubic centimeters of solu- tion plus the usual proportion of acid and ammonium sulphate. 3. One hundred forty grams of molasses in 500 cubic centimeters of solu- tion plus the usual proportion of acid and ammonium sulphate. 4. One hundred fifty grams of molasses in 500 cubic centimeters of solu- tion plus the usual proportion of acid and ammonium sulphate. This makes sample 1 a 22 per cent molasses solution; 2, a 23 per cent; 3, a 24 per cent; and 4, a 25 per cent. The first sample for determination of alcohol content was taken at the end of twenty-four hours after the ferment was completed, and subsequent samples were taken at intervals of twenty-four hours, as recorded in Table XI. TABLE XI.—Yields of alcohol obtained from molasses by the use of the Molhant process. —S— Ss ; 144 | ! \ Alcohol. | 120 hours. Hours! Alcohol. | H Dee Sample No. we e Yield, “| 24 48 72 865 Alay) th Acid, at || Maxi) per’ | hours. | hours. | hours. | hours. | cohol. |_ ity. cohol. yield: lof theo- | | retical. P. cent.: | ii Ussher Ae 22 3.12 4.94|- 6.46 7.16 7.41) 8.52 7.25 7.41 90.7 | (ns GE a ee 23 8.05 4,94 6.70 7.16 7.41 8.40 7.41 7.41 | 86.8 ee ee 24 3.65 4.94 6.79 7.16 7.89 8.40 7.89 7.89 | 88.5 (ASS 2 Se 25 8. 63 4.86 6.61 7.81 8.14 7.76 8.00 8.14] 87.7 1 The maximum alcohol content was attained at the end of the fifth day. The percentage of alcohol yield of the theoretical for sample 1 is the highest obtained in any of the experiments carried out and would thus yield a greater revenue to the manu- facturer. The highest concentrations gave a somewhat less yield of alcohol, but even they are on a par and in many cases 151034 2 984, The Philippine Journal of Science 1917 superior in percentage yield of alcohol to those of the preceding experiments with more dilute solutions. The length of time for the fermentation from beginning to end is two to three days longer than by the method in vogue here, but the initial solution being of smaller bulk requires less space, and the cost of the extra space would be compensated for by the greater yields of alcohol obtained. Besides, much space is at present consumed by the tardiness in distillation when the fermentation is com- plete. It is common practice to allow the must to stand several days after fermentation is finished. The distillers do not realize that the delay results in a loss of alcohol from evaporation and from bacterial action, more especially the latter. In order that further data on this method might be collected from more thorough trials, the nine experiments recorded in Table XII were performed. The nine samples were first made by diluting 30 grams of the stock molasses to 200 cubic centi- meters and adding the regular amount of sulphuric acid and one equivalent of ammonium sulphate. This solution stood two days until the fermentation was proceeding strongly, in the case of the first of each duplicate, while the second. of each duplicate stood for only one day, and then fo: No. 1 were added 300 cubic centimeters of a solution containing 60 grams of molasses and the regular amount of acid ammonium sulphate. No. 2’s were added 300 cubic centimeters of a solution containing 70 grams of molasses and the regular amount of acid and ammonium sulphate. No. 3’s were added 800 cubic centimeters of a solution containing 80 grams of molasses and the regular amount of acid and ammonium sulphate. No. 4’s were added 300 cubic centimeters of a solution containing 80 grams of molasses and the regular amount of acid and ammonium sulphate. No. 5’s were added 300 cubic centimeters of a solution containing 90 grams of molasses and the regular. amount of acid and ammonium sulphate. On the following day the following solution was added to: No. 1, 110 grams molasses, regular amount of acid and ammonium sulphate in 500 cubic centimeters. No. 2’s, 120 grams molasses, regular amount of acid and ammonium sulphate in 500 cubic centimeters. No. 3’s, 120 grams molasses, regular amount of acid and ammonium sulphate in 500 cubic centimeters. ; No. 4’s, 130 grams molasses, regular amount of acid and ammonium sulphate in 500 cubic centimeters. No. 5’s, 130 grams molasses, regular amount of acid and ammonium sulphate in 500 cubic centimeters. XII, A, 6 Brill and Thurlow: Alcohol from Molasses 985 This makes: _Per cent Sample No. molasses solution. 1 20 2’s 22 3’s 2 23 A’s 24 5’s 25 One hundred cubie centimeter samples were withdrawn for the determination of the alcoholic content at twenty-four hour intervals. The results are recorded in Table XII. TABLE XII.—Some further data obtained by use of the Molhant process in the fermentation of molasses. Alcohol. | —— A a 4S Sete ee Mo- | . H Sample No. | | . Yield, | lasses. | 94 48 72 06 | u2 | 144 | Maxi | percent | hours. | hours. | hours. | hours. | hours. | hgurs. > Emanation was high; sample of gas bubbling through a pool of hot water. * Water which, owing to the nature of the source, could not be obtained just as they emerged from the ground, or those which may not have been typical ground waters owing to their derivation from springs believed to be local or temporary. xu,4,6 Heise: Radioactivity of Waters, Northern Luzon 297 TABLE I.—Radioactivity of waters of northern Luzon—Continued. | | | Date tested. | - No. | | | | | | | ‘ cae 39...! Dec., 1916 89_._| May 14,1916 41_.., May 13, 1916 | 42.__| May 15, 1916 | 3 May 11,1916 it oe | aaa ar ee 45___| May 12, 1616 “het See donee 47_..| May 9, 1916 | 48___| May 10, 1916 49__.| May 9, 1916 50.--| May 20, 1916 | 52___| May 17, 1916 538__.| May 16,1917 | 55...| May 17, 1916 | 56...| May 12,1917 57_._| May 13, 1917 | (i Seed Pepe dase. | 59___| May 18, 1916 60..-| May 12,1917 61___| May 19, 1916 62__ | May 19,1917 63...| May 17, 1916 64___| May 11,1917 65.-.| May 17, 1917 66_..| May 8, 1916 67_._| May 17,1917 69__.| May 5, 1917 70_..| May 6,1917 @ Nonthermal. Radium . | | Bleva- emana- Location (province, sub-| “e | tion |'Tempe- tion per| province, and town or | Source. | above} liter as district). | | sea |Frature.| > pams | level Ra < } ° | 10-12 —— a | Meters.| oC. Benguet, Trinidad ___-_- Spring near municipio_._-| 1, 250 a21 0 | Bontoc, Bontoc_____-__- City springs ----see =e ae 920} (8) | trace Se Aes do .____.____.____-_-| Spring near city stables_- 920} (a) trace Saoee do _____________-_-__] 2 springs, barrio Samoki * 920 | « (a) 0 | Bontoc, Mainit --------- Mainit (hot) saltspring---| 1,300) 100 0 Bontoc, Sagada________- Mission spring___-_--_----- ' 1,650 (a) | 111 ete obsess SS Underground river ______- 1,450] (a) | trace een do ._...._____.-____.| Spring, barrio Tetepan_--} 1,750) (a) 0 see do ________._-.__....| Spring at slide, Tetepan_-) 1,300! (a) 263 Lepanto, Cervantes ___.| Municipal supply-_--_-__- 71,000 | (8) | 0 =e 5 do _____..__._--_.-..| Hot spring, river bank __- 03 eee 0 sasct: do _____.._-_-._____.| Comilias hot spring------. | 500 eeteceed 0 hrurdo, Aouad = 9-2 =- e. | Spring at Kilometer 65___| 1,300] (a) trace | Peace do .___..-_______-___| Spring at Kilometer 76*__| 1,300 (a) 0 Ifugao, Banaue_-___-_-___ Bognakan spring_-______- 1, 150 | 23 381 bebe dojec sees eee ee os |e Raakop spring == ee=2—2|h 153000 4(2) 650 Lee Oe ee ene Maranon springes se sseeal tbOo |e ce) 420 eee, CO ee a eaypayal Spring .---—-=-|" 14160") 21 289 | Ifugao, Kiangan________ Adhang spring___-_----_- 1, 000 | 20+, 1,200 | scone do ________....--..-.| Adukpung spring--------| 850 25 | 1,325 on OG nee Ad unr hu spring ace secs 850 25 720 Cee al Gee nee eee PA LOA Sprinip=eee enone) ls LOO) 22 189 Ban doe ee ei bakdolspring ss ee | 11505 22| 190°} nme do ..--..---2-0=-.-| Malpao eprings (2) -....-:| 850] 23) 150 coe da). cee ee DUN gAaM BDL 850 | 24 945 aoe BO ee eee See ET KOISDEING eee SHON eee eed, Obs | a OG: cots ee eee PK OU BDIING 2525.2. ccestee 850 | 23 900 Ifugao, Sapao ____-_--_- Bolanam springs se seen 23 175 Lepanto, Mancayan ____| Spring, Balili trail_______- | 1, 580 (a) 114 NUEVA VIZCAYA | PROVINCE. Bapabags =. 22s ee | Bafios BDringe-- 2 see | 800 26 130 ue donmees eee =| Small pump welle-==2 =|) 800 27 | 180 amibane se 26 ae bes3 dope Me maasite tel ia00 27| 190 Bayombonre=- 2-7-2. Bangan spring ____.----_- 350 27; 130 Bee bt C0 eee eee elaza pumipawmelll. 25. = see 300 26 130 Boscaran sae Spring near school ______- 300 26 325 Wosotss ssi 28 oa ee Spring near rest house_-- 550 24 0 Orcoring 2 ee Spring near road _________ (2) 30 130 Salinapr see Salinas salt spring _______ 500 31 95 Sani buiss2s88=222 2225 Spring in quarry ________- (2) 27 60 Santa he: acs sana oe Santa Fe spring _________. 500 22 480 POlano pees ese ees Solano spring___--------_- 300 27 195 ehus do seescessssectessee| Solano pump well _--.____| 300 | 27 240 * Water which, owing to the nature of the source, could not be obtained just as they emerged from the ground, or those which may not have been typical ground waters owing to their derivation from springs believed to be local or temporary. 298 The Philippine Journal of Science 1917 The table is self-explanatory, for the most part, but there are a few points in connection with it that merit attention. The springs in the list are typical and are representative of the country in which the work was done. They comprise the prominent and better known sources along the route of travel, among them several used for salt manufacture (Salinas, Mainit) and several hot mineral springs with reputations for medicinal virtues (Itogon, Mainit, Comilias). The highest activity recorded (1,325 x 10°”) was found in Adukpung spring,® in Kiangan. It will be noted that Piko spring, in Kiangan, was examined both in 1916 and 1917 and that there is a marked discrepancy between the two determinations. This difference does not neces- sarily indicate a variation in emanation content, nor even a serious error in the determinations, as the water from the spring in question flows into a small, covered reservoir before it is allowed to emerge; therefore a sample cannot be secured directly at the point of emergence. As might be expected in a volcanic region, there are a number of solfataras in the area under discussion, notably at Bolotoc, at Daklan, and near Monhuyhuy. The one at Daklan, which we visited this year, is characterized by a number of vents, from which hot gases and vapors emerge, principally hydrogen sul- phide, sulphur dioxide, and steam. We were unable to find any springs at this place. There were a number of excavations in which surface run-off and perhaps condensed steam had col- lected, forming great caldrons of hot water, some of them used as baths through which the gases and vapors bubbled. There were also a number of hot mud “springs,” where the gases broke through semiliquid mud with the peculiar sound from which the solfatara presumably has derived its Igorot names (Barutbarut, Badukbuk). As the waters in the excavations just mentioned were probably surface run-off, and as they were constantly aérated by the gases bubbling through them, their activity was *This spring is peculiar. It is located in the wall of a rice paddy and emerges at a level only a few decimeters below that of the water in the field. As it is separated from the rice-paddy water by less than 5 decimeters of earth, this spring looks like a mere seepage. We were assured, however, that it is a true spring, whose flow does not fail throughout the year, even during the months when the rice field is quite dry. Analysis of the water in the rice paddy showed marked differences from that from the spring, and the determination of activity seems to furnish further proof that the source is a real spring. xm,a,6 Heise: Radioactivity of Waters, Northern Luzon 299 of minor interest. A collecting can, full of the gas taken from one of the excavations by downward displacement of water, proved to be radioactive, as indicated in Table I. For completeness, I have compiled the available chemical data on the waters studied and have included them in Table II. All of the waters tested for radioactivity in 1917 were analyzed at the source by Mr. A. S. Behrman, chemist of this Bureau, who ac- companied me on the field trip. In the case of highly mineral- ized waters, or when additional gravimetric determinations were desired, samples were taken to Manila in glass-stoppered bottles and analyzed in the laboratory. It should be noted that the data given under “total hardness’? were obtained by a modification of the Blacher’ potassium palmitate method and represent com- bined calcium and magnesium content. Of the numerous salt springs examined, none showed more than small amounts of activity. The hot springs, too, were only slightly or not at all radioactive. These results are in agreement with those obtained elsewhere * and are to be expected from the low solubility of radium emanation in hot water or con- centrated salt solutions. A number of waters low in radio- activity are also low in dissolved mineral matter. This is prob- ably of little significance, except to show that certain sources, instead of being deep-seated springs, were but little more than seepage water, percolating the soil for comparatively short dis- tances. It might be pointed out that the most radioactive waters encountered were high in calcium and magnesium content, in- dicating an origin in calcareous material. The work done in the Philippines up to the present time is still insufficient to justify conclusions, so that the cases noted should be regarded as isolated observations, at least for the present. However, it is worthy of note that this peculiarity is distinctly at variance with the usual observation ° that the water from igneous rocks * Blacher C., Griinberg, P., and Kissa, M., Die Verwendung von Ka- liumpalmitat bei der Wasseranalyse, Chem. Zeitg. (1913), 73, 56-8. This method has been adapted to field work by Mr. A. S. Behrman and now forms one of the regular routine determinations in the Bureau of Science field assay of water. ‘ef. von Hofer, H., Radioactive springs, Intern. Zeitschr. Wasser- versorgung (1914), 1, 52-5, 90-8; through Chem. Abst. (1915), 9, 1714. “ef. Clarke, F. W., Data of geochemistry, Bull. U. S. Geol. Surv. (1916), 616, 315. Sahlbom, N., Arkiv. Kemi. Min. Geol. (1915), 6, No. 3, 1-52; through Chem. Abst. 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L0f pajsaz suaynm ay, fo sashjnun JnnumayQ—TI ATA I, xu,4,¢ Heise: Radioactivity of Waters, Northern Luzon 3038 is generally more radioactive than that from sedimentary deposits.” The geology of the area discussed in this report has unfortun- ately not been worked out in sufficient detail to justify generaliza- tions; hence it is not feasible at this time to attempt to deduce any definite relations between radioactivity and the geology of the water-bearing strata. The following description by Smith ™ of a typical portion of this region is appended for the sake of completeness: This region is typically mountainous, and from the character of the relief we must consider it as being in the stage of “topographic youth.” * * * There are two distinct types of topography in the region covered by this paper, and these are directly to be attributed to the character of the geologic formations. In the country to the west of the Polis Range the formations are mainly volcanic, and we find there an irregular, rugged, accentuated relief. The elevations vary from 370 meters to 2,400 meters or more. East of this range the formations are folded sediments, giving rise to a more regular topography, and in places the hills and mountains are nothing more than tilted blocks of sandstone. On the eastern slopes these present long, gentle inclines, but to the west they form steep escarpments with here and there a saw toothed skyline. As one goes farther to the east, approaching the valley of the Cagayan, the mountains become mere Hoounals.. * +" = A cross section from the west coast at Tagudin northeastward to the edge of Cagayan Valley gives as good a general idea of the formations and structure of the region as one could expect to get by any procedure short of a detailed survey of the whole country. Fig. 2 is a graphic attempt to record my interpretation of the main facts. Near the west coast we find gently folded shales and sandstone whose inclination increases as we go toward the Malaya Range, being much contorted as we get well into the cafion. The Malaya Range is essentially a mass of porphyry or, to be more exact, andesite. * * * The town of Cervantes is situated on a small tongue of high ground between the Abra and one of its branches. The underlying rocks are practically the same as those found in the highland on both sides of the town. As we go toward Bontoe we find the same andesitic mass with, however, several large outcroppings of quartz. When we reach Bagnan and Sagada we find tuffs and reef limestones overlying this igneous mass. é “From Sagada to Bontoc extrusive Packs. almost entirely andesites and dacites, are encountered but east of Bontoc the formations become very shortly diorite and granite. This belt of granitic rocks is only from 8 to 10 kilometers wide. There is more andesite, or rather a very fine-grained, ” One of the most radioactive waters in the lowlands, from Sibul Springs, Bulacan, is also in a caleareous formation, and others high in activity issue from tuffs and conglomerated igneous materials. 1 Smith, W. D., Notes on a geologic reconnaissance of Mountain Province, Luzon, P. I., This Journal, Sec. A (1915), 10, 177-209. 804 The Philippine Journal of Science 1917 almost aphanitic phase of diorite, succeeding the granite on the east as far as the town of Barlig, where steeply dipping sandy shales are encountered. These incline to the southeast. Sandstone makes up the main mass of Mount Amuyao, and from there east to Ca- gayan Valley sediments occur. In places, as at Natonin, there are small areas of extrusive rocks overlying the Tertiary East Coast ~~._ Sea /eve/ oast Range c ¢ > | = | 4 sediments. oan S ‘ : ake 5 Sr---~( R A comparison of.the radioactivity a, o > . se of the waters of the mountains of en northern Luzon and that of the waters examined in the Luzon low- lands indicates that the _ typical lowland waters show the higher radioactivity. The highest radio- activity (1325 x 10-'*) determined in the mountains (Adukpung spring, Kiangan) was practically identical with that (13800 x 10-17) of the most active lowland spring (Sinabac spring, Majayjay, Laguna), but con- siderably less than that (2100 x 10-'°) of the most active lowland ss water (from a flowing well in Batan- gas, Batangas). In Nueva Vizcaya the radioactivity encountered was uniformly low, so that the present work has served to emphasize the peculiarity noted last year, that is, a low radioactivity in all waters except those in a small district in Ifugao. Since the waters studied varied greatly, both in chem- ical quality and in the geological formations from which they were obtained, and since those highly radioactive showed no apparent pe- culiarities or marked differences from other, less active waters, the high activity of the Ifugao waters seems to be due to isolated local deposits of radioactive material. Granite Extrusive Limestone Generalized geologic section across northern Luzon, from Tagudin to the eastern coast 2. and Shale ye a a ee ene eB ee ee ea eee Fic. Sandstone SS Malaya Pa xu,a,é Heise: Radioactivity of Waters, Northern Luzon 805 The general statements in the literature regarding radioac- tivity indicate that— The phenomenon is perhaps most common among waters of volcanic origin, or at least among thermal springs.” The present study seems to show that this generalization does not hold for Philippine waters, though the work is still too preliminary in character to justify positive statements. ™ Clarke, F. W., loc. cit., 215. ILLUSTRATIONS PLATE I. Apparatus used in a field determination of radium emanation. TEXT FIGURES Fic. 1. Map of a part of northern Luzon. 2. Generalized geologic section across northern Luzon, from Tagudin to the eastern coast. 307 ead GETS Tht omen crak Seen to ag re ate pene uh an caer eevthe ss | eet . Hetse, G. W.: RADIOACTIVITY OF WATERS, NORTHERN Luzon.] [PHIL. JourN. Scr, XII, A, No 6. af CS Loe > “€ PLATE |. APPARATUS USED IN A FIELD DETERMINATION OF RADIUM EMANATION. THE CONSTANCY IN THE RADIOACTIVITY OF CERTAIN PHILIPPINE WATERS By GEoRGE W. HEISE (From the Laboratory of General, Inorganic, and Physical Chemistry, Bureau of Science, Manila) Philippine springs and artesian wells frequently show great variations in flow. Many of them are appreciably augmented during the rainy season, and some, situated near the coast, flow only at high tide. However, so far as noted, the chemical qua- lity of deep-seated ground waters is not subject normally to marked variations, in spite of great fluctuations in the quantity of water.2 This observation is in harmony with experience in other countries.’ . The statements regarding the variation in emanation content of natural waters are somewhat confusing. Thus Ramsay * reported an increased emanation content in certain springs during periods of wet weather and great flow, whereas Steichen ° observed an increase in the activity in certain Bombay hot springs during the dry season, in a period of greatly reduced flow. The latter investigator pointed out that lecal conditions might well account for the differences noted. In a previous paper ° it was pointed out that two determina- tions of the radioactivity of Sibul Springs, one made during the dry season, the other during a period of frequent rains, indicated that, under certain conditions, the seasonal variations might be very slight. Recently it has been found possible to test this conclusion by further work both on Sibul Springs and on a flowing artesian well. Apparatus, method, and limits of accuracy were the some as‘those previously described.? The results obtained are shown in Table I. * Received for publication August, 1917. | * Heise, G. W., This Journal, Sec. A (1916), 11, 125-7. . *Hintz, F., and Kaiser, E., Zeitschr. f. prakt. Geol. (1915), 23, 122-6, through Chem. Abst. (1916), 10, 1741. *Ramsay, R., The variation of the emanation content of certain springs, Phil. Mag. (1915), 30, 815-818. * Steichen, A., The variation of the hot springs at Tuwa, Phil. Mag. (1916), 31, 401-3. * Wright, J. R., and Heise, G. W., The radioactivity of Philippine waters, This Journal, Sec. A (1917), 12, 145. * Wright and Heise, op. cit. Heise, G. W., The radioactivity of the waters of the mountainous region of northern Luzon, This Journal, Sec. A (1917), 12, No. 6. ; 309 8310 The Philippine Journal of Science 1917 TABLE I.—Variation in radium emanation content. | Radium Source. | D ate OE eontant a * i(asg.RaXx | 10-12.) — —_—-— = —— ———— | — re — Sibul Springs... 5 oc3. 5 ca a ack. ee Se eee April 10, 1916 | 1284 D0 3 ee ee icles aoe ee Ree OE Soe es July 9,1916 | 1293 ee ee ea See eee eee eee ee es ee OLE PE Ee eee April 22, 1917 1300 ne: doy 2a} 1280 Deeeec cece lae se poktman as Same ecl tee oetwene < -ceen ene eee June 9,1917 1330 Seiden ob cans SSanndewetaenncan acne smeat ones sane RAE ane See neree meee July 1,1917 1270 epee S58 EE ae eee Oe ee ee ees 8 ee ae ee So ee | July 15,1917 1280 Flowing well; Parafiaque; Rizal\so.2=--.0 --2..5-b sence - ase ee June 19,1916 632 dcteee deuce ieee wo ae aneetens mane RoR oe Eaen eee pee Ee Emenee June 2,1916 640 The. differences between determinations of the radioactivity of the same source at various times are well within the limits of experimental error in this class of work. Though the work on Sibul Springs was done in only.a few months in the year, determinations were made under greatly varied conditions. Si- bul Springs has a very large flow throughout the year, but the quantity of water changes appreciably with the season. The readings in April, 1916, and April, 1917, were made after pro- longed seasons of dry weather, at times of minimum water flow. Though there was no sharply defined rainy season in 1916, the July reading was taken during a period of frequent, though not very heavy, rains, at a time of increased flow. There was much heavier rainfall in 1917 than during the corresponding period in 1916, so that the July, 1917, readings were taken during a time of heavy precipitation and great flow. It is, therefore, reasonable to suppose that the readings noted are representative of the radioactivity of Sibul Springs through- out the year. The determinations of the activity of the Paranaque flowing well are too few in number to be conclusive; they are so. con- cordant, however, that they may be regarded as corroboratory evidence. The data at hand clearly indicate, therefore, that the radio- activity of a deep-seated ground water may remain remarkably constant for long periods. As the waters at Sibul Springs have been highly regarded for a long time because of their supposed medicina! virtues, they have been frequently analyzed. It is of interest to point out that surprisingly little, if any, change has been noted in the chemical character of the water for a long period of time. In XII, A, 6 Heise: Constancy of Philippine Waters 311 Table II are shown an analysis published by Centeno* in 1890 and a recent routine analysis made in the Bureau of Science. TABLE I].—Analyses of water from Sibul Springs. ! | Analyzed | Centeno, | by Bureau | ‘ Ingredient. 1890.8 | of Science, 1915.6 | | PT by TUG [Pg ee ee ea em oe ee, See eae 532 650 OS GT GO) recess ease er cee ce es Heseangee beep sorot ase stepmom Sserer =ece| 80 16 Prearnonntesy (EH GOSs)) cance coe senate ane ak Shine on oe dane nceeten cameoeaeat were | ATT 460 | Sulphates (SO) -__-_.__- eee ae eee a eae se ee | 13 | nil Me Mnride(G))ee se esa oe 1. ee er ay Sa ee nt Sor eren eeT 42 32 | Rialertrnnn (Ca) ee schenoe ace enact a oe mask on ena ae eee nee aman a aac 1538 150 EEE PARES EE FH (OE) RS See Be aps et 9 ce en Sn 17 14 “8 Recalculated as parts per million and to same terms as those used in standard practice. > Analyzed by F. Pena, chemist, Bureau of Science. Considering the length of time that has elapsed between the two analyses and the fact that the waters at Sibul Springs were neglected for a year during that interval, better agreement could be hardly expected. *Centeno, J., et al., Memoria descriptiva de los manantiales, ete. de la Isla de Luzon. Madrid (1890), 39. rr ea gh ee et 18 Aes his , any wee ec ” ad : i ie ae We INDEX Abar, 190. Abdong cahoy, 180. Abuab, 169. AGCAOILI, FRANCISCO, sce BRILL, HAR- VEY C., 261. Agelaea, 184. AGUILAR, R. H., A comparison of linseed oil and lumbang oils as paint vehicles, 235. Albihal, 171. Alcohol from discard molasses in the Philip- pine Islands, 267. Alegango, 190. Aleurites cordata, 2386. fordii, 236. moluccana, 167, 235. trisperma, 167, 236. ALINCASTRE, CECILIO, see BRILL, HAR- VEY C., 127. Alstonia scholaris, 167. Anisoptera thurifera, 111. Api-api, 111. Apitong, 111. Argemone mexicana, 167. ARGUELLES, ANGEL WILLIAM H., 221. Asclepidacese, 174. Aspergillus flavus, 67. niger, 66. Atangen, 177. Avicennia officinalis, 111. B S., see BROWN, Babebabe, 172. Bacauan, 111, Bagtican lauan, 230. Bailey, E. H/AS., see Reviews (book). Balangcari, 190. Balitadhan, 172. Balobo, 224. Batingui, 169. Bayabayabasan, 180. Berberis aristata, 178. Bo-nor, 172. Brick and mortar, composition of, in the great wall of China, 257. BRILL, HARVEY C., The antineuritic prop- erties of the infusorial earth extract of the hydrolyzed extract of rice polishings, 199; A chemical investigation of the seeds of Pangium edule and of Hydnocarpus alcalz, 387; The fermentation of Philippine cacao, 1; see also PARKER, HARRISON O., 87. BRILL, HARVEY C., and AGCAOILI, FRANCISCO, Some limitations of the Kjeldahl method, 261. | BRILL, HARVEY C., and ALINCASTRE, CECILIO, The possible maximum vitamine content of some Philippine vegetables, 127. BRILL, HARVEY C., and PARKER, HAR- RISON O., The rancidity of Philippine co- conut oil, 95. BRILL, HARVEY C., PARKER, HARRISON O., and YATES, HARRY S., Copra and coconut oil, 55. BRILL, HARVEY C., and THURLOW, LEA- VITT W., Alcohol from discard molasses in the Philippine Islands, 267. BRILL, HARVEY C., and WELLS, ALBERT H., The physiological active constituents of certain Philippine medicinal plants: II, 167. BRILL, HARVEY C., and WILLIAMS, RO- BERT R., The use of chaulmoogra oil as a specific for leprosy, 207. BROWN, WILLIAM H., and ARGUELLES, ANGEL S.; The composition and moisture content of the soils in the types of vegeta- tion at different elevations on Mount Ma- quiling, 221. Bruguiera parviflora, 111. Bugkan, 177. Buyun, 169. Cc Cacao, the fermentation of Philippine, 1; properties of butter from Philippine, 11. Cacaocacaoan, 180. Caesalpinia bonducella, 167. sappan, 167. Calamantao, 171. Calcium sulphate, the effect of, on cement, 133. Camagsa taquilis, 185. Camagsang baguing, 184. Camunin, 186. Cataban, 225. Catmon, 169. Caua, 87. Cayutanang baguing, 177. Celastracez, 169. Cement, the effect of calcium sulphate on, 133. Charcoal, analysis of bacauan, 121. Chaulmoogra oil as a specific for leprosy, 207. China, composition of brick and mortar in the Great Wall of, 257. Chloride of lime, the interaction of, with the normal constituents of natural waters and sewage, 17. Cnestis, 184. Coconut oil and copra, 55. Coconut oil, methods for the production of pure, 87; the rancidity of Philippine, 95. Coconut products, the study of copra and other, 49. Cogon, 223. Combretacex, 172. Congoura, 188. Connaracez, 184. 3138 —— Se 314 Index Connarus, 184. Copra-drying methods in use, 76. Copra, coconut oil and, 55; the study of, and other coconut products, 49. COX, ALVIN J., The study of copra and other coconut products, 49. Cratoxylon celebicum, 225. D Dail, 174. Dalinding, 169. Datura fastuosa, 167. Dauag, 177. Dauag manoc, 177. Dayandag, 169. Dillenia philippinensis, 169. Diplodiscus paniculatus, 224. Dipterocarp forest, 224. Dipterocarpus sp., 111. Distillation, destructive, of Philippine woods, 111. Dudu dudu, 44. E Elatostema, 225. Entada scandens, 167. Erythroploeum densiflorum, 171. guineense, 171. Erythroxylon burmanicum, 167. Exostemma philippicum, 190. G Gangé, 184. Gata, 87. Gelsemium sempervirens, 194. Great Wall of China, composition of brick and mortar in the, 257. Guayacan, 186. Guicos guicos, 185. Guijo, 111. Guyong guyong, 225. Gynocardase, 42. Gynocardia odorata, 87, 208. Gynocardin, properties of, 39. H Hanmabao, 185. HEISE, GEORGE W., The constancy in the radioactivity of certain Philippine waters, 809; The crater lake of Taal Voleano, 247; The interaction of chloride of lime with the normal constituents of natural waters and sewage, 17; The radioactivity of the waters of the mountainous region of northern Lu- zon, 293; see also WRIGHT, J. R., 145. Hopea sp., 111. Huliganga, 190. Hydnocarpus alcale and Pangium edule, a chemical investigation of the seeds of, 37. Hydnocarpus alcalze, 209. anthelmintica, 219. venenata, 37, 208. wighttiana, 208, Hymenodictyon excelsum, 190. obovatum, 190. I Iluhan, 88. Imperata exaltata, 223. Infusorial earth extract, the antineuritic prop- erties of the, of the hydrolyzed extract of rice polishings, 199. Intsia bijuga, 111. Ipil, 111. J Jatropha cureas, 167. K Kjeldahl method, some limitations of the, 261. Kukui, 235. L Labao, 180. Lake, crater, of Taal Volcano, 247. Langarai, 111. . Lanitan, 169. Lauan, white, 111. Leguminosz, 171. Lenamo, 184. Leprosy, the use of chaulmoogra oil as a specific for, 207. ‘ Linseed oil, a comparison of, and lumbang oils as paint vehicles, 2385. Lophopetalum fimbriatum, 170. toxicum, 169. Lubilubi, 180. Lumbang banucalag, 236. Lumbang bato, 235. Lumbang oils, a comparison of linseed oil and, as paint vehicles, 235. Lunas, 180. Lunas bondoc, 180. Lunas na puti, 180. a Lunasia amara, 180. costulata, 181. Luzon, the radioactivity of the waters of the mountainous region of northern, 293. M Mag-talisay, 190. Malabunao, 171. Malacacao, 180. Malagranada, 184. Malaligas na babde, 180. Malasanqui, 180. Malatabaco hibao, 190. Malatabigui, 171. Malatuba, 225. Maquiling, Mount, the composition and mois- ture content of the soils in the types of vegetation at different elevations on, 221. Mavindato, 185. Medicinal plants, the physiological active con- stituents of certain Philippine, 167. Microérganisms and their effect on copra and coconut oil, 63. Molasses, aleohol from discard, in the Phil- ippine Islands, 267. Mold, black, 66, brown, 67. green, 69. white, 64. N Narra, 111. Neolitsia villosa, 225. | Neiriengic, i71. ,Niogniogan, 172. Index Oo Oreocnide trinervis, 225. = Paetan, 180. Paint vehicles, a comparison of linseed oil and lumbang oils as, 235. ; Pait, 180. Paitan, 180. Pait-pait, 180. Palo santo, 184. Palosapis, 111. Pangium edule, 209. Pangium edule and Hydnocarpus alcal, chemical investigation of the seeds of, 87. Parashorea plicata, 224. Parastaca plicata, °230. PARKER, HARRISON O., and BRILL, HAR- VEY C., Methods for the production of pure coconut oil, 87; see also BRILL, HARVEY C., 55, 95. Pasuca, 174. Penicillium glaucum, 69. Pentacme contorta, 111. PENA, F., review of Bailey's A Laboratory Guide to the Study of Qualitative Analysis, 47. Philippine cacao, the fermentation of, 1. Philippine coconut oil, the rancidity of, 95. Philippine medicinal plants, the physiological active constituents of certain, 167. Philippine vegetables, the possible maximum vitamine content of some, 127. Philippine waters, the radioactivity of, 145. a Philippine woods, destructive distillation of, | LE Pine, Benguet, 111. Pinus insularis, 111. Pifiones, 172. Plants, Philippine medicinal, the physiological active constituents of certain, 167. Poonac, 88. Pterocarpus sp., 111, Puti-i-babae, 169. Puti-i-lalaque, 169. Q Quercus solariana, 225. Quisqualis indica, 172. R Rabelaisia, 180. Radioactivity of Philippine waters, 145; of the waters of the mountainous region of northern Luzon, 293; the constancy in the, of certain Philippine waters, 309. Radix indica lopeziana, 177. REVIEW: Baily, E. H. S., A Laboratory Guide to the Study of Qualitative Analysis, 47. REYES, F. D., see WITT, J. C., 133. Rhizophora sp., 111. Rhizopus sp., 64. Rice polishings, the antineuritic properties of | the infusorial earth extract of the hydrolyzed extract of, 199. 1510344 315 Rourea erecta, 184. heterophylla, 185. volubilis, 184. Rubiacesx, 190. Rutacez, 177. Ss) Saccharomyces, 273. Saccharum spontaneum, 223. Saguit, 180. } Salsal, 171. Saltiqui, 180. Santiqui, 180. | Saruncad, 174. Sarungear, 174. | Sauraunia barnsii, 225. | Sayoncal, 174. | Seeds, a chemical investigation of the, of Pangium edule and of Hydnocarpus alcale, | Selaginella, 225. Sewage and natural waters, the interaction of chloride of lime with the normal con- stituents of, 17. Shorea guiso, 111. polysperma, 111. | Soils, the composition and moisture content of the, in the types of vegetation at different elevations on Mount Magquiling, 221. Strobilanthus plurifomis, 225. Strombosia philippinensis, 169. Sudead, 169. | Sulphur dioxide, preparing copra by use of, 80. AY Taal Volcano, the crater lake of, 247. Tagarao, 172. Talahib, 223. Tal-lolang, 172. Talolon, 172. Talulong, 172. Tamauyan, 169. Tangolo, 172. Tangolong, 172. Tanguili, 111. Tangulong, 172. Tapahan method, 51. Taraktogenos, 37. kurzii, 208. Tars, 118. Tartaro, 172. Tartaraoc, 172. Taungon, 172. THURLOW, LEAVITT HARVEY C., 267. Tinospora crispa, 167. Toddalia aculeata, 178. asiatica, 177. Tubo-bat6, 199. | Tylophora asthmatica, 176. brevipes, 174. W., see BRILL, | U | Ungali na mapulf magtabig, 185. 316 Index Vv Vegetables, Philippine, the possible maximum vitamine content of some, 127. Vitamine content, the possible maximum, of some Philippine vegetables, 127. Ww Water, absorption of, by copra, 73. Waters, the interaction of chloride of lime with the nermal constituents of natural and sewage, 17; the constancy in the radioac- tivity of certain Philippine, 309; the radio- activity of Philippine, 145; the radioactivity of the, of the mountainous region of northern Luzon, 293. WELLS, A. H., Destructive distillation of Philippine woods, 111; see also BRILL, HARVEY C., 167. WILLIAMS, ROBERT R., see BRILL, HAR- VEY C., 207. WITT, J. C., Composition of brick and mor- tar in the Great Wall of China, 257. WITT, J. C., and REYES, F. D., The effect of calcium sulphate on cement, 133. Woods, destructive distillation of Philippine, 111. WRIGHT, J. R., and HEISE, GEORGE W., The radioactivity of Philippine waters, 145. pg Yacal, 111. YATES, HARRY S., see BRILL, HARVEY C., 56. O Wes ene Ena Po ‘ Mapu of. Wo. 419. Pao 420 6 Vi; “postoalds. ma - Practical! uanntetn flora of the! a3 vate ateeile o* the Philippines. Bogie with: Keys, of. over 1,000 - asa oan : anes milles, with hat nocee terms, ator a e Pr eamep ot joplde. Dipteroonrp. Forests reset w Very. papnt behave rer he growth’ and: development: of dip: trees \and “of © fies other, elements of _ Iuoaatayn “Wodds, Dactor. “Foo jb together a. eyamount ges information » concerning: . Meee. ng ‘woods. of economic value. : Y ST * ‘0 Fe OF | MAMMATS: OF © THE: Htestee ISLANDS, EXCLU vig SIVE OF THE C The: distrabution of each spdoles ae the original: -desosiotione are shea ¥e ree ARE alee, ‘CURRENCY pany;, 64-6 6 Fitth Order Now! 103.' ae peace! us We } Paper, a pats 769) Pages, $4, -postpald,” ; i anual. {Philippine Gaui alae AR -oampact | “form. descriptions of: all. the” known hate of Philippine: birds.’ The ‘Usual “Keys. pre nip the not of Paden, fariities, ° and” amigsen nowide In’ bye opti Rn'$ fils. list, wiit ‘ba found’ to. the aaah, of. Philippine, abies Thies nomenclature, is. thoroughly’ revised, 'a the ‘distribution ‘of each species. wit! i Pisihepat ah Blane, It ailye she * oamdroore OF Spade peatie: COLEQETERA’ “This Gatiltauce? Iiehéaest tha) names ok atl Jspecies of Coleoptera that have beén recorded: from: a definite locality ap. the’ Phifipping f ‘References +6 original descriptions. and’ other important» notes afe-given, The: ‘.eeonomig’ appendix. includes: /oomment. on! ‘those spectes of beetles. which ate known, to's “be. sinuous: oF bentiotst: ee, eres ie Hae ry : a » re periek New York, tr a5 s. Fae Wesley &: ‘Son’ 28 Essex. Street, Strand,’ London, W, Gy England Marton: Papel Lange Voorhout 9,,The Hague, Holland. Mayer 1 Pring. Lonis Ferdinandstrasse 2, Berlin N. W., Gerw roth aes Ltd., 32 Rafi Singapore, Straits Settleme Ferguson, 19 Balltie. ptrect Colonind, Ces a. eee f Cor», ming Box $4, acral as see “WON WW 9088 01307 6