BOSTON PUBLIC LIBRARY
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3 9999 06317 757 8 2 •
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METABOLISM OF PESTICIDES
UPDATE II
UNITED STATES DEPARTMENT OE THE INTERIOR
EISH AND WILDLIFE SERVICE
Special Scientific Report- Wildlife No. 212
METABOLISM OF PESTICIDES
UPDATE II
By Calvin M. Menzie
UNITED STATES DEPARTMENT OF THE INTERIOR
FISH AND WILDLIFE SERVICE
Special Scientific Report— Wildlife No. 212
Washington, D.C. • 1978
^D W.V.0^
TABLE OF CONTENTS
Page
Introduction xiii
Acknowledgment xiv
Abar 163
Acarol 51
Accothion 254
Acephate 193
Acephate-met 193
Alar 1
Aldicarb 2
Aldrin 4
Allyl alcohol 18
Ametryne 271,272
Ami nopyri dine 19
Aminotriazole 20
Aniline 21
Aniten 142
Aresin 297
Aroclor 206
Arsenate, sodium 23
Arsenicals 23
Arsenite, sodium 23
Asulam 24
Asulox 24
ATA 20
Atrazine 271,273
Azinphosmethyl 25
Banvel 112
Bas 392 26
Basalin 26
Bay 68138 195
Bay 94337 278
Benazolin 27
Benefin 28
Benlate 29
Benomyl 29
Bentazon 35
Benthiocarb 261,262
Benzoyl chloride trichlorophenyhydrazide 36
Benzoyl prop-ethyl 37
n
Page
Betanal 222
BHC 38
Bidrin 116
Bio-allethrin 236
Bioresmethrin 234
Bi phenyl 45
Blasticidin S 47
Botran 49
BPBSMC 50
BPMC 50
Bromacil 288
Bromopropylate 51
Bromosimazine 271
Bromoxynil 52
Busulfan 53
Buturon 290
Butyl dinitroaniline 119
Butylate 261
C 709 116
C 2307 54
C 6989 141
Cacodylic Acid 23
Calixin 284
Captan 55
Carbaryl 56
Carbendazim 29
Carbicron 116
Carbofuran 60
Carboxin 63
CCC 75
CDAA 65
Cela W524 287
CEPA 66
Chevron RE 5365 50
Chevron RE 11775 50
Chloral hydrate 67
Chlorbromuron 291
Chlordane 68
Chlordene 68
Chlordimeform 74
Chlormequat 75
Chlorodioxin 76
Chloronaphthalene 219
m
Page
Chloroneb 78
Chi orop ropy late 51
Chlorothalonil 79
Chlorpropham 80
CIPC 80
Clophen 206
Clopidol 83
Cobeko 121
Cobex 121
Counter 256
Credazine 84
Cyanazine 276
Cyanide 85
Cycloate 261
Cyolane 86
Cyprazine 276
2,4-D 88
Dasanit 139
DBNPA 94
DCB 95
DCNA 49
DD 114
DDD . 98
DDE 98
DDOD 96
DDT 98
DDVP 115
Demosan 78
Destun 105
Dexon 106
Dial late 261
Dianisylneopentane 107
Diazinon 109
Dibromo nitrilopropionamide 94
Dicamba 112
Dichlobenil 113
Dichloroanisic acid 112
Dichlorobenzene 95
Dichloropropene 114
Dichlorvos 115
Dichlozoline 96
Dicofol 98
Dicrotophos 116
Dicryl 117
IV
Page
Dieldrin 4
Diethamine 121
Diethion 136
Diflubenzuron 292
Dimecron 223
Dimethoate 118
Dimi
Dim'
Dim'
Dim
Dim'
Dim'
lin 292
tramine 121
tro compounds 119
troaniline, methyl -propyl -t-butyl 124
troaniline, sec, butyl -t-butyl 119
trodi propyl cumi dine 123
Dinobuton 120
Dinoseb 120
Diphenamid 125
Di phenyl 45
Diquat 126
Disugran 112
Disyston 127
Dithiocarbamate 128
DNBP 120
DS 15647 130
DuPont 1179 184
DuPont F 1991 29
Dyfonate 131
Dymid 125
EBC 29
EDB 132
Edifenphos 149
Ektafos 116
EMD-IT 3233 142
Endosulfan 133
Endothall 135
Endrin 4
Enide 125
ENT 27696 267
E0 137
EPTAM 261
EPTC 261
Ethion 136
Ethoprop 192
Ethoxychlor 185
Ethylene di bromide 132
Page
Ethylene oxide 137
Ethyl propylphosphonate 197
ETO 137
ETU 128
Fenazaflor 138
Fenitrothion 254
Fensulfothion 139
Fentin 266
Flu 140
Fluchloralin 26
Fluenethyl 140
Fluometuron 294
Fluoroacetate 140
Fluorodifen 141
Fluorosimazine 271
Flurecol 142
Flurencol 142
Flurenol 142
FMC 1103 243
Folpet 55
Formetanate 143
Frescon 144
Fulvicin 147
Furadan 60
Furamethrin 237
Galecron 74
Gardona 145
Glyphosate 146
Gramoxone 126
Griseofulvin 147
GS 13005 182
HCB 148
HCE 4
HCH 38
HEOM 4
Heptachlor 68
Hinosan 149
Imidan 151
VI
Page
Iodoatrazine 271
Iodopropazine 271
Iodosimazine 271
Ioxynil 52
IPC 80
Irgasan DP 300 152
Isodrin 4
Isopropalin 123
Isopropyl carbanilate 80
Isopropyl chlorocarbanilate 80
Isopropyl dibromobenzilate 51
Isopropyl dichlorobenzilate 51
Isoxathion 153
IT 3233 142
Kanechlor 20b
Karphos 153
KC 206
Kelevan 155
Kelthane 98
Kepone 155
Kerb 229
Kitazin 159
L 34314 125
Lambrol 140
Landrin 161
Lannate 184
Lauryl valine 162
Leptophos 163
Linuron 295
Lovozal 138
Luprosil 164
Mafu 115
Malathion 165
Maleic hydrazide 167
Maneb 128
Matacil 168
MBC 29
MBT 296
MCA 29
MCPA 92
VI l
Page
Meobal 169
Mercury compounds 170
Mesurol 178
Methamidophos 193
Methazole 179
Methbenzthiazuron 296
Methidathion 182
Me thorny 1 184
Methoxychlor 185
Methylchlor 188
Methyl enedioxy compounds 190
Methyl guthion 25
Methyl propyl butyl dinitroanil ine 124
Metribuzin 278
Mexacarbate 301
MH 167
Mi rex 155
Mobam 191
Mocap 192
Molinate 261
Monitor 193
Monolinuron 297
Monuron 298
NAA 194
NC 2983 138
NDA 196
Nemacur 195
Neodecanoic acid 196
Neo-Pyamin 243
Neoron 51
NF 48 29
NIA 9260 243
Niagara 10637 197
Nitrapyrin 198
Norflurazone 253
N-Serve 198
Nuvan 115
OMS 1804 292
Ordram 261
Orthene 193
Ortho 9006 193
Oryzemate 199
vm
Page
Oxadiazon 200
Oxydiazol 179
Oxycarboxin 63
Paraquat 126
Parathion 202
Parbendazole 29,32
PCB 206
PCN 219
PCNB 220
PCP 221
Pebulate 261,264
Perf luoridone 105
PH 6040 292
Phaltan 5b
Phenisobromolate 51
Phenmedipham 222
Phenoclor 206
Phenothrin 238
Phosphamidon 223
Phosvel 163
Phthalthrin 243
Picloram 224
Piperonylic acid 190
Pirimiphos-methyl 226
Plantvax 63
Preforan 141
Probe 179
Prolan 227
Prometone 280
Prometryne 271
Pronamide 229
Propanil 230
Propazine 271,281
Propham 80
Propionic acid 165
Proximpham 231
Pyramin 232
Pyrazon 232
Pyrethrin 234
Ouintozene 220
IX
Page
R 7465 245
Racuza 112
Randox 65
Resmethrin 239
Rhothane 98
Robenidine 247
Robenz 247
Ro-Neet 261
Rotenone 249
S 1358 250
S 2539 238
Salithion 252
San 6706 253
San 9789 253
SD 3562 116
Saturn 261,262
Sencor 278
Sevin 56
Simazine 271,282
Simetryne 271
SP 1103 243
Suffix 37
Sumithion 254
Supracide 182
Sutan 261
2,4,5-T 93
Tamaron 193
TBZ 259
TDE 98
Tenn'k 2
Terbufos 256
Terraclor 220
Terracur 139
Tersan SP 78
Tetramethrin 243
TFM 257
TH 60-40 292
Thiabendazole 259
Thiodan 133
Thiofanox 130
Thiolcarbamates 260
Thiophanate 29
Page
Thiophanate-methyl 29
TIBA 265
Till am 261,264
Tin compounds 266
Tirpate 267
Toluenesufenyl carbofuran 62
Toxaphene 268
TPE 29
TPM 29
Triallate 261
Triazine 270
Tribunil 296
Tn'demorph 264
Trifenmorph 144
Trifluralin 285
Triforine 287
Uracil 288
Urea 289
USB 3584 121
Vapona 115
VCS 438 179
VCS 506 163
Vernam 261
Vernolate 261
Vitavax 63
Warfarin 300
WL 8008 144
WL 9385 283
Zectran 301
Zineb 128
1080 140
Bibliography 303
Bibliography - Addendum 378
XI
Page
Appendix I Effect of Temperature on Carbamate
Insecticides 379
Appendix II Jjn Vivo Inhibition of Live Arylamidase . . . 380
Appendix III Effect of Substitution in Parathion
Analogs 381
XI 1
Metabolism of Pesticides
Update II
by
Calvin M. Menzie
U.S. Fish and Wildlife Service
Division of Habitat Preservation-Research
Washington, D.C. 20240
INTRODUCTION
This publication supplements the preceding Metabolism of
Pesticides (1969) and Metabolism of Pesticides -- An Update (1974).
Readers are also advised that, during the period from preparation
to printing of this volume, a considerable additional literature
on this subject matter has been published.
xm
ACKNOWLEDGMENTS
I should like to express my appreciation to the following
people who have graciously given of their time to read this manuscript
and who have offered helpful suggestions:
R. Barron (NIEHS) P. Datta (EPA)
C. Collier (EPA) D. Severn (EPA)
H. Day (EPA) G. Zweig (EPA)
and to Marge Bader and Larry Koehler for their diligence and patience
in the preparation of the manuscript.
xiv
ALAR [Succinic acid 2,2-dimethylhydrazide]
N-Methyl-ll4C- labeled alar was applied to four soils under greenhouse
conditions. The data indicated that microbial degradation was the
major route of alar dissipation from soil. The half-life of alar
war 3 to 4 days on all soils and the major degradation product was
11+C02. In 14 days, about 84% of the label was recovered as 14C02
and most of the remainder of the lkC was associated with the soil
organic matter (Dannals et al . , 1974).
ALDICARB (Tenik) [2-Methyl -2- (methyl thio)propionaldehyde 0-
(methyl carbamoyl )oxime]
Five soil fungi were tested in culture media for their ability to
degrade aldicarb. The results indicated the following order of
effectiveness: Gliocladium catenulatum > Penicill ium multicolor =
Cunninghamella elegans > Rhizoctonia sp. > Trichoderma harzianum.
Metabolites found included aldicarb sulfoxide and sulfone, nitrile
sulfoxide and sulfone, and oxime sulfoxide and sulfone. A
considerable amount of water-soluble metabolites were also observed,
including the alcohol and amide sulfones and sulfoxides. Small
amounts of the acid sulfone and sulfoxide were also observed
(Jones, 1976).
In soil treated with aldicarb, the sulfoxide and sulfone were
observed (Jamet et al . , 1974).
After administration of a single dose (0.7 mg/kg) of Temik-S35
to hens, about 1% of the radioactivity was observed in eggs over
a 10-day period. Analyses of tissues, eggs and feces showed the
presence of the sulfoxide and sulfone metabolites (Hicks, 1970).
Boll weevils (Anthonomus grandis Boheman) and houseflies (Musca
domes tica L. ) were treated with carbonyl-^C-aldicarb. Following
topical application of the insecticide, aldicarb disappeared
rapidly. The sulfoxide was the major non-conjugated metabolite
in boll weevils and houseflies. The sulfone formed subsequently
in smaller amounts. 11+C02 detected was very small. Water soluble
products that formed were suspected of being conjugated metabolites
but were not identified (Andrawes and Dorough, 1970).
ch -s-c-ch=noh
£h3
Aldicarb oxime
(VII)
CH.
CH3
J-CH=NOH
Aldicarb oxime
sulfoxide(VIII)
Sulfoxide alcohol
Conjugate
CH3 0
CH_-S-C-CH=N-0-C-fd!,
CH3
CH3-S-C-CH=N-0-C-N^„
Aldicarb sulfoxide(II)
0
CH -'^-C-CH=N-0-C,-NH.
Aldicarb N-demethyl
sulfoxide (XV)
0
ch=n-o-c-nC-u
^-M3
Aldicarb sulfone(III)
CH
,4U-
1 » i
0 CH,
=N-0-C-NH„
0
it H
°"C"NXH20H
Aldicarb N-CH OH sulfone
(IV)
Aldicarb N-demethyl
sulfone (XVI)
I
CH.
-(?H=N0H
QfH3
^X* Aldicarb oxime
Nitrile
sulfoxide(X)
\
0 CH „
CH_ ""5"C-Cviliu
3 fcH^NH2
Sulfoxide amide
/ (XI)
0 CH.
C-CN sulfone (V)
CH, . * ,
0 CH
Nitrile
sulfone(XIV)
u CH
cH3-!U-d*
CH -
it I
51
■CHO
H,
\
*T A. -*
Conj.
I I 3
ffll&O / I fa
^6cH3^2]/CH3t^H20H
Sulfone amide / Sulfone a13cohol
" 0 CH, T
CH3-s'-C-C^,
&>
Sulfoxide acid
(XII)
CHi1Hc3v°H
Sulfone acid(XIII)
cohol(VI)
Conjugate
-' :•--
1,8,9,10,11 ,11 -Hexachloro-2,3-7, 6- endo-2.1-" . :-e«;o-tetracyc1o
~J.ir.":-z- ::";:::e;--.r-:--e
I" =* --~~
' .: .9,10,11 ,11 -Hexa:-" :-:--.:- = = :-;::=•-:. ':-' . f-endo-2, 1-7, 8-exo-
:e: -=: . :" z'.z.l.' .' - •"' :; ■""::: = : -.:- =- =
1 ,8,9,10,11 ,11-Hexach1oro-2, 3-7, 6-endo-2, 1-7, 8-endo-tetracyclo
If.:/ ." : :: ;:::e:-^.r-: ee
,8,9,10,11 ,ll-Hexachloro-4,5-ej»-epoxy-2,3-7 ,5-endo-2,l-7,8-endo-
-":---
Dieldrin
-■
. : '.'
When labeled trans-4,5-aldrindiol was administered to rats, a small
portion (6%) of the radioactivity was excreted as a polar metabolite
which was identified as the hexachloro-tetrahydroindane-1 ,3-
dicarboxylic acid (dihydrochlordene dicarboxylic acid) by TLC, GLC,
IR and mass spectrometry (Oda and Muller. 1972). This compound
was administered with labeling intravenously to rats. The
radioactivity was rapidly excreted and almost half consisted of
metabolites. Of the nine compounds isolated from feces and urine,
three have been identified as: dihydrochlordene dicarboxylic acid
dimethyl ester; and two isomers of the monodechlorinated dihydro-
chlordene dicarboxylic acid. Two compounds were \iery polar and,
after hydrolysis with methanol/HCl , could be methylated to form
the dimethyl ester of dihydrochlordene dicarboxylic acid. The
other four compounds have molecular weights ranging from 244 to
336 and four to six chlorines (Lay et al . , 1975).
Dieldrin was administered intravenously to rhesus monkeys. Excreta
was collected and four metabolites were isolated by TLC. Three
were identified: 12-hydroxydieldrin; 4,5-aldrin-trans-dihydrodiol
and a glucuronic acid conjugate of the diol (Muller et al . , 1975b).
The same metabolites were found in urine of Swiss white mice,
Sprague-Dawley rats, New Zealand white rabbits, and a female
chimpanzee when they were fed dieldrin (Muller et al . , 1975a).
In other studies, aldrin- trans- dihydrodiol and the di- acid were
observed in treated rats and mice. The pentachloroketone was also
excreted by rats but not the mice. Rhesus monkeys excreted 9-
hydroxydieldrin but no pentachloroketone. Bile contained the
glucuronide of 9-hydroxydieldrin (Baldwin, 1971).
Using microsomal preparations, the conversion of aldrin to dieldrin
was found to be much slower in trout liver microsomes than in male
rat liver microsomes (Chan et al . , 1967).
Mixed function oxidase (MFO) activity in liver of bluegill (Lepomis
macrochirus) converted aldrin to dieldrin in the presence of NADPH.
Optimal activity occurred at pH 8.2-8.4 and 22-26C. Bass (Micropterus
dolomeiux) MFO was linear with aldrin for 4.6 min at pH 7.4 and 25C.
Mouse MFO also epoxidized aldrin to dieldrin (Stanton and Khan,
1973).
Hepatic mixed function oxidase with aldrin substrate
Epoxidation Vmax Km
Bluegill (adult) 0.62 8.58
Bluegull (fry) 1.72 6.98
Bass (fry) 1.72 5.97
Aldrin
H .OH
I
Aldrin ketone Dihydrochlordene
dicarboxylic acid
cu-^rp
trans-Diol
N,
Glucuronide
Vmax Hepatix mixed- function oxidase
Dieldrin Photodieldrin Endrin
Bass (fry) 1.19
Bluegill (fry) 1.45 - 0.81
Mouse 3.35 2.15 1.17
(Stanton & Khan, 1973)
Susceptible and resistant mosquitofish (Gambusia affinis) were
treated with 14C-aldrin. Resistant fish converted aldrin to
dieldrin and other unidentified materials at a greater rate than
did susceptible fish (Wells et al . , 1973).
When hepatopancreases from male lobsters (Homarus americanus) were
incubated with aldrin, dieldrin was formed. The pH optimum was 8.0
and greatest activity was observed in the 105,000xg soluble fraction
(Carlson, 1974).
The freshwater ostracod [Chlamydotheca arcuata (Sars.)] metabolized
aldrin to dieldrin. No metabolism of dieldrin was observed (Kawatski,
1970).
Resistant and susceptible strains of the house fly (Hylemia antigua)
metabolized aldrin to dieldrin at the same rate when aldrin was
applied at the rate of 0.02 ug/fly. At 25 yg/fly, metabolism of
aldrin by the resistant strain was ^ery low (Temizer, 1970).
Radiolabeled dieldrin was observed in hemolymph of adult male
Periplaneta americana and P_. brunnea after application of lhC-
aldrin to the pronotum. There were indications that dieldrin was
bould to a protein of about 18,900 MW and two groups of proteins
of MW > 160,000 (Olson, 1973).
Larvae of Hel iothis zea and He! iothis virescens metabolized aldrin
to dieldrin. Larvae of the latter exhibited a greater rate of
conversion. Most of the labeled material used was excreted as
metabolites more polar than dieldrin. Treatment with HC1 indicated
that these polar metabolites were primarily conjugated. None were
identified. Within 24 h of treatment with labeled aldrin, H. zea
excreted the radioactivity as aldrin (5%), dieldrin (12%), and
polar metabolites (83%). With H. virescens, it was 3, 5 and 92%,
respectively (Plapp, 1973).
Pea and bean root preparations degraded aldrin to a series of
related polar metabolites (in addition to dieldrin, aldrin ketone,
cis- and trans-aldrin diols, and exo-aldrin alcohol). Exo-aldrin
alcohol gave rise to traces of aldrin ketone. An unidentified
major component was observed and thought to be 12-hydroxydieldrin
from GC relative retention times.
An isomer of dieldrin, possibly the endo-epoxide isomer, was also
observed (McKinney and Mehendale, 1973). The aldrin epoxidase
enzyme from peas is particulate and not soluble. Almost all activity
was located in the pellet from centrifugation at 250,000xg.
Epoxidation of aldrin was not stimulated by addition of NADPH to
high centrifugation fractions. Addition of Mg++ inhibited the
reaction but the addition of ~\0~k M p_- ami no ben zoic acid increased
the activity of dwarf bean root homogenates. The results of the
studies suggested the presence of two or more aldrin epoxidizing
systems (Mehendale, 1973). In other studies cell-free pea root
preparations metabolized aldrin to dieldrin. In 0.02 M phosphate
buffer, the optimum pH was 6.5. The reaction increased up to 35C
and decreased thereafter. In these studies, a need was not shown
for the cofactors NADPH2 and Mg++ (Oloffs, 1970).
In Japanese soils, on which organochlorine compounds has been
sprayed for 2-20 years, photodieldrin was observed in 14 of 52
soil samples tested (Suzuki et al . , 1974). Ten years after a
single application of aldrin to soil, dieldrin and photodieldrin
were detected (Lichtenstein et al . , 1971).
Maize and wheat were grown in soils treated with aldrin-^C at
locations in Europe and the U.S. Aldrin-ll*C treated wheat seeds
were also planted. When the grains were harvested, residues in
the grain did not exceed 0.01 ppm. The main labeled products
identified in soils and plants from all locations were dieldrin,
dihydrochlordene dicarboxylic acid, photodieldrin, aldrin and some
unidentified acidic and non-polar compounds (Weisgerber et al . ,
1974). Sugar beets grown in soil treated with ll*C-aldrin, gave
similar results. At harvest, dieldrin and a group of hydrophylic
compounds comprised more than 95% of the luC-label recovered from
soils. Besides dihydrochlordene dicarboxylic acid, photodieldrin
and two minor acidic compounds not identified were observed
(Kohli et al., 1973).
In England and Germany, aldrin-ll+C was applied to soils outdoors
and potatoes were sown. Traces of aldrin were found in potato
hulm and peeled tubers. Small amounts of aldrin were detected in
the peel. The main metabolite in potato samples and upper soil
layers from Germany was dieldrin. In the potato hulm from England,
but not from Germany, a compound was observed which behaved like
photodieldrin. Small amounts of photoaldrin were also observed.
In all samples, after aldrin and dieldrin, most of the radioactivity
recovered was in the form of hydrophilic material. The main
8
compound was identified as dihydrochlordene-11+C-dicarboxylic acid
(1 ,2,3,4,8,8-hexachloro-l ,4,4a,6,7,7a-hexahydro-l ,4-ejido-methylene-
indene-5,7-dicarboxylic acid). Formation of this acid apparently
does not take place via dieldrin (Klein et al . , 1973).
Vapor phase ultraviolet irradiation of aldrin gave rise to photo-
aldrin, dieldrin and photodieldrin. Irradiation of dieldrin
produced photodieldrin (Crosby and Moilanen, 1974).
Diquat inhibited microsomal aldrin epoxidation. I50 = 6.6xlO"6M
(Krieger et al . , 1973). Fenton's reagent, modified by addition of
bovine serum albumin, effected epoxidation of aldrin (Marshall, 1972)
Rat liver preparations transformed dieldrin in vitro to the cis-
and trans^ isomers of dihydroaldrindiol . An epimerase, also present
in the same fraction of rat liver homogenate, rapidly epimerized
the cis-isomer to the trans- isomer. The epimerase, located in the
microsomes, required NADPH and cytochrome P-450 but not molecular
oxygen (Matthews and McKinney, 1974).
A major animal metabolite of dieldrin was identified as the syn-9-
hydroxy derivative. When photolyzed, it rearranged to form an
isomer analogous to that of the photosiomer of HEOD. The syn-9-
hydroxydleldrin was oxidized to 9-keto-dieldrin by refluxing for
1 h at 100C in a saturated solution of chromium trioxide in dry
pyridine. Reduction of the ketone with sodium borohydride gave a
product identified as 9-anti-hydroxydieldrin. Neither by photolysis
nor after oral administration to a male CFE rat was the 9-anti-
hydroxydieldrin converted to the pentachloroketone metabolite of
dieldrin (Baldwin et al . , 1973 and 1974).
Dieldrin half-life in lake water was 4.7 days. When freshwater
mussels were exposed to the lake water, dieldrin concentration in
the mussels increased 1200-fold (Bedford, 1971).
After injection of two female American cockroaches with dieldrin,
extraction and analysis of an homogenate of the roaches indicated
the presence of at least eight metabolites. The major metabolite
was found to be cis-aldrindiol . Trans-aldrindiol, syn-hydroxy-
dieldrin, 9-hydroxy analog of photodieldrin, 9-keto analog of
photodieldrin and one unidentified compound were also observed.
Metabolites from German cockroaches differed only quantitatively.
Metabolites isolated from houseflies after exposure to dieldrin
differed only in that cis-aldrindiol was not observed (Nelson and
Matsumura, 1973).
In houseflies, dieldrin metabolism was very slow. Six metabolites
were observed and one was characterized in five to seven chromato-
graphic systems as trans-aldrindiol . Another resembled one metabolite
from rats (Sellers, 1971).
Four weeks after application of 11+C-trans-aldrindiol to leaves of
lettuce heads, the radioactivity was in the form of extractable and
non-extractable residues. Less than 1% was in the soil. In addition
to unchanged aldrindiol, analyses showed the presence of non-polar,
methanol insoluble, and hydrophilic material. The latter consisted
of at least 4 radioactive substances, the main product being about
one-third of the mixture and identified by GLC/MS as aihydrochlor-
denedicarboxyl ic acid (Kilzer et al . , 1974).
ltfC- trans -aldrindiol was applied to soil. Seven weeks later, the
soil analyses revealed the presence of 90.7% of the radioactivity
as unchanged aldrindiol. In addition to non-polar material which
could not be chromatographed, there was hydrophilic material. In
this fraction, dihydrochlordenedicarboxylic acid was observed (Kilzer
et al., 1974).
Aldrin was stable in demineralized water irradiated with UV at
A>300nm. When sensitizers (acetone and actaldehyde) were added,
dieldrin formed (Ross and Crosby, 1975).
When 14C-dieldrin-treated onion-seed was grown, residues found in
skins, roots and soil consisted of photodieldrin, hydrophilic
products and some non-extractable material (Kohli et al., 1972).
1LfC-Dieldrin was applied to soil in which kohlrabi was grown.
Leach water contained a compound identified by GC and mass spec-
trometry as dihydrochlordenedicarboxylic acid. Studies indicated
that this compound was formed in the plants. Photodieldrin was
also observed in soil and plant material. Similar results were
obtained with carrots. Some radioactive material was not extract-
able (Kohli et al., 1973).
Studies on the effect of waste composting on dieldrin indicated
little or no further degradation of dieldrin in a 3-week period
(Muller and Korte, 1975).
Various species of marine algae differed significantly in ability
to take up dieldrin. Two hours after treatment, the percent removal
of dieldrin from the medium was:
Skeletonema costatum
Tetraselmis chuii
Isochrysis gallana (Chrysophyta)
Olisthodiscus luteus (Xanthophyta)
Cyclotella nana (Bacillariophyta)
Amphidinium carteri (Pyrrophyta)
42.0
16.0
15.5
13.0
13.0
2.3
(Rice
and Sikka, 1973)
After 4-day exposure of Daphnia pulex or 30-day exposure of
Ankistrodesmus spiralis to ll4C-die1drin and 11+C-photodieldrin at
4 ppb, both compounds were recovered unchanged (Neudorf and Khan,
1975).
10
Little or no degradation of dieldrin occurred in skim milk containing
E. coli , B_. subtil is, P. fluorescens or S. aureus (Collins, 1969).
The epoxide ring of dieldrin is unusually stable and does not react
with Grignard compounds or LiAlH4 nor in molten K0H/KN03 at 230C.
No reaction occurred in alkali at elevated pressure. With acid
catalysis, in methanol/benzene at 13K bar and 140C, the epoxide
ring of dieldrin reacted to form a series of compounds (Roemer-
Mahler, 1973).
In a model ecosystem, the accumulation, metabolism and degradation
of dieldrin was studied. About 97% of the dieldrin was recovered
unchanged. In addition to about seven unidentified metabolites,
the 9-hydroxy and 9-keto derivatives were observed.
Algae Clam Crab Daphnia Elodea Mosquito Fish Snail
Dieldrin
9-keto
9-hydroxy
Unknown 1
2
3
4
5
6
7
Polar 1
+
+
(In water only)
+
+
+ +
+
+ +
+
+
Dieldrin C.F. 7480 1015 247 2145
1280
6145 114,935
C.F,
Concentration Factor
(Sanborn and Yu, 1973)
ll+C-Photodieldrin was administered orally and ip to make rabbits.
Most of the radioactivity in urine and feces was in the form of
water soluble and/or conjugated material. Two of the urinary
metabolites were identified as trans-di hydro photodieldrin and
photodieldrin ketone (Reddy and Khan, 1975a) or trans-photoaldrin
diol and photodieldrin ketone (Reddy and Khan, 1975c) .
The in vitro metabolism of photodieldrin was studied with microsomal
mixed function oxidase (MFO) of mouse, rat and houseflies. Photo-
dieldrin was converted at very low levels to three metabolites in
preparations from male and female mice; two metabolites in male rat
and none in the female; one metabolite in female houseflies. Piperonyl
butoxide blocked formation of these metabolites. None were identified
11
(Reddy and Khan, 1974). Photoaldrin was oxidized by mouse MFO to
photodieldrin (Stanton and Khan, 1973). In other studies with CFE
rats and beagles, there was evidence of some metabolism of photo-
dieldrin to pentachloroketone (Baldwin, 1971).
Photodieldrin was applied to primary leaves of bush red kidney beans
(Phaseolus vulgaris). Under laboratory light and sunlight, photo-
dieldrin decreased by 17% during an 8-day period. No metabolites
were detected. When freshwater algae (Ankistrodesmus spiralis)
were exposed to dieldrin, no metabolites were detected. UV irradia-
tion of photodieldrin on silica gel plates produced two metabolites
not identified (Reddy and Khan, 1975b).
Soil was treated with labeled photodieldrin at the rate of 5 ppm on
a dry-weight basis. Fifteen months later, the treated soil was
removed and analyzed. Most of the radioactivity was not extractable
with organic solvents. Three metabolites were isolated and identified
1. Bridged isomer of dihydrochlordene dicarboxylic acid.
2. Bridged isomer of dihydrochlordene dicarboxylic acid,
methoxylated.
3. Bridged isomer of aldrin-trans-diol .
The latter compound, because of the bridged skeleton and the
asymmetry from the diol group, should exist in a total of four
isomeric forms (Weisgerber et al . , 1975).
Endrin in arachis oil was administered by stomach tube to six male
and six female rats. In a 6-day period, males excreted in feces
66% of the dose whereas females eliminated only 37%. Excretion
in urine was small but females excreted three times that of males.
Feces from rats fed endrin was collected and analyzed. Analysis
revealed the presence of endrin (11%), anti-12-hydroxyendrin (83%),
syn-1 2-hydroxyendrin (<0.01%), 3-hydroxyendrin (5%), 12-ketoendrin
(1%) and A-ketoendrin (<0.01%). A polar metabolite was identified
as trans-4,5-dihydroisodrin-4,5-diol . Another polar metabolite
was not identified. Collected urine from male rats contained
endrin, 12-ketoendrin, anti - 1 2- hydroxyendr i n and 3-hydroxyendrin
(17:19:2:1, respectively). The extracts from female rats did not
contain the 12-ketoendrin. The major metabolite in female rat
urine was identical to 1 2-hydroxyendrin 0-sulfate by paper and
thin-layer chromatography and paper electrophoresis (pH7). In
tissues analyzed, 12-ketoendrin was the major compound in fat of
males; endrin, in females, but 12-ketoendrin was also present.
In liver of males no endrin was detected and the 12-ketoendrin was
the major metabolite. Liver of females contained endrin and traces
of 12-ketoendrin. Kidneys of males primarily contained 12-keto-
endrin; those of females contained endrin. Much of the residue
was not identified. Bile contained anti -1 2-hydroxyendrin, 12-
12
ketoendrin and 3-hydroxyendrin as glucuronides (Hutson et al . , 1975)
After exposure of rats to endrin, analyses have also shown the
presence of 9-ketoendrin in tissues and urine and the presence of
5- and 9-hydroxyendrin in feces (Baldwin, 1971).
^C-Labeled isodrin was applied to leaves of young white cabbage
(Brassica oleracea var. capitata). After 4 weeks, only 2% was
unchanged isodrin. After 10-weeks, there were only conversion
products as residues. Endrin and A-keto-endrin were found (Klein
et al., 1972).
In other studies when isodrin-ll4C was applied to cabbage leaves,
six metabolites were isolated and identified or characterized:
I (27%) Endrin
II (27%) A-keto-endrin
III (14%) A monohydroxy acid
IV (0.5%) A monohydroxy acid
V (1%) A dicarboxylic acid
VI (1.4%) A dicarboxylic acid
(Weisgerber et al., 1975)
After application of 11+C-isodrin to soil, carrots (Daucus carota
ssp. sativus) grown in the soil contained 3.1% of the radioactivity
after 4 weeks. The soil contained 48% unchanged isodrin after
4 weeks and 41% after 12 weeks. Endrin and A-keto-endrin were
identified as conversion products of isodrin. Four water-soluble
compounds were also found but not identified (Klein et al . , 1972).
In vitro studies showed that MFO of bluegill and mouse converted
isodrin to endrin (Stanton and Khan, 1973).
After exposure of third instar larvae of tobacco budworm (He! iothis
virescens) , 14C-labeled endrin was more readily extracted from nerve
tissue of the susceptible strains. Susceptible budworms degraded
endrin somewhat to the aldehyde and ketone. The same metabolites
plus two unidentified decomposition products were recovered from
resistant strains (Polles, 1971).
Endrin in hexane was exposed to sunlight. The main photolysis
product, identified as the ketone, was also obtained by UV irradia-
tion of endrin in hexane (Fujita et al . , 1969).
A dieldrin analog, HEOM, was incubated with enzyme preparations
from pupae of blowfly (Calliphora erythrocephala) , larvae of the
southern armyworm (Prodenia eridania) , and adult Madagascar cock-
roaches (Gromphadorhina portentosa). HEOM was hydrated by the
three enzyme systems to the corresponding diol . Maximum activity
s associated with the 100,000xg pellet (Slade et al . , 1975).
13
wa
Homogenates and microsomal preparations from livers of rabbits,
rats, quail and pigeons were used to study the transformation of
HCE, a dieldrin analog. The results are summarized in the following
tables.
% HCE
Converted
To Diol
PERCENTAGE OF TOTAL METABOLITES
% HCE % HCE Trans Di hydroxy
Oxidized Metabolized Diol HHC HCE Ui U2 U3
Rabbit
M
73 29
33
10
20
4
S
20
75
95
37
12b
18
3b
Rat
M
27 5
95
a
S
13
39
48
55
b
b
Quail
M
17 8
92
a
S
2
31
67
57
b
b
Pigeon
M
27 0
90
4
6
S
0
95
95
42
34b
11
a = formed
from HCE
where
more
than
70?4 of substrate
had been
converted.
b = formed
from HHC
under
oxide
iti ve
conditions .
M = liver microsomal
preparation.
5 = 11,
,000xg superno
itant
from 1
iver
homogenate
After rabbits were dosed with labeled HCE, only 35-40% of the radio-
activity was extractable with ether. After refluxing with acid, most
of the remainder became ether extractable. HHC and an unidentified
polar compound were released by the acid hydrolysis.
PERCENT OF DOSE
HHC
HCE Diol
Di hydroxy
HCE
Ui
U3
Others
Rabbit
Rat
Pigeon
Quail
42.0
29.0
5.7
20.0
2.2
1.9
<2.0
6.3
6.0
5.0
1.0
36.0
0.0
0.0
6.7
3.0
0.0
0.0
21.0
(Walker and El Zorgani , 1973 and 1974)
The shag (Phalacrocorax aristotel is) has been found to contain
rather high dieldrin levels. A study of shag enzymes indicated
that the epoxide hydrase and the hydroxylating capacity of liver
preparations was substantially lower in the shag than in the rat.
Liver microsomes of the shag exhibited <8% of epoxide hydrase and
<14% of the hydroxylating activity of a similar preparation from
a rat (Walker et al . , 1975).
14
CI
crW
HEOM
HO
HEOM trans-diol
CI ^Cl
HCE trans-diol
Other Compounds
o + U,
Oi hydroxy HCE
15
Dihydrochlordene dicarboxylic acid was irradiated by UV (a>300 nm). After
treatment with diazomethane, the following compounds were observed:
Compound 1 UV> CH3N2> Compounds 5 to 11
or 2 Acetone
Compound 2
n-Hexane
>• Compound 3
Compound 2 M^M^ Compound 4
(Gab et al., 1974)
OOH
OOH
T-COOCHj
COOCH,
■.COOCH3
OOCH,
CI CI
OOCH3
OOCH3
YCOOCH3
OOCH3
X.iCOOCH.
rci/V
Cl COOCH.
;ooch,
'3
...j^-COu^nj
COOCH,
OOCH
OOCH
OOCH,
OOH
11
16
^OOCHg
ci^q
COOCH3
H-.
N
H^l j
Cl
(CI) (H)
12
13
:oocH3
:ooch,
ci
' — 7COOCH3
00CH3
(H)Cl4^(£l)
14
OOCH.
COOCH,
OOCH
COOCH.
OOCH 3
: cooch 3
15
16
17
OOCH
COOCH
OOCH:
OOCH.
OOCH. CI
C 1 6 — ^V^~ -7-COOCH :
XT T '
18
19
20
^
OOCH2C1
COOCH2CI
21
>- 12,13 ,14
15, 16 ,17
M9
uv
18 , 20. 21
CC14 ' '
(Gab et al., 1973)
Incubation of compound 1 with rat liver homogenate produced two isomers
of the monodechloro analog as the main metabolites (Lay et al., 1974).
17
Ally! alcohol
When allyl alcohol was added to growing cultures and washed mycelium
of Trichoderma viride, acetate and acrylate were produced. Additional
studies with arsenite-inhibited mycelium indicated that allyl alcohol
was metabolized by T. viride by a pathway that includes acrylate,
lactate, or their acyl-CoA esters, and pyruvate (Jackson, 1973).
Acrylic acid appeared to be an intermediate in metabolism of allyl
alcohol by Pseudomonas fluorescens and Nocardia coral! ina (Jensen,
1961).
13
AMINOPYRIDINE [4-Aminopyridine]
After application of 14C-labeled ami nopyri dine to corn and sorghum
grown in nutrient cultures, studies showed that the ami nopyri dine
was readily absorbed by the roots of both plants and translocated
to foliar portions of the plants. There was a general distribution
pattern throughout the plants. After one week, no acetone-soluble
metabolites were found in corn. In sorghum, however, autoradiograms
indicated some degradation within shoots and roots. The presence
of acetone-soluble radioactivity suggested that some of the amino-
pyridine was bound by cellular components (Starr, 1972; Starr and
Cunningham, 1974).
Adsorption to soil increased with pH. Soil metabolism studies
indicated the need for aerobic conditions for degradation. After
a one-week lag period, in soils having optimum temperature, moisture
and oxygen requirements, 42 to 60% of the ll*C-labeled aminopyridine
was degraded to 11+C02 within two months. The rate of breakdown
decreased with increasing soil pH. Two metabolites were detected
in trace amounts (Starr, 1972; Starr and Cunningham, 1975).
19
AMINOTRIAZOLE [3-Amino-l ,2,4-triazole]
When couch grass
triazole, two mai
identically with
thistle [Cirsium
observed but none
studies with Cana
identified as B-(
system from pea (
lized aminotriazo
was metabolized v
metabolic pathway
(II) ■* lb (Smith
[Agropyron repens (L.)] was treated with amino-
n metabolites were observed. These chromatographed
two metabolites previously observed in Canada
arvense (L.)]. Several other metabolites were also
were identified (Fiveland et al . , 1972). In other
da thistle, three compounds were observed. One was
3-amino-l ,2.4-triazolyl-l )-a-alanine) . An enzyme
Pisum sativum L. cv. Thompson Laxton) also metabo-
le. The pea studies indicated that aminotriazole
ia a pathway similar to tryptophan synthesis. The
appeared to be: aminotriazole ■*■ alanine derivative
and Chang, 1973).
After a 39-year-old woman ingested 20 mg/kg of aminotriazole, urine
taken some hours later contained unchanged aminotriazole (100 mg/
100 ml). No metabolites were found (Geldmacher-v. Mallinckrodt and
Schmidt, 1970).
C02 +
H2N-
■NH.
H2N-CN
N=CH^
/
= N'
N-CH2-CH2-NH2
/
H,N
N=CH
^N-CH2-C0OH
C= \\y
Ia
N=C
U
I
NH
^
M-
NH
N=
I
N
':M
\
HN-CH
;n-
N^C-NH
'" ^C=
Ho
2
Aminotriazole
I
H,N
N=CH.
^=N
y
•N-CH-
■CH-C00H
2
1
II
N=CH
C=N
^-CH=CH=C00H
H,N
N=CH,
C=N
/
'N-CH;
■C00H
M=CH
\
C«N'
OH
N-CHo-CH-COOH
HoN
/
lb
20
ANILINE
When soil was treated with more than one substituted aniline, asym-
metric azobenzenes were produced. Phenyl hydro xyl amine was identified
as a key intermediate which condensed with excess aniline to form the
corresponding hydrazobenzene. This was then oxidized to the azobenzene
(Bordeleau, 1972).
The fungus Geotrichum candidum produced two extracellular enzymes, an
aniline oxidase and a peroxidase, capable of transforming anilines.
The apparent Km (aniline) were 3.1 x 10"4M and 4.4 x 10_1+M for perox-
idase and aniline oxidase, respectively. Susceptibility to transfor-
mation was dependent on electron distribution in the molecule with
increased susceptibility to enzymic transformation correlated to increased
electron density at the amino group. Anilines substituted at both
2 and 6 positions by electron attracting groups were not transformed.
Sequential transformation of propanil to 3,3' ,4,4' -tetrachloroazobenzene
and other complex materials was affected by synergistic interaction of
the two common fungi Penicillium piscarm and Geotrichum candidum
(Bordeleau, 1972).
Chloroanil ine residues of herbicides were immobilized in soil by
formation of complexes with humus. In studies with labeled 3, 4-di chloro-
anil ine (DCA), it was found that P. frequentans degraded DCA-humic
complexes by creating humic oligomers with considerable radioactivity
still attached. When the fungus A. versicolor was used, the aniline
ring was mineralized (Hsu and Bartha, 1974).
An aryl acylamidase, inducible in Bacillus sphaericus, was obtained
and purified. Molecular weight was 75,000 and Km (1 inuron) was 2 x
10" 6. Substrate specificity of the enzyme was rather low. The enzyme
was inducible by linuron, maloran, monalide, propanil, propham, 2-
chlorobenzanilide, and 2,5-dimethylfuran-3-carboxanil ide (Engelhardt
et al., 1973).
A mixture of microorganisms was cultured on propham as the sole carbon
source. The microorganisms grew rapidly on nonchlorinated anil ides.
Ring chlori nation depressed respiration and inhibited growth. Acyl anil ides
were hydrolyzed more rapidly than carbanilates and chlorinated rings
were degraded more slowly than unchlorinated rings. Ring degradation
was affected by chlorination in order: 0 > 2, 4 > 2,4,5 > 3 > 4 > 3,4.
Compounds tested were isopropyl N-phenyl carbamate and the 3-, 4-, 3,4-,
2,4-, and 2,4,5-chlorinated analogs; karsil; propanil; swep; propionanilide;
fenuron; and phenylurea. The mixture of organisms used was identified
as Mycobacterium sp., Arthrobacter sp., Nocardia sp., Fusarium sp.,
Streptomyces sp., Aspergillus sp. , Penicillium sp., and possibly
Corynebacterium sp. (McClure, 1974).
21
The soil fungus Fusarium oxysporum metabolized 4-chloroaniline via
oxidation as well as acylation of the amine moiety. The oxidative
route was the major metabolic pathway. Products isolated and iden-
tified included: 4-chlorophenyl hydro xyl amine; 4-chloronitrosobenzene;
4-chloronitrobenzene; 4-chloroacetani 1 ide; 4,4' -dichloroazoxybenzene;
and 4,4'-dichloroazobenzene. Chloride ion and three phenolic metabolites
were also detected. One phenol has been identified tentatively as
2-chloro-4-nitrophenol . The latter implies chlorine migration and
requires further identification (Kaufman et al., 1973).
In the presence of a NADPH-generating system, heparinized rat blood,
and a liver homogenate, a methemoglobin-forming metabolite was produced
with 3,4-DCA (Chow and Murphy, 197b). Other studies have also shown
the formation of N-hydroxylated derivatives of £-chloroaniline (Debackere
and Uehleke, 1964, from Chow and Murphy, 1975).
22
ARSENICALS
Sodium arsenate (Na3AsOi+)
Sodium Arsenite (Na3As03)
Cows and dogs were fed sodium arsenite and sodium arsenate daily
for five days. Urine was collected and analyzed for methylarsenate
and inorganic arsenate. In the cow, the levels rose to 0.1 to 0.5
and 1.0 to 4.0 ppm, respectively. When the cows were returned to
normal diets, all values returned to control levels (0.02 to 0.10
ppm and 0.1 to 0.2 ppm). In dogs, arsenite feeding produced identical
peak values 5.0 to 7.0 ppm for both methylarsenate and inorganic
arsenate. Feeding of sodium arsenate to dogs produced a rise to
10 ppm methylarsenate and 5.0 ppm inorganic arsenate. Six days
after withdrawal from the arsenic-containing diet, all values
reached control levels (Peoples and Lakso, 1973).
Cacodylic acid [Dimethyl arsinic acid]
When applied to soil, cacodylic acid decreased by two routes. The
observation of a pungent garlic odor suggested production of alkyl-
arsine and a source of arsenic loss. Degradation to CO2 and arsenate
by microbial action was another route for cacodylic loss (Wool son
and Kearney, 1973).
When exposed to DMA and MMA, the three fungi Candida humicola
(Dazewska) Diddens and Kodder, Giocladium roseum Bain, and
Penicillium sp. produced trimethylarsine. Of these three, Candida
humicola only was able to metabolize arsenate and arsenite to
trimethylarsine (Cox and Alexander, 1973).
23
ASULAM (Asulox) [Methyl 4-aminobenzenesul fonyl carbamate]
Asulam exhibits rapid mobility in soil and would be expected to
readily leach into subsurface water. Mobility of asulam in soil
would be pH dependent, where the undissociated form would leach
less rapidly than the associated form (Babiker and Duncan, 1975)
24
AZINPHOSMETHYL (Methyl guthion) [0,0- Dimethyl S-(4-OXO-l ,2,3-
benzotriazin-3-(4H)-ylmethy1 )phosphorodithioate]
The kinetics of azinphosmethyl persistence in soil was studied.
Losses of insecticide followed first-order kinetics.
[A]0 = initial concentration
x = amount of A decomposed per unit volume at time t
= rate constant
-l
log([A]0-x)
■i
2.303
t + log [A]
plotting of log([A]0-x) vs t, y intercept = log[A](
and ki = -2.303 (slope)
Tl/2 _ to + ti/2
where t0 = lag period
'1/2
time for half of
to
t
1/2
azinphosmethyl to be lost
experimentally determined
0.693k!
Moisture and temperature affected the persistence of azinphosmethyl
The half-life varied from 5 days (40C and wet) to 484 days (6C and
wet or dry) (Yaron et al . , 1974).
The degradation of azinphosmethyl in water was studied. The effect
of pH and temperature was determined.
Aqueous solution
Temperature
°C
PH
tl/2
Kl
25
40
8.6
9.6
10.7
8.6
9.6
10.7
8.6
9.6
10.7
36.4
1.9
x lO-2
4.95
1.4
x 10-1
3.9
1.8
x 10"1
27.9
2.5
x lO"2
2.4
2.46
x 10"1
2.0
3.4
x 10_1
7.2
9.5
x lO"2
0.65
1.06
0.41
4.1
x 10"1
(Heuer et al . , 1974)
25
BASAL IN (Fluchloralin, BAS-392) [N-(2-Chloroethyl )-N-propyl-2,6-dinitro-
4-trifluoromethylanil ine]
Irradiation of basalin in methanol -water with a photoreactor yielded
nine products. Identification was based mainly on mass spectral
data.
When basalin was irradiated in water-methanol in sunlight for
48 days, compounds 3,5,6,7,8 and 11 were observed (Nilles and
Zabik, 1974).
n-C3H7— N-CH2-CH2C1
02N«»^S-N02
Y
Basalin
2
-CjH^Cl
C H
ON-r^VVM).
V '
CF,
-C^Cl
C3H7
m
02"jr^p°2
CF.
|^Muc2vh
10
11
26
BENAZOLIN [4-Chloro-2-oxobenzothiazol in-3-ylacetic acid]
The breakdown of 11+C-benazolin was studied in wild mustard [Brassica
kaber (DC L.C. Wheeler var. pinnatifida (Stokes) L.C. Wheeler], turnip
rape (Brassica campestris L. 'Echo' ) , and rape (Brassica napus L.
'Target'). Negligible amounts of ^CC^ were released by the three
species after treatment with benazolin. The Brassica species metabolized
benazolin to four less toxic derivatives. None of the metabolites were
identified but one was characterized as a conjugate of unchanged benazolin
(Schafer and Stobbe, 1973).
27
BENEFIN [N-Butyl -N-ethyl -a ,a ,a-tri f 1 uoro-2 ,6-di ni tro-p_-to1 ui di ne]
Roots of tobacco seedlings (Nicotiana tobacum L. Kentucky) accumulated
benefin from nutrient solutions containing labeled benefin. Two
compounds were detected but not identified (Long et al . , 1974).
28
BENOMYL (Benlate, Dupont F - 1991) [Methyl N-(N- butyl carbamoyl )-
2-benzimidazolyl carbamate]
EBC [Ethyl N-(2-benzimidazolyl )carbamate]
MBC (Carbendazim) [Methyl N-(2-benzimidazolyl )carbamate]
PARBENDAZOLE [Methyl N-(5(or 6)-butyl-2-benzimidazolyl )carbamate]
THIOPHANATE (TPE) [l ,2-Bis(ethoxycarbonyl thioureido)benzene]
THIOPHANATE-METHYL (TPM) [l ,2-Bis(methoxycarbonyl thioureido)benzene]
MCA (NF 48) [2-(3-methoxycarbonylthioureido)aniline]
The fate of benomyl was studied in mice, rabbits, and sheep and with
enzyme preparations made from mouse liver, kidney, heart, brain,
intestine and blood. Preparations were also made from sheep blood,
liver and rumen fluid and from rabbit liver and blood. A summary of
the pattern of metabolites is given in Table 1. The pattern of
metabolites with mouse kidney, heart and brain was similar to that
with liver; but with the intestinal preparation, compounds III and
IV were not observed. The butyl carbamoyl side chain was stable at
pH 7.5 but became increasingly labile with increased acidity.
Optimal pH for hydroxylation was between pH 7.0 and 8.0, and at
about pH 8.0 for ester cleavage. After benomyl was administered
per os to animals, urine and feces were collected at 24-h intervals
for 96 h. Results are shown in Table 2 (Douch, 1973).
TABLE 1
In Vitro prep. Mouse Rabbit Sheep
Liver II - VI II - VI II - VI
Blood II, III, V, VI II, III, V, VI II, III, V, VI
Rumen Fluid ™ ™ II, III, V, VI
After melon plants were treated with benomyl containing 3H-MBC, most
of the label was recovered in the leaves after three weeks. In addi-
tion to MBC, 2-AB, conjugates of MBC and 2-AB, benzimidazole, o-amino-
benzonitrile, and aniline (Rouchaud et al . , 1974). In other studies,
benomyl degradation occurred in non-sterilized soil. Cleavage of the
benzimidazole ring and production of C02 was observed (Siege! , 1975).
29
Urinary
Metabol ites
(%)
Fecal
Metabol
ites (%)
Metabolite
Free
Cor
ljugated
Free
Con
jugated
Mice
VI
12.2
7.8
IV
1.6
3.9
1.5
3.8
II
29.2
15.0
III
3.0
5.1
3.3
5.6
Rabbit
VI
11.1
6.5
IV
5.4
5.1
3.5
3.2
II
23.0
9.9
III
3.1
8.3
3.0
8.0
Sheep
VI
23.5
12.1
IV
1 .1
1.9
1.6
2.6
II
18.6
4.4
III
4.1
6.5
3.0
4.7
[2-11+C]-Benomyl was applied to soil and turf. After 3 months, the
parent compound was not detected in soil. Soil residues consisted
of [2-11+C]-MBC and [2-li+C]-AB. The "half-life" of the total labeled
residues was about 6-12 months on bare soil and 3-6 months on turf
(Baude et al . , 1974).
When benomyl was applied to plant foliage, only MBC was found (Baude
et al., 1973).
Some studies indicated that benomyl hydrolysis was not rapid in plant
tissues nor in aqueous solution. The complete hydrolysis indicated
by others may be the result of extraction procedures used (Jhotty
and Singh, 1972).
From air over moistened benomyl, a volatile compound was trapped in
hexane and identified by GLC on two different columns and by infrared
spectroscopy as butyl isocyanate (BIC) (Hammerschlag and Sisler, 1973),
2-ll+C-Benomyl was fed to a rat. After hydrolysis, the urine contained
5-hydroxy analog (III). Similar results were obtained with 2-11*C-MBC.
Three conjugates were indicated. When administered to a beagle dog,
benomyl was metabolized to 5-HBC. The dairy cow metabolized benomyl
to 4- and 5-HBC. In the eggs of chickens fed benomyl, only 5-HBC
was observed at the high (25 ppm) feeding level. No residues (<0.02
ppm) were observed in eggs from hens on the low (5 ppm) feeding level
(Gardiner et al . , 1974).
Dwarf pea plants were grown in nutrient solutions and root-treated
with li+C-benomyl . MBC was present in large quantities. Hydrolysis
of plant-bound residues with hot NaOH released half the bound label,
part of which was 2-aminobenzimidazole (Siegel and Zabbia, 1972).
30
31
Cells of apple and cucumber leaves were exposed in nutrient media
to MBC. Cytoplasmic uptake by apple cells was constant for 26 h,
whereas uptake by cucumber cells was negligible. When applied to
cucumber leaves, 1.56% of the [ring-14C]-MBC was metabolized to
C02 (Solel et al . , 1973).
Benomyl decomposes in many solvents to give MBC as a precipitate.
Solvents included: benzene, ethyl ether, ethanol , acetone, ethyl
acetate, methylene chloride, chloroform (Chiba and Doornbos, 1974).
Benomyl was taken from sprays, waxes, and alkaline peeling solutions
and brought to pH 6 with 0.1N HC1 . The precipitate was removed and
analyzed. After characterization on the basis of evidence derived
from infrared, nmr, and mass spectra, verification of the structure
as that of STB was made by synthesis and comparison of the preceding
physical evidence plus m.p. or decomposition point. Standing alkaline
solutions also produced a second precipitate which was identified as
BBU (White et al . , 1973).
PARBENDAZOLE
In cattle and sheep, one of the major parbendazole metabolites was
identified as compound II by means of UV and mass spectra. The
other major metabolite in sheep and cattle was identified as the
glycol, compound III. Other metabolites obtained from sheep were
the alcohols, compounds IV, V and VI. The phenol VII was obtained
from cattle (Dunn et al . , 1973). In other studies with sheep, after
an oral dose of 14C-parbendazole (labeled at C-2), urine was collected
and analyzed. Structures of the metabolites were determined by
means of UV, IR, proton magnetic resonance, mass spectrometry and
chemical synthesis. Seven metabolites were identified as compounds
II, III, IV, V, VI, VII and IX. Incubation of the metabolites with
glucuronidase resulted in 38% hydrolysis of the total radioactivity
and supported the fact that compounds II, III and IX were excreted
primarily unconjugated, whereas compounds IV, V, VI and VII were
excreted mainly as glucuronides. Other studies with glusulase
indicated little excretion of the metabolites as sulfates (DiCuollo
et al., 1974).
The metabolites identified as compounds II and VI were obtained
from Cunninghamella bainieri ; and the fungus Paecilomyces sp. ,
produced compound VIII (Dunn et al., 1973). Other studies with
C. bainieri ATCC 9244 also gave compounds II and VI (Valenta et al . ,
1974T
32
H 0
I ll
■N-C-OCH3
Parbendazole (I)
R
i. ch3-ch2-ch2-ch2 -
ii. h00c-ch2-ch2-ch2-
iii. ch3-ch2-ch ch -
~ 6h 6h
iv. ch3-ch2-ch2— ch -
v. ch3-ch2-ch— ch2-
vi. ch2-ch2-ch2-ch2-
OH
VII. CH3-CH2-CH2- CH2-
VIII. CH3-C — CH2- CH2-
H-
H-
H-
H-
IX. H00C-CH2-CH -CH2-
H-
HO-
H-
H
VI
II
/
IX
'4
^ch3-£h-ch2-ch7J
VIII
VII
IV
III
33
THIOPHANATE
When thiophanate or the methyl analog was irradiated with UV in
the solid state, no reactions occurred. When exposed in aqueous
solution to UV and sunlight, both fungicides were converted to their
respective alkyl benzimidazol-2-yl carbamates (EBC and MBC).
Residues of the fungicides on cotton plants, following spray appli-
cation, were also converted by sunlight to EBC and MBC (Buchenauer
et al., 1973).
In soil, thiophanate underwent rapid conversion to MBC. Conversion
was reduced by treating the soil with steam or increasing the
alkalinity. At pH 7.4 the rate was more than 4 times that at pH 5.6.
Very little (less than 1%) of ring-14C-labeled MBC was converted to
lt+C02 even after 51 days incubation of soil. When 11+C-methyl label
was used, about 15% of the label appeared as CO2 after 51 days
(Fleeker et al . , 1974).
Photoisomerization of benzimidazole gave rise to two compounds iden-
tified as the dimers XII and XIII (see diagram on page 31) (Cole
et al., 1973).
34
BENTAZON [3-Isopropyl -1H-2 ,1 ,3-benzothiadiazin-4(3H)-one-2,2-dioxide]
After oral administration to rats, bentazon was rapidly absorbed.
Excretion, primarily (84%) in urine, was rapid and largely unchanged
bentazon. Two metabolites, one of which may be the N-glucuronide
of bentazon, were detected. Traces of radioactivity were also
found in the bile (BASF, 1973; Chasseaud et al . , 1972).
When 11+C-bentazon was applied to spring wheat, Opal variety, the
active ingredient was taken up via roots from a nutrient solution.
At harvest, 173 days after test start, two-thirds of total activity
could not be extracted from the straw. The remainder consisted of
soluble complexes of the active ingredient and of free bentazon.
Fifty days after foliar spraying of soya plants, more than 40% of
the methanol extractable residues was in the form of complexes of
mono- or ol igo-saccharides with hydroxylation of the aromatic ring
(BASF, 1973).
Bentazon does not persist in loamy sand soil. Within 15 weeks,
bentazon broke down quantitatively at room temperature and 15%
soil moisture. Anthranilic acid-isopropylamide was identified.
This broke down quickly (BASF, 1973).
35
N-Benzoyl chloride-N/-(2,4,6-trichlorophenylhydrazide)
The photolytic half-lives of this compound were 12 and 16 h, with and
without a filter. Under the experimental conditions, using a combin-
ation of TLC, GLC and MS, eight products were identified:
I. Benzoyl 2-(2,4-dichlorophenyl )hydrazide
II. 2,4,6-trichlorobenzophenone
III . l^-(2,4,6-trichlorophenyl )benzamide
IV. P[-(2,4-dichlorophenyl )benzamide
V. N-(2,6-dichlorophenyl )benzamide
VI. 2,4-dichlorobenzophenone
VII. 1 ,2-dibenzoyl-l-(2,4,6-trichlorophenyl hydrazine
VIII. 1 ,2-dibenzoyl-l-(2,4-dichlorophenyl )hydrazine
(Koshy et al . , 1975)
36
BENZOYLPROP-ETHYL (Suffix) [Ethyl N-benzoyl N-(3,4-dichlorophenyl )-
2-aminopropionatel
lltC-Benzoyl prop-ethyl was applied to foliage of wheat (Triticum
aestivum), oat (Avena sativa), and barley (Hordeum vulgare) seedlings.
Metabolism of herbicide was similar in all three plant species. Extracts
of wheat seedlings sampled up to 15 days after treatment indicated the
presence of as many as five metabolites: des-ethyl analog and its
3-glucoside, debenzoylated analog, g-hydroxybenzoic acid as a conjugate,
and one unidentified compound (Beynon et al . , 1974d). In other studies
with labeled herbicide and spring and winter wheat, the crop was sampled
at harvest and the following compounds were observed: N-benzoyl 3,4-
dichloroaniline; benzoyl prop; several sugar complexes. Other products
present were not identified (Beynon et al . , 1974a and c).
In soil, benzoyl prop-ethyl was de-ethylated. The acid, upon standing,
became tightly bound to the soil before undergoing slow debenzoylation
to N-(3,4-dichlorophenylalanine) and benzoic acid. 3,4-Dichloraniline
which formed was present as humic acid complexes. Polar products
observed were shown to arise from the dichloroaniline. No 3,31,4,41-
TCAB was detected. The rate of degradation for various soils varied
from 1 to 12 weeks (Beynon et al . , 1974a, b,c).
After 14C-benzoyl prop-ethyl was applied to the leaves of cereal plants,
only 7% of the total applied radioactivity moved from the treated leaf
during a 3-day period. Movement of this herbicide occurred in the
form of the acid and acid conjugates (Jeffcoat and Harries, 1973).
37
BHC (HCH) [1,2,3,4,5,6-Hexachlorocyclohexane]
When a, 6, y and 6 isomers of BHC were orally administered to rats,
some B isomer accumulated in the tissues, presumably from isomeriza-
tion. The level of accumulation was B>>a>y>6 (Kamada, 1971).
y-PCCH was metabolized by rats primarily to 2,4,5-TCP and a trace of
2,3,5-TCP; B-BHC was metabolized to 2,4,6-TCP. When a- and 6-BHC
were administered to rats, 2,4,5- and 2,4,6-TCP formed. The y-isomer
was metabolized to 2,4,6-, 2,3,5- and 2,4,5-TCP and 2,3,4,5- and
2,3,4,6-tetrachlorophenol (TTCP) in addition to a configurational
isomer of 2,3,4,5,6-pentachlorocyclohex-2-en-l-ol (Freal and Chadwick,
1973). When rats were fed y-BHC plus DDT, there was significantly
more excretion of 2,4,5-TCP and 2,3,4,6- and 2,3,4,5-TTCP than in
the absence of DDT (Chadwick and Freal, 1972).
Wistar rats were orally administered a-BHC. Controls and treated
rats were sacrificed; the livers were removed, homogenated and then
centrifuged for 10 min at 12,000g. The supernatant was centrifuged
at an average 100,000g (140,000g maximum) for 90 min. Portions of
these fractions were dialyzed or gel-filtered. When these prepara-
tions were incubated with labeled (ll+C, 3H, or 36C1) a-BHC in the
presence of air (2 h, 37C, and pH 7.4), 5 to 10% of the label was
converted to water-soluble materials. Longer incubation, more
alkaline pH, and preparations from treated rats increased the amount
of water-soluble labeled materials. GSH was required for the reaction.
These studies indicated that dechlorination was part of the overall
reaction and that four atoms of chlorine per molecule HCH were elim-
inated. Although the main product of the reaction was not established,
there was evidence that it was a conjugate of glutathione with the
BHC-moiety rendered aromatic, probably S-2,4-dichlorophenylglutathione.
Alkaline hydrolysis produced a thiophenol or mixture of thiophenols
(Kraus et al . , 1973; Noack and Portig, 1973; and Portig et al . , 1973).
After adaptation of rats to lindane, 14C-lindane was orally admin-
istered. Fat, kidney and musculature were the main sites of deposition.
Pituitary and thyroid glands had highest activity. Differences between
cortex, stem and cerebellum were marked. The metabolites y-PCCH,
pentachlorobenzene and hexachlorobenzene were observed. Large
amounts of conjugates and strongly polar, hexane-soluble metabolites
were also present in feces, urine and organs. Glucuronides and other
unidentified water-soluble conjugates were observed. Half of the
administered lindane was excreted within 3 or 4 days (Seidler et al . ,
1975).
38
Studies with mice indicated differences in excretion rates of a, 6
and y isomers. The data indicated that metabolism of the y-isomer
was greater than the 3-isomer and that the a-isomer was intermediate.
Most metabolites from the y- and B-BHC were conjugated as sulfates
and glucuronides . After hydrolysis, chlorophenol s were obtained.
About 25% of the total metabolites in urine was 2,4,6-trichlorophenol .
2,4-Dichlorophenol was also prominent. From 3-HCH, traces of 2,4,5-
trichlorophenol were also identified. Free chlorophenols were also
observed. One behaved like 2.4-dichlorophenol (Kurihara and
Nakajima, 1974).
Uniformly labeled lindane-14C was fed in gelatin capsules to rabbits
for 26 weeks. About 54% of the label was excreted in urine and 13%
in feces by the end of the feeding period. Of the urinary metabolites,
55% was ether-soluble, in which 14 chlorophenols were observed.
Four were identified by infrared: 2,3,5-, 2,4,5- and 2,4,6-tri-
chlorophenol and 2,3,4,6-tetrachlorophenol . Three were identified
by gas chromatography and mass spectrometry: 2,3- and 2,4-dichloro-
phenol and 2,3,4,5-tetrachlorophenol . Seven chlorophenols were
tentatively identified by gas chromatography: 2,5-, 2,6- and
3,4-dichlorophenol ; 2,3,4-, 2,3,6- and 3,4,5-trichlorophenol ; and
pentachlorophenol . Six chlorobenzenes were also observed: 1,2-
dichlorobenzene; 1 ,2,4-trichlorobenzene; 1,2,3,4-, 1,2,4,5- and/or
1 ,2,3,5-tetrachlorobenzene; and pentachlorobenzene (Karapally et al . ,
1973).
After injection of uniformly ll+C-labeled a-BHC into adult rats,
urine and feces were collected. In 4 weeks, 65% of the label was
excreted in urine and 16% in feces. Most of the urinary metabolites
apparently contained chlorine. Nearly all of the fecal lkC was
unchanged a-BHC (Noack et al . , 1975). Urinary metabolites obtained
in other studies indicated that the proportion of free chlorophenols
was 5% or less of all urinary BHC metabolites. Both 2,4,5- and
2,4,6-trichlorophenol were identified by UV, IR and cocrystal lization
with authentic compounds. There were indications that 2,3,5-tri-
chlorophenol and 2,3,4,6-tetrachlorophenol were also present but
this could not be confirmed. After alkaline and acid hydrolysis,
2,4,6-trichlorophenol was found. The presence of 2,3,4,6-tetra-
chlorophenol, 2,4,5- or 2,3,5-trichlorophenol were indicated.
The presence of dichlorothiophenols was also observed (Koransky
et al., 1975).
Incubation of lindane with rat liver homogenates produced hexa-
chlorocyclohexene (HCCH). When rats were administered HCCH,
previously observed lindane phenolic metabolites were observed:
2,4,6-, 2,3,5-, and 2,4,5-trichlorophenol ; 2,3,4,5- and 2,3,4,6-
tetrachlorophenol. In addition to these, 2,3,4,5,6-pentachloro-
2-cyclohexen-l-ol was also found. Similar results were obtained
with in vitro studies. The enzyme system involved in the initial
39
dehydrogenation of lindane to HCCH was characterized as a hepatic
microsomal MFO and a cytochrome P-450 which requires molecular
oxygen and NADPH (Chadwick et al . , 1975).
When pentachlorobenzene was orally administered to rabbits, uniden-
tified dechlorinated compounds appeared in feces and tissues. In
urine, data indicated the presence of p_-chlorophenol , pentachloro-
phenol and some less chlorinated benzenes. After administration
of 1 ,3,5-trichlorobenzene to rabbits, monochlorobenzene was expired
and found in feces and tissues. Urine contained 2,4,6-trichlorophenol ,
4-chlorophenol , 4-chlorocatechol and perhaps other monochlorophenols
(Parke and Williams, 1960).
When the three tetrachlorobenzenes were orally administered to
rabbits in arachis oil they were partly excreted unchanged in feces.
The 1 ,2,3,4-tetrachlorobenzene was slowly metabolized to 2,3,4,5-
tetrachlorophenol which was excreted in urine as such and conjugated.
In 6 days, 43% of the 1 ,2,3,4-tetrachlorobenzene was oxidized.
1 ,2,3,5-tetrachlorobenzene was oxidized (5% in 6 days) to the
2,3,4,6-tetrachlorophenol . Approximately 2% of the administered
1 ,2,4,5-tetrachlorobenzene was oxidized to 2,3,5,6-tetrachlorophenol
in 6 days. Some dechlorination products were also probably formed.
The phenols were excreted as glucuronides and sulfates as well as
unconjugated (Jondorf et al . , 1958).
Percent of dose excreted
Tetrachlorobenzene
administered
Glucuronide
Sulfate
Mercapturic Free
1,2,3,4-
1,2,3,5-
1,2,4,6-
30
6
4
3
2
1
A
O O — ■
— ■ — ' 00
The mussel Mytil
us
edulis was ex
posed to lkC-
•labeled lindane.
Analyses indicated the formation of two highly polar compounds
amounting to about 3% of the lindane. Neither metabolite was
identified (Ernst, 1975).
14C-Lindane was added to a nutrient solution in which lettuce plants
were grown. Radioactivity extracted from the nutrient solution
after 4 weeks amounted to 7.8% of the applied material. About 14.1%
of the applied radioactivity was recovered from the plants and the
remainder was lost, possibly by evaporation. Of the material
recovered from the nutrient solution, 82% was unchanged lindane;
15%, polar material; and 3%, nonpolar. The polar material was
identified with the aid of GLC/MS as 2,3,4,6-tetrachlorophenol
(<1%), pentachlorophenol (ca. 5%) and conjugated pentachlorophenol
(1%). An unidentified highly hydrophilic substance (8%) was also
present. In the nonpolar fraction, there was 1 ,2,3-trichlorobenzene,
1 ,2,3,4-tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene,
40
Y-pentachlorocyclohexene and an unidentified compound that is
probably a hexachlorocyclohexene. From the lettuce plants, the
extracted radioactivity consisted of unchanged lindane (77%), polar
material (20%), and nonpolar material (about 3%). Again, the polar
fraction contained free 2,3,4,6-tetrachlorophenol (ca. 1%), conjugated
phenols including a tetrachlorophenol (ca. 3%), pentachlorophenol
(ca. 4%) and a highly polar unidentified compound (11 to 12%). The
nonpolar material consisted of 1 ,2,3-trichlorobenzene, 1,2,4-tri-
chlorobenzene, pentachlorobenzene, y-pentachlorocyclohexene and a
hexachlorocyclohexene. There were also indications of a tetra-
chlorobenzene (Kohl i et al . , 1976).
S-R 0H
41
Wheat plants were grown from seeds. From the roots, metabolites
identified included 1 ,3,5-trichlorobenzene; 1 ,2,4-trichlorobenzene;
1 ,2,3-trichlorobenzene; 1 ,2,3,4-tetrachlorobenzene; 1,2,4,5- and/or
1 ,2,3,5-tetrachlorobenzene; y-PCCH; and pentachlorobenzene. The
presence of m- and p_-dichlorobenzene were also indicated. Also
observed, but lacking confirmation because they appeared in quanti-
ties too small, were a number of chlorophenols: pentachlorophenol ;
2,3,5,6- and/or 2,3,4,6-tetrachlorophenol ; 2,3- and 2,4-dichlorophenol ;
2,3,4- and/or 2,4,5-trichlorophenol ; and 2,4,6-trichlorophenol (Balba
and Saha, 1974).
Use of lindane for protection of stored wheat grain against insects
has been suggested. When the fate of lindane residues in wheat flour
under normal conditions of bread making was studied with 14C-labeled
compound, about 75 to 82% of the radioactivity was retained by the
baked bread and 94% of this was present as lindane. Identified in
the bread were: y-PCCH; 1 ,2,4-trichlorobenzene; 1 ,2,3,4-tetrachloro-
benzene; 1,2,4,5- and/or 1 ,2,3,5-tetrachlorobenzene (Saha, 1974).
After treatment with 11+C-labeled lindane, wheat grains were stored
in closed containers at varying temperatures and times, with and
without added water. Less than 3% of the lindane was degraded.
Small amounts of y-PCCH were present as residues. No other products
were detected (Saha and Lee, 1974).
Houseflies were dosed topically with 14C-y-BHC. Homogenation and
chromatography of the extract indicated the presence of S_-2,4-
dichlorophenyl glutathione. Studies with grass grubs gave similar
results. Houseflies and grass grubs also converted y-PCCH and
6-PCCH into metabolites that had chromatographic properties identical
with S_-2,4-dichlorophenylglutathione. Inhibitors and colorimetric
assays lead to the conclusion that a PCCH is not a major intermediate
metabolite of y-BHC in these insects. These studies tend to support
earlier assumptions that a pentachlorocyclohexylglutathione is the
initial metabolite of y-BHC (Clark et al . , 1969).
A mold capable of degrading lindane was isolated but not identified.
The main metabolite, short-lived, was identified as y-pentachloro-
cyclohexene. The following compounds were also found in varying
amounts: hexachlorobenzene; pentachlorobenzene; 1,2,3,4-, 1,2,4,5-
and 2,3,4,6-tetrachlorobenzene; 1,2,3-, 1,2,4- and 1 ,3,5-trichloro-
benzene; 2,3,4- and 2,4,6-trichlorophenol; 1,2- and 1 ,4-dichloro-
benzene; 2,3,4,5-tetrachlorophenol ; and pentachlorophenol (Engst
et al., 1974).
In laboratory studies, P_. putida normally produced y-PCCH from
y-BHC. In the presence of NAD, a-HCH was also formed. y-Tetrachloro-
cyclohex-1-ene was observed (Benezet and Matsumura, 1973).
42
In an aerobic artificial lake impoundment, 15% of y-BHC was converted
in 2100 h to the a-isomer. Under anaerobic conditions, 90% of
the y-isomer was converted to a- and 6-isomers in 2100 h (Newland,
1969).
Two-thirds to three-fourths of the material lost from a calcareous
soil treated with lindane was lost by volatilization as PCCH (Cliath
and Spencer, 1972). Fifteen years after application of HCH to soil,
samples were taken and analyzed. Isomeric composition of BHC in
the soil samples was considerably different from that of technical
BHC. Persistence was of the order 6>6>y>a (Stewart and Chisholm,
1971).
A bacterium was isolated from rat feces and identified as Escherichia
coli . When incubated in trypticase soy broth with lindane, 10% of
the lindane was metabolized to y-PCCH. Structure was confirmed by
synthesis, gas chromatography and mass spectra (Francis et al . , 1975).
The relationship between concentrations of BHC in the medium and the
concentration in bacteria (living and dead) is given by the relation-
ship
CB = KCM
Cg = concentration in bacteria (ppm)
C^ = concentration in media (ppm)
a-BHC K = 4.2 x 101 n = 0.7
6-BHC K = 3.7 x 102 n = 0.7
Y-BHC K = 2.6 x 101 n = 1.0
The process is apparently not energy dependent (Sugiura et al . , 1975).
An apparent half-life equal to 16 days was calculated for y-BHC
degradation in an anaerobic artificial impoundment. Under aerobic
conditions, degradation was considerably slower. Onset of degradation
occurred at 264th and 840th hour anaerobically and aerobically,
respectively. After 2100 h of incubation of lindane in anaerobic
and aerobic sediments, 83.2 and 19.0% respectively, of the added
14C activity was volatilized. Chromatograohy of the hexane-acetone
extract of the aerobic impoundment sediment showed only y- and a-BHC.
With the anaerobic sediment, chromatography of the extract showed
a-, y- and 6-BHC. These studies indicated that y-BHC could undergo
isomerization in. natural systems. Thermodynamic stability of the
isomers is of the order 3>6>a>y (Newland et al . , 1969).
Lindane was added to a sandy loam soil and incubated for 6 weeks
under flooded conditions. The soil and water was extracted and
chromatographed. Five peaks were observed and the retention times
43
corresponded to 1 ,2,4-trichlorobenzene, 1,2,3,5- and/or 1,2,4,5-
tetrachlorobenzene, 1 ,2,3,4-tetrachlorobenzene, y-PCCH and y-3,4,5,6-
tetrachlorocyclohexene (y-BTC). GC/MS was used to confirm the
identities of the compounds except 1,2,3,5- and/or 1 ,2,4,5-tetra-
chlorobenzene whichwerenot present in sufficient quantity (Mathur
and Saha, 1975).
When pentachlorocyclohexene (PCCH) was synthesized by partial
additive chlorination of chlorobenzene, combined gas chromatography-
mass spectrometry revealed that at least five different Isomers of
pentachlorocyclohexene had been formed. Dechlorination products of
various isomers of BHC or PCCH in NaOH and in pyridine were compared.
Results indicated that 3-PCCH was the monodechlorination product
of a-BHC (Munster et al . , 1975).
The isomerization of 1 ,3,4,5, 6-pentachlorocyclohexene-l (y-PCCH)
was studied in dimethyl sulfoxide. After a long reaction time,
starting with any isomer, y-PCCH became the most abundant component.
Three new isomers were also isolated for the first time (Kurihara,
et al., 1974b).
Recent studies have also shown that lindane forms a colored complex
with montmorillonite clay (Haque and Hansen, 1975).
44
Pi phenyl [Bi phenyl]
Adult male Wistar rats were fed a diet containing biphenyl. Urine
was collected and analyzed. Five metabolites were isolated and
identified by means of melting point depression, chemical test, and
infrared spectra as:
IX. 4-hydroxydi phenyl
X. 4,4-dihydroxydiphenyl
XII. 3,4-dihydroxydi phenyl
XV. p_-(e-D-glucuronosidodiphenyl )
XVI. N-acetyl-p_-(S_-di phenyl )-L-cysteine
(West et al., 1956)
Studies with rabbits fed biphenyl, showed that the 3-hydroxybi phenyl
(XI) and a mixture of monomethylated analogs of 3, 4-dihydroxybi phenyl
(XIII and XIV) were present in urine (Raig and Ammon, 1972).
The ability of several phyla of marine organisms to metabolize biphenyl
was investigated with in vitro studies: mature skate (Raja ocellata) ,
mussels (Mytilus edulisj, starfish (Asterias vulgaris), rock crab
(Cancer irroratus), red crab (Gerydon quinquidens) , lobster (Homarus
americanus), brook trout (Salve! inus fontinal is), and plankton that
consisted mainly of large zooplankton. Tissue homogenates and intact
plankton samples were used. Biphenyl was metabolized in vitro by all
tissues primarily to 4-hydroxybi phenyl (IX) and to some extent to
2-hydroxybi phenyl (II). Rates of formation of the 4-hydroxy analog
ranged from a high of 400 n moles/g skate tissue to a low of
2 n moles/g starfish tissue (Willis and Addison, 1974).
Metabolism of biphenyl by Pseudomonas putida apparently proceeded by
way of 2 , 3-di hydro-2 , 3-di hydro xybi phenyl (III), 2, 3-dihydroxybi phenyl
(IV), and 2-hydroxy-6-oxo-6-phenylhexa-2,4-dienoic acid (V) to benzoic
acid (VI) (Catelani et al . , 1971 and 1974). The presence of either
2-hydroxypenta-2,4-dienoate (VII) or 4-hydroxy-2-oxovalerate (VIII)
was also indicated (Catelani et al . , 1973).
45
3:
o
o
* z:
o o
O II
g
/
V 3
7>
H>^
46
BLASTICIDIN S
After application to rice plants via culture solution, Blasticidin S(I)
was degraded. A small amount of cytomycin(III) and the deamino-
blasticidin S analog II were also observed. When incubated with micro-
organisms, Blasticidin S was also degraded: soil bacterium (unident-
ified) > Ps. aernginosa > Phytophythora parasitica > Fusarium
oxysporum > soil fungus (unidentified) > Ps. oval is 1002 > Ps.
marginal is. The main products after exposure to washed mycelia of
a soil fungus were compounds II, III, and IV (Yamaguchi et al . , 1972).
In other studies, a strain of Aspergillus fumigatus, isolated from soil,
converted blasticidin S into four metabolites. One was identified as
deaminohydroxyblasticidin S ( 1 1 ) . Another was identified as deamino-
hydroxycytomycin(IV) (Seto et al . , 1966).
When hydrolyzed with acid, compound III gave rise to uracinine(V) and
pseudoblastidone(VII) ; XI gave uracinine(V) and blastidone(VIII);
blasticidin S(I) gave cytosine(IX), cytosinine(VI) , blastidic acid(X);
cytomycin(III) gave pseudoblastidone(VII) (Seto et al., 1966).
Cytosinine acid hydrolysis gave cytosine, levulinic acid, NH3, and
C02- Analysis of this data plus that derived from Pt02 reduction
and ozonolysis of the N,j^- diacetyl methyl ester permitted assignment
of the structure of cytosinine. Similarly, acid hydrolysis of
uracinine gave uracil and permitted assignment of a structure
(Otake et al . , 1966a).
Acid hydrolysis of blasticidin S gave cytosinine and blastidic
acid. Products of alkaline hydrolysis and Pt02 hydrogenolysis
permitted structural assignments to blasticidin S and cytomycin
(Otake et al . , 1966b).
47
I / \ m i-
C / 2: *J
: — \ z-t_> in
c
o
o
o
^
c
o
o
■o
0
II
I
10
CO
o
48
BOTRAN (DCNA) [2,6-Dichloro-4-nitroanil ine]
Incubation of botran with cultures of bacteria indicated that
metabolism proceeded via 2,6-dichloro-£-phenylenediamine (DCPD)
to 4-amino-3,5-dichloroacetanil ide (ADCAA) (Van Al fen and Kosuge,
1974).
Cl-
■Cl
■CI
DCPD
ADCAA
49
BPBSMC (Chevron RE 11775) [3- (2-Butyl phenyl )N-benezenesulfenyl
N-methyl carbamate]
BPMC (Chevron RE 5365) [3- (2-Butyl phenyl )N-methyl carbamate]
Male albino rats (Sprague-Dawley strain) were orally administered lkC-
carbonyl and ll+C-butyl-labeled BPBSMC and BPMC in dimethyl sulfoxide.
Urine was collected for 48 h and then analyzed. Quantitatively the
major urinary products were identified in the order 2-(3-hydroxyphenyl )
butan-2-ol (4), the butan-3-ol analog (5), and then the butan-1-ol
analog ( 3 ). In addition to these, compounds 2 and 6 to 18, inclusive,
were also observed and identified using syntheses and infrared, electron
impact mass, chemical ionization and NMR spectra and TLC (Cheng and
Casida, 1973).
When BPBSMC was exposed to either UV, sunlamp, or sunlight irradiation
for one hour, six compounds formed. BPMC degraded only under UV
irradiation to form six or more products of which only compounds 2
and 18 were identified. BPBSMC yielded compounds 2, 10, 18, 19, and
22. Under more rigorous conditions, compounds 2, 4, 10, 12, 18, 19,
20 and 21 were observed (Cheng and Casida, 1973).
1 . BPBSMC
2. 3-(2-butyl)phenol
3. 2-(3-hydroxyphenyl )butan-l-ol
4. 2-(3-hydroxyphenyl )butan-2-ol
5. 2-(3-hydroxyphenyl )butan-3-ol
6. 2-(3-hydroxyphenyl )butan-4-ol
7. 2-(3-hydroxyphenyl )butan-3-one
8. 2-(3-hydroxyphenyl )butanoic acid
9. 3-(3-hydroxyphenyl jbutanoic acid
10. BPMC
11. 3-(2-butan-l-ol )N-methyl phenyl carbamate
12. 3-(2-butan-2-ol ) N-methyl phenyl carbamate
13. 3-(2-butan-3-ol )N-methyl phenyl carbamate
14. 3-(2-butan-4-ol ) N-methyl phenyl carbamate
15. 3- (2-butan-3-oneTN-methyl phenyl carbamate
16. 2- (3-N-methyl carbamoyl phenyl )butanoic acid
17. 3- (3-N-methyl carbamoyl phenyl jbutanoic acid
18. 3-butyl N-hydroxymethyl phenyl carbamate
19. 3-(2-butyl )phenyl carbamate
20. 3-(2-butyl )N-benzenesulfinyl N_-methyl phenyl carbamate
21. 3-(2-butyl )N-benzenesulfonyl N-methyl phenyl carbamate
50
BROMOPROPYLATE (Acarol , Phenisobromolate, Neoron, Isopropyl 4 .41-
dibromobenzilate) [Isopropyl 2-(4,41-dichbromophenyl )-2-
hydroxyacetate]
CHLOROPROPYLATE (Isopropyl 4,41-dichlorobenzilate) [Isopropyl 2-(4,
"X^dTchTorophenyl )-2-hydroxyacetate]
When chloropropylate was fed to a cow, the major route of elimination
was via urine (>80% of total dose). About 28% of the material was
identified as 4,41-dichlorobenzil ic acid and 55% as conjugates, not
further identified. Chloropropylate was stable (up to 7 h) in
rumen fluid but decomposed in 10,000xg supernatant fraction of beef
liver (St. John and Lisk, 1973).
When exposed to bromopropylate, spider mites (Tetranychus urticae
Kock) and house flies (Musca domestica L.) metabolized this material
to the bromine analogs of benzilic acid, benzhydrol , benzophenone,
and benzoic acid (Al-Rubae and Knowles, 1972).
Spider mites and house flies also metabolized chloropropylate to
the corresponding chlorine-containing analogs of benzilic acid,
benzhydrol, benzophenone, and benzoic acid (Al-Rubae and Knowles,
1972).
51
BROMOXYNIL [3,5-Dibromo-4-hydroxybenzonitrile]
IOXYNIL [3,5-Diiodo-4-hydroxybenzonitrile]
Labeled bromoxynil was applied as the octanoate to wheat (Triticum
vulgare var. Kloka). Under outdoor conditions, when ring-labeling
was used, 88% of the radioactivity was gone in 28 days. Using
11+C-cyano labeling and 11+C-ring labeling, the studies indicated
elimination of label occurred more rapidly with the former and
that metabolic attack occurred on the cyano group (Buckland et al . ,
1973a). After application to leaves of wheat seedlings, bromoxynil
octanoate was initially hydrolyzed. This was followed by hydrolysis
of the cyano group to the amide and acid and decarboxylation; replace-
ment of bromine by hydroxy; and replacement of bromine by hydrogen
(Buckland et al . , 1973b).
When exposed to a flexibacterium, strain BR4, bromoxynil was rapidly
degraded. After five weeks, only 5% of the herbicide remained.
The benzamide and benzoic acid analogs were identified. A third
metabolite was not identified (Smith and Cullimore, 1974). In other
studies, when the octanoate ester of bromoxynil was applied to soils,
80% of lt+C-label in the cyano group and as much as 63% of luC-ring
label were liberated as carbon dioxide. Small amounts of benzamide
and benzoic acid analogs were detected (Collins, 1973). At 25C,
50% of bromoxynil applied to Regina heavy clay was degraded in
2 weeks. The amide and acid were detected (Smith, 1971).
Ioxynil was degraded in a clay loam with high organic matter content.
Most of the 14C-label, both cyano and ring, was recovered as lt+C02.
Mercuric chloride (10_5M) and p-chloromercuribenzoate (5xlO"5M)
inhibited production of ^C02. Ferricyanide was slightly inhibitory
at lO'^M. The benzamide and benzoic acid analogs were identified
as metabolites (Hsu and Camper, 1975).
52
BUSULFAN [1,4-Butanediol di (methylsulfonate)]
The hydrolysis of busulfan (I) proceeded through the unstable
4- (methyl sulfonate)butanol (II) to the cyclic tetrahydrofuran (III).
At pH 3 and 7.4 and 37C, the cyclization reaction was determined to
be first order with a half-life of 12 min (Feit and Rastrup-Andersen,
1973).
CH3S020-(CH2)l+-0S02CH3 >- CH3S020-(CH2)4-0H
I II
HtC CHo
I I
■or
III
53
C-2307 [0,0- Dimethyl 0-3-(N-methoxy-N-methyl-cis-crotonamide)
phosphate]
Rats were treated with 32P- and lt+C-labeled C-2307. With both
labels, r[-dealkylation occurred to produce the unsubstituted amide
derivative. An intermediate, thought to be the N-hydroxy-N-methyl
analog, was detected (Bosik, 1971).
54
CAPTAN [N-Trichloromethyl thio)-cyclohex-4-ene-l ,2-dicarboximide]
FOLPET (Phaltan) [N-(trichloromethylthio)phthal imide]
1LtC-Captan, orally administered to rats, was rapidly metabolized.
Urinary metabolites four days after oral dosing consisted of thiazo-
1 idine-2-thione-4-carboxylic acid (18.6%), dithiobis (methane-
sulfonic acid) (54%) and its disulfide monoxide (13.8%) . After
ip administration, the latter two metabolites were not seen.
T. viride and R^. solani degraded captan by a pathway different
than in rats (DeBaun et al . , 1974a and b).
Captan was degraded in wort. Tetrahydropthal imide was detected
chromatographically and HC1 was inferred from the pH change. CS2
and H2S were not observed (Davidek et al . , 1973).
Hydrolysis of captan in water was pH independent in the range 2-6
and exhibited a half-life of less than one day at 27C. Products of
hydrolysis indentified were 4-cyclohexene-l ,2-dicarboximide, sulfur
and chloride (Wolfe et al . , 1974).
Folpet was degraded in wort with formation of phthalimide.
detected but CS2 and H2S were not observed (Davidek et al .
HC1 was
1973).
H + RSSCCI3
0 H
" I
H2C CH-C-N-CHo-COOH
I I *
S\r/N"CsCH2-CH2-CH-C00H
1 Peptidases
H,C
\^/
CH-COOH
NH
Thiazol idine-2-thione
4-carboxyl ic acid
H03S-CH2-S-S-CH2-S03H
Dithiobis(methanesulfonic
acid) monosulfoxide
CO-
55
CARBARYL (Sevin) [1-Naphthyl N-methyl carbamate]
Selected human tissues were incubated with carbaryl labeled in the
ring or in the [[-methyl group. Five of the 11 metabolites were
identified.
Male
Female
Li
K Lu
Li P V U
UL
Dihydro-dihydroxycarbaryl glucuronide
+
+ +
+
Hydroxycarbaryl glucuronide
+
+ +
Napthyl glucuronide
+
+ +
+ +
tr
Hydroxycarbaryl sulfate
+
+ +
Naphthyl sulfate
+
+
+ + + tr
tr
Li = Liver P = Placenta
K = Kidney V = Vaginal mucosa
Lu = Lung U = Uterus
UL = Uterine Leiomyoma
(Chin et al . , 1974)
Discrepancies between toxic level of carbaryl in various studies were
the result of varying absorption associated with the mode of adminis-
tration and vehicle (Pekas and Giles, 1974).
Absorption from perfused swine intestinal loops
% Absorption in 1 h
Baygon
Carbaryl
Carbyne
Mobam
Zectran
55-56
67-69
66-71
64-70
66
(Pekas, 1974)
Studies have shown that
stomach of a fasted rat
1-naphthol by intestine
When injected into cats,
as sulfate conjugates.
some carbaryl can be absorbed intact from the
(Casper et al . , 1973). The glucuronidation of
was also observed (Bock and Winne, 1975).
1-naphthol was excreted in urine almost entirely
When injected in pigs, 1-naphthol was excreted
as the glucuronide and sulfate in the ratio of 2:1 (Cape! et al . , 1974)
Treatment of rats with l-naphthyl-glucoside-14C showed that hydrolysis
preceded formation of sulfate and glucuronide formation (Dorough et al .
1974).
After 72 h of incubation with HEL (human embryo lung) cell cultures,
carbaryl was almost completely altered but not to C02. The major
metabolite was 1-naphthol. Other metabolites included 4-hydroxy-,
5-hydroxy-, 1 ,4-di hydroxy-, and 1 ,5-dihydroxy-carbaryl and 5,6-dihydro-
5,6-dihydroxycarbaryl . Other unidentified more polar metabolites were
also observed. After acid hydrolysis of the aqueous extraction phase,
three compounds freed from conjugates were identified as 4-hydroxy-
carbaryl , 1 ,4-naphthalenediol , and 5,6-dihydro-5,6-dihydroxycarbaryl .
Carbaryl was also incubated with sonicated HEL cells and cofactors
for 3 h. About 90% of the carbaryl was converted to ether soluble
metabolites. Cochromatography revealed five spots which were identi-
fied as 1-naphthol, carbaryl, 4- and 5-hydroxycarbaryl and 5,6-dihydro-
5,6-dihydroxycarbaryl . The controls also contained 1-naphthol (Lin
et al., 1975).
Incubation of rat enzyme preparations with carbaryl indicated the
formation from carbaryl of C02 and three unidentified hydroxy deriv-
atives, free and conjugated (Palut et al . , 1970).
In vivo resistance varied substantially with age and sex in the sar-
cophagids (S. bullata Parker, S. crassipalpis Macquart, S^. argyrostoma)
and there was a corresponding variation in in vitro ring hydroxylation
of carbaryl. In Phornia regina (Meigen), carbaryl resistance and ring
hydroxylation also increased with age but N-demethylation remained
constant. In vitro ring hydroxylation was lower and N-demethylation
was higher in Musca autumnal is than in the sarcophagids or Phormia.
Optimal incubation was at 30C and pH 7.3 for ring hydroxylation and
N-demethylation. The I50 values of carbaryl to brain cholinesterase
ranged from 1.2 x 10-7 to 6.6 x 10"7 M (Brattsten, 1972).
Houseflies were allowed to feed on 1-naphthol in milk plus sucrose.
Ionophoretic studies indicated the presence of a sulfate, glucoside,
phosphate and glucoside phosphate conjugate. Blowflies (Lucilia
sericata) and grass grubs (Costelytra zealandica) behaved in a similar
manner (Heenan and Smith, 1974) .
Alfalfa leafcutting bees (Megachile pacifica) were exposed to carbaryl.
In the water-soluble fraction, five unidentified metabolites were
observed. The organosol uble fraction contained two unidentified
metabolites as well as 5,6-dihydro-5,6-dihydroxycarbaryl , N-hydroxy-
methyl carbaryl , 4-hydroxy- and 5-hydroxy-carbaryl , N-hydroxycarbaryl
and 1-naphthol (Guirquis and Brindley, 1975).
Male and female Periplaneta americana metabolized injected 11+C-carbaryl
to about the same extent as measured by 1UC02 (Cocks, 1974).
In pond water, carbaryl rapidly hydrolyzed to 1-naphthol. One bac-
terium, possibly a flavobacterium, rapidly degraded 1-naphthol. Of
57
58
three compounds observed, two were identified as a hydroxycinnamic
acid and salicylic acid (Hughes, 1971). In other studies, bacterial
isolates from river water were used. When ^C-labeled 1-naphthol
was used, 11+C02 was observed, indicating rupture of the naphthyl
ring. Also isolated and identified by IR, NMR and mass spectroscopy
was 4-hydroxy-l-tetralone (Bollag et al . , 1975).
Carbaryl and 1-naphthol are stable in weakly acid solutions. In
basic solutions, 1-naphthol turns yellow and then amber. Photo-
oxidation of 1-naphthol gave rise to 2-hydroxy-l ,4-naphthoquinone.
Hydrolysis studies with carbaryl indicated a difference between sea
water and NaOH solution (Wauchope and Haque, 1973).
pH
°C
Obs. T1/2 k2 x 102
10.0
12
10.0
25
10.0
35
9.8
25
9.5
25
9.2
25
9.0
25
Water)
8.0
3.5
8.0
17
8.0
20
8.0
28
99 min
20
8
27
58
116
173
0.7
3.4
9.0
4.3
3.8
3.8
4.0
(Wauchope and Haque, 1973)
1 mo . 0 . 08
4.8 days 1 .0
3.5 days 1 .4
1.0 day 4.6
(Karinen et al . , 1967)
In vitro oxidation and N-demethylation of carbaryl was observed in
the Udenfriend chemical hydroxylation system. The N-methyl oxidation
product, 1 -naphthyl N-hydroxymethyl carbamate, and the N^demethyl
product, 1-naphthyl carbamate, were isolated and identified by mass
and/or infrared spectrometry (Locke and Mayer, 1974).
59
CARBOFURAN (Furadan) [2,3-Dihydro-2,2-dimethyl-7-benzofuranyl-N-methyl-
carbamate]
The metabolism of carbofuran in laying hens was studied with ring- and
carboxyl-^C labeling. Highest residues occurred in livers. About
of ring-11+C and about 20% of carboxyl-11+C appeared in feces. About
of the latter appeared as ll+C02. The following metabolites were
detected in combined and/or conjugated form: 2,3-dihydro-2,2-dimethyl-
3-hydroxylbenzofuranyl N- hydro xymethyl carbamate (III); 3-hydroxy
carbofuran (IV); 2,2-dihydro-2,2-dimethyl-3,7-dihydroxybenzofuran (VII);
3-ketocarbofuran (VIII); 2,3-dihydro-2,2-dimethyl-3-keto-7-hydroxbenzo-
furan (IX) (Hicks, 1970).
After injection of labeled carbofuran into earthworms (Lumbricus
terrestris) , five radioactive materials were excreted. In addition to
carbofuran and two unidentified metabolites, 3-hydroxycarbofuran and
3-hydroxycarbofuran phenol were identified (Stenersen et al., 1973).
14C-Carbofuran was applied to solutions in which the roots of 3-4 year
old mugho pine were immersed. Radioactivity appeared in needles within
3 days and rose to 3.12% of the total radioactivity after 70 days. In
addition to two unidentified compounds, carbofuran phenol and lesser
amounts of 3-hydroxyfuran and 3-ketocarbofuran phenol were present.
As the content of one compound, tentatively identified as f[-hydroxymethyl'
carbofuran, leveled off, the content of carbofuran phenol increased.
Although 3-ketocarbofuran was not isolated in these studies, its
transient occurrence was suggested by the increase of 3-ketocarbofuran
phenol as the 3-hydroxycarbofuran content leveled off. All metabolites
were found conjugated as well as free (Pree and Saunders, 1974).
60
CM::;-
Conjugate
Conjugate
61
N-(2-To1uenesul fenyl )carbofuran [2,3-Dihydro-2,2-dimethyl-7-
benzofuranyl -N-methyl -N- (2-tol uenesul fenyl )carbamate]
N-(2-Toluenesul fenyl )carbofuran (I) was rapidly metabolized by white
mice. Most of the administered radioactivity appeared in urine
within 24 h. Most identities were confirmed by cochromatography
in at least four different solvent systems. In the urine were:
N-(2-toluenesul fenyl )-3-ketocarbofuran (VI ) ; 3-hydroxycarbofuran
TVIII); 3-ketocarbofuran (X); 3-hydroxy-N-hydroxymethylcarbofuran
(VII); carbofuran phenol (IV); 3-hydroxycarbofuran phenol (IX);
3-ketocarbofuran phenol (XI). In feces, there was the sulfinyl
analog of carbofuran (II); carbofuran (III); and compound VI.
11+C02 was also formed (Black et al . , 1973).
When compound I was applied to flies, carbofuran and metabolites VII
and VIII were observed free. In addition, metabolites VII, VIII
and X were found as conjugates (Black et al . , 1973).
62
CARBOXIN (Vitavax) [2,3-Dihydro-5-carboxanil ido-6-methyl-l ,4-
oxathiin]
OXYCARBOXIN (Plantvax) [2,3-Dihydro-5-carboxanil ido-6-methyl-l ,4-
oxathi i n-4 ,4-dioxi de]
Carboxin was administered to female rabbits (New Zealand White
strain) and female rats (Wistar strain) by stomach tube. Urine
and feces were collected and analyzed. In addition to unchanged
carboxin, p_- and o-hydroxy derivatives were observed. Trace amounts
of the m-hydroxy analog were also found occasionally. Three other
minor metabolites observed appeared to be a hydroxylated sulfoxide,
a di hydroxy and a di hydroxy sulfoxide of carboxin. The hydroxy
metabolites were excreted largely as glucuronides in both species
(Waring, 1973).
When carboxin was applied to bean plants (Phaseolus vulgaris L.)
in nutrient solutions, roots readily oxidized this fungicide to the
sulfoxide. The 4,4-dioxide, oxycarboxin, was detectable in roots
and unifoliate leaves for 21 days after application. Most of the
fungicide residue in the roots was in the form of acetone-insoluble
material (Snel and Edgington, 1970). Other studies have indicated
that carboxin is hydrolyzed with formation of aniline which is bound
probably as a glucosylamine (Newby and Tweedy, 1970).
Barley plants formed carboxin-1 ignin complexes in the leaves. These
were liberated by hot dimethyl sulfoxide and identified as carboxin
(30%) and its sulfoxide (70%) (Chin et al . , 1973).
Rhizopus japonicus, a synthetic glucose medium, converted carboxin
into the corresponding sulfoxide and sulfone. Under anaerobic
conditions the sulfoxide and a substituted anilide (not further
identified) were observed. No sulfone was observed (Wallnofer et al . ,
1972).
Carboxin-treated barley seed was grown in vermiculite saturated
with distilled water. Plants were harvested at intervals over a
21-day period and analyzed. Paper chromatography, GLC and mass
spectrometry were used to identify metabolites. Young shoots
contained carboxin, p_- hydroxy phenyl analog and unidentified dihydroxyl
derivatives. Mature plants contained carboxin, £- hydroxy phenyl
derivative, polymeric material and traces of the sulfoxide. Hydrolysis
of the 1 ignin produced material that gave a chromatographic band
coincident with the £-hydroxyphenyl (Briggs et al . , 1974).
63
64
CDAA (Randox) [2-Chloro-jM-dial lylacetamide]
CDAA rapidly decomposed in plants. In rumen fluid of cows, it was
stable for 24 h. When incubated with beef liver 10,000xg super-
natant, CDAA was not detectable after 30 min. No metabolites were
identified (St. John and Lisk, 1974).
When 1UC-CDAA administered as a single dose to rats, 86% was excreted
in the urine during the first 48 h; 16%, in feces. About 89% of the
urinary 14C was the mercapturic acid of CDAA. Studies also showed
that CDAA reacted non-enzymatically with glutathione (Lamoureux
and Davison, 1975).
65
2-CEPA [2-Chloroethylphosphonic acid]
In leaf and stem tissue of Hevea brasil iensis , 2-CEPA was converted
into 13 and 20 compounds, respectively. One of the compounds
obtained from stem and leaf was identified by TLC as 2-hydroxyethyl-
phosphonic acid (Archer et al . , 1973).
This compound also formed in small amounts when 2-CEPA was incubated
for several days in buffer solutions at room temperature, When
heated in alkali, ethylene and non-volatile material, identified
as 2-hydroxyethylphosphonic acid by autoradiography and TLC, was
formed (Audley and Archer, 1973).
66
CHLORAL HYDRATE
Within a few days after application to soil, chloral hydrate was
oxidized to trichloroacetic acid (TCA). TCA degraded with evolution
of C02. Some formaldehyde was also detected at the beginning of
the decomposition (Schutte and Stephan, 1969).
67
Chlordane and Related Compounds
a - (or cis-) chlordane
l-exo,2-exo,4,5,6,7,8,8-octachloro-2,3,3a,4,7,7a-hexahydro-4,
7-methanoindene
y- (or trans-) chlordane
1 -exo,2-endo,4,5,6,7,8,8-octachloro-2,3,3a,4,7,7a-hexahydro-4,
7-methanoindene
Chlordene
4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahyoro-4,7-methanoindene
Chlordene epoxide
4,5,6,7,8,8-hexachloro-exo-(cis)-2,3-epoxy-3a,4,7,7a-tetrahydro-
4, 7-methanoindene [also an endo-( trans )-2,3-epoxy- isomer].
Oxychlordane
l-exo>2-endo>4,5>6>7,8,8-octachloro-2>3-exo-epoxy-2,3)3a>4,7,7a-
hexahydro-4, 7-methanoindene
Heptachlor
1 ,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene
68
Human adipose tissue specimens routinely collected from postmortem
examinations and therapeutic surgery procedures were analyzed for
a series of organochlorine pesticide residues. Oxychlordane was
found in 21 of 27 specimens and ranged from 0.03 to 0.40 ppm (Biros
and Enos, 1973).
HCS-3260"ll4C (a 3:1 cis-chlordane and trans-chlordane) was admin-
istered to rats. After a single oral dose, over 90% was eliminated
in 7 days. Feces was the main route of excretion. After feeding
HCS-3260" 14C to rats for 56 days, cis- and trans-chlordane, oxy-
chlordane, dichlorochlordene and seven unidentified compounds were
observed. Oxychlordane was observed after single doses of either
cis- or trans-chlordane. After feeding a male rabbit HCS-3260" 14C
for 2 days, in addition to cis- and trans-chlordane, oxychlordane
and dichlorochlordane were observed in liver and kidney. Seven
unidentified compounds were also found in urine and feces (Barnett
and Dorough, 1974).
Sugar beets were grown in soil treated with HCS-3260 or chlordane.
Sugar beet pulp processed from these plants was fed to cows. In
milk fat, there were detectable amounts of a- and y-chlordane and
oxychlordane. The major product in the milk fat was identified
as oxychlordane by mass spectrum. Similar residues were found in
the fat (Dorough and Hemken, 1973).
The hepatic mixed function oxidase (MF0) of several fish was inves-
tigated. When chlordene was used as substrate, hydroxylation preceded
epoxidation. With preparations from the Kissing Gourami (Helostoma
sp.) and pigeon, l-hydroxy-2,3-epoxychlordene formed after the epoxide,
Vmaix and K„ were also determined (Garretto and Khan, 1975; Runnels
and Khan, 1973; Stanton and Khan, 1973).
Chlordene substrate MF0 Vm,v MF0 Km
Epoxidation
Kissing Gourami
Bluegill (Young)
0.26
0.18
15.59
15.00
Hydroxylation
Kissing Gourami
Bluegill (Young)
0.47
1.25
11.06
13.00
Epox.-Hydrox.
0.08
10.90
69
MFO V
max
Substrate
Chlordene
Hyd
rox.-Epox.
epoxide
Hydi
"oxychl
ordene
Chlordene
Kissing Gourami
0.16
0.32
0.09
Bluegill fry
0.16
1.05
Trout
0.33
0.38
Bluegill try
0.13
0.99
Pigeon
0.26
0.44
0.10
Mouse
0.23
1.13
— • ™ -
A 3-day aquatic system was used to evaluate uptake and biotrans-
formation of chlordene, heptachlor and heptachlor epoxide. Results
are tabulated. Water samples indicated the rapid formation (^24 h)
of heptachlor epoxide and 1-hydroxchl ordene and its epoxide.
Compd. Used
Oedogonium
Physa
Culex
Gambusia
Metabolite
(Snai
1)
(Snail)
(Mosquito)
(Fish)
Chlordene
Chlordene epoxide
+
+
+
+
1 -Hydroxychl ordene
+
+
+
+
1 -Hydroxychl ordene
epox.
+
+
+
+
Unknown I
+
+
Unknown II
+
+
Polar
+
+
+
+
Heptachlor
Heptachlor epoxide
+
+
+
+
1 -Hydroxychl ordene
+
+
+
1 -Hydroxychl ordene
epox.
+
+
+
Unknown I
+
+
Unknown II
+
+
Unknown III
+
+
Unknown IV
+
+
+
Unknown V
+
+
Polar
+
+
+
+
Heptachlor
Epox.
1 -Hydroxychl ordene
epox.
+
+
+
+
Polar
+
+
+
+
70
Hexachlorocyclopentadiene was also evaluated ana found in all phases
of the system. In addition, four unidentified compounds and polar
material were also found in all phases (Lu et al., 1975).
Other studies with the salt marsh caterpillar, Estigmane acrea, and
sheep liver microsomes were summarized in the following table.
Compound
Used
Metabolite
Salt Marsh
Caterpillar
Sheep Liver
Microsomes
Chlordene Chlordene epoxide +
1-Hydroxychlordene +
1-Hydroxychlordene epox. +
Unknown I +
Unknown II
Unknown III +
Polar +
+
+
+
+
+
+
Heptachlor Heptachlor epoxide
1 -Hydroxychl ordene
1-Hydroxychloroene epox.
Unknown I
Unknown II
Polar
+ +
+ +
+ +
+( feces only) +
+( feces only)
+ +
Heptachlor
Epoxide
Polar
(Lu et al., 1975)
In less than one day, heptachlor was converted to heptachlor epoxide
in skim milk and try pti case soy broth, with or without the presence
of the test bacteria (Collins, 1969).
Soil was treated with high purity chlordane (-95% a plus 6 chlordane;
cis/trans - 3:1). Alfalfa was grown on the treated soil. It was
sampled 2 months after treatment; cut back at 3 months; and then
sampled at 4 months and again at 1 year. Analysis by GLC indicated
the presence of a-, y- , oxy- and photo-cis-chlordane. Oxychlordane
comprised 9 to 13% of the total residues in the alfalfa but was not
detected in the soils. The intermediate compound, 1 ,2-dichloro-
chloroene, was found at 0.011 ppm in the alfalfa from plots treated
at 10 lb a.i./A and in trace quantities at 5 lb a.i./A. Photo-cis-
chlordane accounted for 9 to 16% of the total residues in the alfalfa
and was also found in the soil (Wilson and Oloffs, 1973).
71
Ultraviolet irradiation of cis- and trans-chloroane in acetone
produced 3 products. The half-caged analog of cis-chlorciane, photo-
cis-chlordane, was obtained in high yield. Two products were formed
from trans-chlordane. One was identified as photo- trans-chl or dane.
The other was not identified, but a molecular composition of Cio^Cls
appears likely (Onsuka and Comba, 1975). Irradiation of 6-chlordane
in acetone produced II and III. Irradiation of IV gave VI (Parlar
and Korte, 1973).
A mixture of oxychlordane and xanthone was streaked on the surface
of silica gel chromatoplates and then exposed to sunlight. Two
photo-isomers were formed. Several structures were possible for
each compound and this has not been resolved (Ivie, 1973).
Chlordene was adsorbed on silica gel and then irradiated with ultra-
violet light at x^290 and A^230nm. Differences observed were mainly
quantitative. Chlordene required 1.5 h for 50% conversion of the
starting materials. Products included: chlordene epoxide, photo-
chlordene, 1-exo-hydroxy chlordene, ketochlordene, an unidentified
compound and polar and polymer material. When quartz was used,
instead of pyrex, heptachlor was also obtained (Gab et al., 1975).
The decomposition of heptachlor epoxide in KBr disks with exposure
to ultraviolet radiation and sunlight was studied. The products
obtained were identical to those obtained by exposure of solid
heptachlor epoxide to sunlight and ultraviolet radiation (Graham
et al., 1973).
72
.CI
"M, -— v 2
( -)trans-Chlordane
Photo- trans-chlordane
'OH
CI
^ ^^M«
l-Hydroxychlordane Oxychlordane
Cls-C^T^CI
CI
1 ,2-Dichlorochlordene
CI
Photoheptachlor
hvy
Photoheptachlor Epoxide
hv OH
<$£»-*. %y -+ *££*
Heptachlor
\
Heptachlor Epoxide Heptachlor diol
^-aft^O^.
Chlordene
\
Chlordene Epoxide
1 -Hydroxychl ordene 1 -Hydroxy-2 ,3-epoxy-
chlordene
CI,
OH
OH
Chlordenediol
73
CHLORDIMEFORM (Galecron) [N-(4-Chloro-o-tolyl )- N' -N' - dime thy lformami dine]
Chlordimefonn (I) was quite susceptible to degradation by cultures of
primary human embryonic lung cells. Dimethyl ation to N-demethyl-
chlordimeform (II) preceded cleavage to N-formyl-4-chloro-o-toluidine
(III). Three unidentified compounds were also found in addition to
4-chloro-o-toluidine (IV) (Lin et al., 1975b).
Aqueous solutions of ]ltC-chlordimeform were administered by stomach
tube to Sprague-Dawley rats. Thin-layer chromatography was used to
separate the metabolites and IR and UV were employed for identification.
Half of the dose was excreted in urine in 24 h; 87.1 and 95.4% in
96 h by males and females, respectively. In addition to I, compounds
II, III and IV were found in urine. Five unidentified compounds were
also present. In vitro studies with liver homogenates produced the
same metabolites (Morikawa et al., 1975).
Absorption and metabolism of chlordimeform by the rice stem borer
was slow. Analyses, however, indicated the formation of compounds
II, III, IV and five unidentified compounds (Morikawa et al., 1975).
From cultures of mixed populations of soil microorganisms to which
chlordimeform had been added, a new metabolite of the pesticide was
isolated and identified as 4'-chloro-2'-methylmalonanilic acid.
Confirmation of structure was obtained by synthesis and mas spectral
data (Ross and Tweedy, 1973).
P=Plants
^Mammals
0=Microorganisms y—
I=Insects
=CH-N-CH3
N-Glucosyl amine
Conjugate
H 0
/>N-C-CH2-C00H
TH
CI-/ Vn-cho
^~^C00H
VI
^OOH
VII
74
CHLORMEQUAT (CCC) [2-Chloroethyl trimethyl ammonium chloride]
CCC-14CH3 was metabolized to choline in barley, wheat, tobacco and
maize. Choline isolated from these plants contained 10-20% of the
applied radioactivity. A small part of the radioactivity was also
found in the betaine fraction. In Nlicotiana rustica L., methyl
groups of CCC-lt4CH3 were incorporated into the alkaloid nicotine;
in Hordeum vulgare, into the alkaloid gramine (Stephan and Schutte,
19701^ Radioactivity from l,2-ll+C-CCC was also found in the choline
moiety of phosphatidyl choline in winter barley (Hordeum vulgare L.
var. Dover) (Belzile and Willemot, 1972).
When applied to coastal bermudagrass (Cynodon dactyl on L. Pers.),
1 ,2-1LfC-CCC was metabolized; and, within 24 to 48 h after application,
about 25% of the label was found distributed among choline, betaine
hydrochloride, serine, ethanolamine, glucose and C02 (Ayeke, 1969).
Wheat seedlings were root-treated with 1 ,2-ll4C-chlormequat. Trans-
location was rapid and choline was formed. The latter was metabolized
via betaine, which was demethylated, to glycine and serine. These
were then incorporated into the plant protein fractions. Some 14C02
was also formed (Dekhuijzen and Vonk, 1974).
75
CHLORODIOXIN
(See also Irgasan.)
Although these compounds are not pesticides, their presence as contam-
inants in phenol based pesticides and their potential hazard to the
environment places them in a position of great interest. Consequently,
these compounds have been included in this compilation.
When fed to rats, 2,3,7,8-tetrachloro-dibenzo-p_-dioxin (TCDD) was
stored primarily in the liver. Total retention was dose dependent
and varied from 5.5 to 10.0 times daily intake between 14 and 42 days.
At steady state, analyses indicated that retention would approximate
10.5 times daily intake. After removal of TCDD from the diet, the
half-life for elimination was 12 and 15 days for males and females,
respectively (Fries and Marrow, 1974 and 1975).
Thermal decomposition of 2,4,5-trichlorophenol gave rise to 2,3,7,8-
TCDD (Milnes, 1971).
Irradiation of TCDD in methanol produced 2,3,7-trichloro-dibenzo-p_-
dioxin and in a dichloro analog. 0ctachlorodibenzo-p_-diox1n yielded
a series of dechlorinated dioxins (Plimmer et al., 1971).
Irradiation of photosensitized 2,4-dichlorophenol in water yielded
dimeric materials primarily and traces of dechlorinated products.
Using mass spectrometry, two tetrachlorophenoxyphenols and two tetra-
chlorodi hydroxy bi phenyls were detected. A trace of trichlorophenoxy-
phenol was also detected but there was no evidence of substituted
dibenzo-£-dioxin. The major product was identified as 4,6-dichloro-
2-(2,4-dichlorophenoxy)phenol . An unidentified isomer of this compound
was also present. The presence of riboflavin and oxygen was necessary
(Plimmer and Klingebiel, 1971).
2-Hydroxy nonachlorodi phenyl ether (pre-dioxin) was found as a contam-
inant in PCP. This material is thermally unstable and undergoes ring
closure to form octachlorodioxin. An iso-predioxin was also found
in a technical organic salt of PCP (Jensen and Renberg, 1972).
The persistence of 2,3,7,3-tetrachlorodibenzo-p_-dioxin (TCDD) in
Hagerstown and Lakeland (fid.) soils was found to be 56 and 63%,
respectively, after one year. When 2,4-dichlorophenol or 2,4,5-
trichlorophenol were added to soil, neither the 2,7-dichloro- nor
the tetrachloro-dibenzo-p_-dioxin was detected after 70 days. However,
a polar metabolite of the dichloro analog was observed but not identified,
Neither of these two dioxins was synthesized bv microbial actions
(Kearney et al . , 1972).
76
Predioxin
Iso-Predioxin
Dibenzofuran
Dibenzofuran
77
CHLORONEB (Demosan, Tersan SP) [1 ,4-Dichloro-2,5-dimethoxybenzene]
After exposure to chloroneb, young bean plants absorbed the chloroneb
and accumulated it mostly in roots and lower stem. Chloroneb was
metabolized to 2,5-dichloro-4-methoxyphenol (DCMP) and then converted
to the 6-D-glucoside (Thorn, 1973).
Incubation of chloroneb, and DCMP indicated that methylation of the
phenol, as well as demethyl ation of chloroneb, occurred. Twenty-
three different microorganisms were studied. Eight organisms de-
methyl ated chloroneb and methylated DCMP:
Fusarium solani f. pi si
Fusarium solani f. phaseoli
Mucor ramannianus
Cephalosporium gramineum
Aspergillus fumigatus
Verticil 1 ium albo-otrum
Cephalosporium gregatum
Chaetomium globosum
Six organisms were capable only of demethyl ating chloroneb:
Sclerotinia sclerotiorum
Helminthosporium victoriae
Cory nebacteri urn fascians
Stemphyll ium sarcinaeforme
Cladosporium cucumerinum
Helminthosporium sativum
Three organisms were capable of methylating DCMP but did not degrade
chloroneb to DCMP:
Trichoderma viride
Penicillium frequentans
Rhizoctonia solani
(Wiese and Vargas, 1973)
In other studies, however, mycelium of R. solani degraded chloroneb
to DCMP, which was identified by IR, NMR, and mass spectrographic
analyses. N. crassa metabolized chloroneb slowly to a compound
thought to be an aglycoside (Hock, 1969).
78
CHLOROTHALONIL [2,4,5,6-Tetrachloroisophthalonitri le]
In cells of Saccharomyces pastorianus, chlorothalonil acted as an
alkylating agent. Initial uptake resulted in the formation of
glutathione derivatives. The fungicide also reacted with proteins
(Tillman et al., 1973).
79
CHLORPROPHAM (CIPC, Isopropyl -m-chlorocarbani late) [Isopropyl N-(3-
chlorophenyl )carbamate]
PROPHAM (IPC, Isopropyl carbanilate) [Isopropyl N-phenyl carbamate]
After dosing a goat and chicken with labeled propham, analyses conducted
showed the presence of the £-sulfate derivative in goat milk and goat
and chicken carcasses. The glucuronide was also found in chicken
carcass (Paulson and Jacobsen, 1974).
The main route of excretion of propham by a goat was via the urine.
Small amounts appeared in milk and feces. After administration of
phenyl-ll,C-labeled propham to a goat, 13 labeled metabolites were
obtained and purified. Identification procedures included deriva-
tization and chromatography, mass spectrum analyses, enzyme hydrolysis,
syntheses and IR spectrometry. The metabolites identified were:
1. glucuronic acid conjugate of 4-hydroxypropham
2. sulfate ester of 4-hydroxypropham
3. glucuronic acid conjugate of 4-hydroxyacetanilide
4. sulfate ester of 2-hydroxyaniline
5. conjugate of 2-hydroxy isopropyl 4-hydroxycarbanilate
6. sulfate ester of 2-hydroxypropham
[7. sulfate ester of 4-hydroxyacetanilide — not obtained from
goats.]
Compounds 1 and 2 were obtained from dosed rats as well as goats.
Compound 7 was obtained from rats only. All others appeared in
both animals. Partial identification of four other metabolites
from the goat indicated the presence of:
1. a 4-hydroxypropham conjugate
2. a 2-hydroxypropham conjugate
3. a £-aminophenol conjugate
4. a 3,4-dihydroxypropham conjugate
(Paulson et al., 1973)
80
In rats, the average biological half-life for IPC in internal organs
was 5.0 h; in brain, muscle and fat tissue, 13.3 h. Tentative
identification was made for the following urinary metabolites: 4-
hydroxy-IPC; l-0H-2-propyl-IPC; 1 -carboxy-1 -ethyl -IPC; l,3-(0H)2-2-
propyl-IPC; and 4-hydroxy-IPC-sulfate. Several other metabolites
were observed but not identified (Fang et al., 1974).
Rats and sheep were fed alfalfa which had been root-treated with
propham- C. In sheep urine, the major labeled metabolite was
4-OH-IPC sulfate ester. Another metabolite was identified as the
glucuronic acid conjugate of 4-OH-IPC. Co-chromatography, IR and
mass spectral analyses were used for identification (Paulson et al.,
1974).
Alfalfa was root-treated with CIPC. Analyses of the root and shoot
tissues indicated the presence of two aglycones. After hydrolysis,
2-OH-CIPC was found in root and shoots, 5.1 and 51.3%, respectively.
The 4-OH-CIPC was also found, 26.4 and 17.6% in shoots and roots,
respectively. The nature of the conjugates was not determined.
However, both aglycones were liberated by treatment with hesperidinase,
glucuronidase or cellulase (Still and Mansager, 1974).
Alfalfa, which had been root-treated with chlorpropham-phenyl-ll*C,
contained chlorpropham and glycoside conjugates of 2-OH-CIPC and
4-OH-CIPC. This plant material was fed to rats and a sheep. Little
difference was observed in metabolite patterns in urine and feces of
the sheep and rats. Sulfate and glucuronic acid conjugates were
present in urine from both rat and sheep. The 4-OH-CIPC and 2-OH-
CIPC conjugates were most abundant. The 2-OH-CIPC sulfate appeared
in sheep urine. Glucuronide or sulfate conjugates of 2-0H-5-chloro-
acetanilide and 4-0H-3-chloroacetanilide were found in rat urine
(Still et al., 1974a).
Soybean [Glycine max (L.) Merr. variety Hawkeye] were germinated,
grown and root treated with chlorpropham-1 ^C. A polar metabolite
was obtained from the roots and identified by enzymatic studies,
derivatization and GLC, mass spectrum and NMR as an 0-glucoside of
2-hydroxychlorpropham. Similar analyses of shoots showed the presence
of the 2- and 4-hydroxychlorprophams as 0-glucosides. The latter was
found to be unstable to aqueous acid hydrolysis (Still and Mansager,
1973a). In cucumbers, only 4-hydroxychlorpropham conjugates were
observed (Still and Mansager, 1973c).
In resistant soybeans, the major metabolite of CIPC was 2-hydroxy-
CIPC whereas in susceptible soybeans it was the 4-hydroxy analog.
The phenolic metabolites were conjugated in both susceptible and
resistant plants (Still et al., 1974b).
81
Soybeans were grown in the presence of 14 C-CIPC . Polar extracts
of shoots, when subjected to alkaline hydrolysis, yielded some 3-
chloroaniline. Analyses also showed the presence of 1-OH-CIPC.
When grown in soil, soybeans metabolized CIPC primarily by alkyl
hydroxylation and only small amounts of 2-0H- and 4-OH-CIPC were
formed. In hydroponic culture, metabolism was primarily to aryl
hydroxylated metabolites (Wiedmann and Ecke, 1975). In oats, the
4-OH-CIPC formed is converted to an S-cysteinyl hydro xychlorpropham
(Rusness and Still, 1975).
Soybean plants were root-treated with propham-14 C. Analyses of the
metabolites indicated that they were glycosides of 2-hydroxypropham
and that one of these metabolites was probably 6-0-glucoside (Still
and Mansager, 1973b).
82
CLOPIDOL [3,5-Dichloro-2,6-dimethylpyridin-4-ol]
When administered to rabbits, clopidol was rapidly absorbed and
excreted mostly via urine. Less than \% of the dose remained in
the tissues at 16 h after dosing. In addition to unchanged clopidol,
3,5-dichloro-2-hydroxymethyl-6-methylpyridin-4-ol and its glucuronide
were present in urine. Another metabolite may be the 2,6-dihydroxy-
methyl analog (Cameron et al., 1975).
83
CREDAZINE [3-( 2-Methyl phenoxy )pyri dazi ne]
When this herbicide was irradiated with sunlight in aqueous solution
at pH 6.8, about 65% of the credazine was unchanged after 3 weeks
of exposure. The photolytic decomposition was greater at pH 9.0 and
produced primarily 3-pyridazinone-(2H) and o-cresol . o-Cresol decom-
posed rapidly but pyridazinone was unaffected. Also identified were
salicylic acid, hydroxylated credazine, and 3-( 2-methyl phenoxy )
pyridazine-1 -oxide (Nakagawa and Tamari, 1974).
84
CYANIDE
Opposums were dosed with sodium cyanide by means of a stomach tube.
Feces and urine were collected and analyzed.
Analysis indicated that the major route of detoxication of cyanide
was via conversion to thiocyanate, which was excreted in the urine.
Traces of 2-imino-4-thiazolidine carboxylic acid were observed in the
crude concentrated extract of the urine (Turner, 1969).
Studies with a basidiomycete showed that ammonia, HCN, and acetalde-
hyde condense to form a-aminopropionitrile which can be hydrolyzed
by nitrilase to alanine (Strobel , 1966 and 1967). In other studies,
HCN was added to cultures of Rhizoctonia solani . a-Aminobutyronitrile
was isolated and has been proposed as an intermediate in cyanide fixa-
tion by Rhizoctonia solani (Mundy et al . , 1973).
Cyanide was administered to C57 Black mice by i.p. injection. When
given alone, cyanide was extensively converted to thiocyanate and
excreted in the urine. Pretreatment of animals with nitrite and
thiosulfate increased thiocyanate excretion. Pretreatment with cobalt
compounds alone or in combination with thiosulfate decreased the
formation of thiocyanate and gave increased urinary excretion of
cobalt ions and strongly bound cyanide complexes (Frankenberg and
Sorbo, 1975).
85
CYOLANE [2-Diethoxyphosphinylimino-l ,3-di thiol ane]
Cyolane-treated alfalfa hay was fed to a cow one year after treatment
of the alfalfa. Cholinesterase was depressed and did not return to
normal levels until 3 months after feeding of the cyolane-contaminated
hay had been discontinued. Identification of the residues was not
made (Tadjer and Egyed, 1974).
86
2,4-D and RELATED COMPOUNDS
2,4-D [2,4-Dichlorophenoxyacetic acid]
2,4-DB [4-(2,4-Dichlorophenoxy)butyric acid]
Erbon [2-(2,4,5-Trichlorophenoxy)ethyl 2,2-dichloropropionate]
MCPA [4-Chloro-2-methylphenoxyacetic acid]
Si 1 vex [2-(2,4,5-Trichlorophenoxy)propionic acid]
2,4,5-T [2,4,5-Trichlorophenoxyacetic acid]
CPA [Chlorophenoxyacetic acid]
87
2,4-D [2,4-Dichlorophenoxyacetic acid]
Two h after ingestion by human volunteers, 2,4-D appeared in the urine.
More than 75% of the dose was excreted within 96 h. No metabolites
were detected.
Pharmacokinetics
C. =
A k
' = vd(kf-Ke) Cexp(-ket)-exp(Kft)]
After a 5 mg/kg dose:
kf x 102(h_1) = 27.4 ± 4.0
k x 102(h_1)
e
-0.5
(e)(h)
= 2.1 ± 0.2
= 33.0 ± 3.1
Where:
C. = Plasma concentration at time t
A = dose in mg/kg
kf = first order rate constant -
absorption
k = first order rate constant -
clearance
Vd x 102 (1/kg) = 10.1 ± 0.3 Vd = Volume of distribution
(Kohli et al., 1974)
Bovine serum albumin and 2,4-D interact. Binding of 2,4-D is rather
extensive but is greatly reduced in the presence of palmitic acid
(Kolberg et al . , 1973). The properties of the binding site resemble
the properties of the amino acid sequence adjoining the tryptophan at
the binding site of bovine serum albumin (Mason, 1975).
After feeding 2,4-D to sheep and cattle, analysis of muscle, fat,
liver and kidney showed the presence of 2,4-dichlorophenol (Clark et
al., 1975).
The butyl ester of 2,4-D is unstable in water and undergoes hydrolysis
in 9 to 10 days with formation of 2,4-D. If fish are present, high
residue levels may accumulate within a few days and persist for a week
or more (Shcherbakov and Pol uboyari nova, 1970).
In studies with maize leaf tissues, 2,4-D bonded to some extent with
cellular protein (Zemskaya et al . , 1971). Oat, wild cucumber, and
to a lesser extent cocklebur were able to bind or alter large amounts
of 2,4-D (Dexter, 1970). Yellow nutsedge (Cyperus esculentus L.) did
not absorb 2,4-D as well as some of the susceptible broadleaf plants.
Analysis of methanol -soluble extracts indicated that yellow nutsedge
does not appreciably degrade the 2,4-D (Bhan et al . , 1970).
88
Shortly after exposure of Ribes sativum leaves to 1 -ll+C-2,4-D, 37.8%
of the label appeared in glycolic acid in the water-soluble metabolites.
11+C-Glycine was also observed (Fleeker, 1973).
Soybean (Glycine max L. var. Acme) cotyledon callus stock cultures
were grown on an agar medium. After 2 ,4-D-l -1£+C was added, 2,4-D-
glutamic acid and 2,4-D-aspartic acid were the major amino acid
conjugates found. In addition to these, five other conjugates were
isolated and observed: alanine, leucine, phenylalanine, tryptophan,
and valine. Two other conjugates were not identified. When 2,4-D-
glutamic acid was added to the media, 2,4-D and the aspartate complex
were formed. The aglycones 4-hydroxy-2,5-D and 4-hydroxy-2,3-D were
also formed. These studies also indicated a more rapid conversion of
the glutamate complex to the foregoing inactive aglycones than of 2,4-D
itself (Feung et al . , 1973). Additional studies were conducted with
callus tissues of carrot, jackbean (Canavalia ensiformis), sweet corn
(Zea mays) , tobacco and sunflower (Helianthus annusT After the five
plant callus species were exposed to 2,4-D, metabolism produced amino
acid conjugates and hydroxylated metabolites as glucosides. After 3-
glucosidase treatment of water soluble extracts, 2,4-D, 4-0H-2,3-D and
4-0H-2,5-D were found in callus tissue of all five plants. Corn callus
tissue alone contained 4-hydroxy-2-chlorophenoxyacetic acid and 3-0H-2,4-D.
The glutamate conjugate of 2,4-D was found in all five plants; and the
aspartate conjugate, in corn, tobacco and jackbean (Feung et al . , 1975).
In studies with labeled 2,4-D and seedlings of wheat, insoluble complexes
of protein and 2,4-D formed. Water-soluble compounds also formed
(Hallmen and Eliasson, 1972). Other studies have also shown that plants
form water-soluble complexes and hydroxylated 2,4-D derivatives
(Eidel'nant and Mostovaya, 1972).
After treatment of tomato plants of the variety "Eurocross A," acid
hydrolysis of the n-butanol extracted glycosides yielded 4-0H-2,3-D
and smaller amounts of 4-0H-2,5-D, 2,4-D and an unidentified metabolite
(Muller and Schuphan, 1975).
In potatoes, the differences between total and free residue levels of
2,4-D were small but statistically significant and indicated the
presence of conjugated 2,4-D. Residues of 2,4-dichlorophenol were
also present (Bristol et al . , 1974).
The results of studies in susceptible rape (Brassica napus L. cv.
Nilla) and sunflower (Helianthus annus L. var. uniflorus) indicated
that 2,4-D existed mainly in the free state and only to a small extent
in water-soluble complexes (Hallmen, 1974). Similar results were
obtained with wheat (Triticum aestivum L. cv. Starke) and Norway spruce
[Picea abies (L.) H. Karst] (Hallmen, 1975).
89
The influence of four algae on 2,4-D residues in water was studied.
Of the four algae used [Chlorella pyrenoidosa Chick., Chlamydomonas
reinhardtii Dangeard, Euglena gracilis Krebs. 'urophora', and
Scenedesmus quadricanda (Turp.) Breb.], only the latter was effective
in removing the herbicide. When ring-labeled 2,4-D was incubated with
Scenedesmus, the main metabolite observed was 3-0H-2,4-D (26% of total
radioactivity). The 5-hydroxy analog was also identified. Two other
metabolites having higher R^ values than 2,4-D were not identified
(Valentine and Bingham, 1974).
Molds grown in culture broths containing 2,4-D analogs produced growth-
inhibiting principles. Active principles were isolated as crude yellow
oils (Naito, 1958; Naito and Kojima, 1957; Naito and Tani , 1955 and
1956a and b). When the molds Gloeosporium olivarum, Gloeosporium kaki
and Schizophyllum commune were grown on media containing 2,4-D, color-
less needles were isolated and identified by IR spectrum, mass spectrum,
elemental analysis and M.P. as the ethanol analog (Nakajima et al . ,
1973).
Arthrobacter sp. cultures were grown on 2,4-D. An enzyme preparation
prepared from these cultures converted cis,cis-2,4-dich1oromuconate to
chloromaleyl acetate. The enzyme that converts dichloromuconate to
2-chloro-4-carboxymethylene but-2-enolide was separated from the enzyme
that opens the butenolide lactone (Sharpee et al . , 1973).
In other studies with an enzyme preparation from Arthrobacter sp.,
the ether linkage of 2,4-D was cleaved to produce initially 2,4-
dichlorophenol and glyoxylate. Evidence for the latter was indirect
with observation of the formation of a-alanine. Neither acetate nor
glycol ate was metabolized by the bacterial enzyme preparation. Catechols
were cleaved to cis,cis-muconic acids. The products of 4-chloro- and
3,5-dichloro-catechol were the 6-chloro- and a,Y-dichloromuconic acids,
respectively. The latter was proposed on the basis of its UV spectrum
and analogous formation of 3-chloromuconic acid from 4-chlorocatechol .
Acidification caused lactonization to the corresponding butenolides.
Some cis,trans-B-chloromuconic acid also formed. a-Chloromaleyl acetate,
formed from a,Y-dichloromuconic acid, was identified by GLC, UV and mass
spectrometry. This compound decarboxylated readily to form the lactol
of cis-a-chloro-Y-ketopent-2-enoic acid and was identified by GLC, IR,
mass spectrometry and nuclear magnetic resonance. In the presence of
NADH, a-chloromaleyl acetate was metabolized to yield succinate. Prelim-
inary studies indicated a-chloro-y-ketoadipate and chlorosuccinate as
intermediates (Tiedje, 1969).
In studies with 2,4-D and MCPA, applications of either to soil affected
a cross adaptation. After a period of 19 years, repeated applications
reduced the time for 50% degradation for 2,4-D and MCPA from 10 and 20
weeks to 4 and 7 weeks, respectively (Torstensson et al . , 1975).
90
The irradiation of aqueous solutions of 2,4-D and several of its
esters indicated differences in mode of decay. The free acid undergoes
mono- and di-dechlorination, ortho and para hydroxylation, and polymer
formation. Intact esters (ethyl, butyl and 2-methylheptyl ) undergo
monodechlorination. In light stronger than sunlight, further dechlor-
ination and rearrangement occurs (Binkley and Oakes, 1974a and b,
Binkley et al . , 1974).
Irradiation of 2,4-D aqueous solutions with UV above 280 nm gave little
reaction. When a sensitizer such as riboflavin was also used, the
products included tetrachlorophenoxyphenols and two isomeric tetra-
chlorodihydroxybi phenyls. The major product was 4,6-dichloro-2-
(2,4-dichlorophenoxy)phenol . A trace of a trichlorophenoxy phenol
was also observed (Plimmer and Klingebiel, 1971).
Studies have also shown that photochemical degradation of 2,4-D
derivatives follows two paths. In water, the predominant path, except
for esters, involves removal of a chlorine and replacement with a
hydroxyl group and cleavage of the ether to form the phenol. In
methanol, a chlorine is abstracted from the ring (Binkley et al . , 1974).
2,4-D was formulated as a urea type polymer and exposed to irradiation
at 356 nm. This form of 2,4-D was less resistant to degradation than
conventional 2,4-D. UV degradation of the polymerized 2,4-D was
eliminated by incorporation of UV absorbers. Resistance to thermal
degradation, however, was greater in the polymerized form than in
non-polymerized 2,4-D (Baur and Bovey, 1974).
Pyrolysis of amine salts of 2,4-D produced corresponding amides.
Above 160C, 2,4-dichlorophenol , imines, lactones, and other compounds
also formed. Above 200C, the amides seemed to decompose (Hee and
Sutherland, 1974).
Basic and acid hydrolysis of 2,4-D esters yielded 2,4-D and the
corresponding alcohol. The hydrolysis half-life of the butoxyethyl
ester at 25C increased from 9 h at pH 8 to more than one year at pH 5.
The major photoreaction of 2,4-D esters at \<290 nm involved cleavage
of the ortho C-Cl bond. Calculated sunlight photolysis half-lives
of butoxyethyl ester, at latitude 34°N ranged from 59 h in summer to
430 h in winter, and 13 h and 109 h, respectively, in hexadecane
(Zepp et al., 1974).
91
MCPA [4-Chloro-2-methylphenoxyacetic acid]
MCPA was applied to a rice field. About 70% of the material reaching
the target area was lost by evaporation and soil percolation. Photo-
lysis of MCPA with an indoor photoreactor or sunlight yielded 4-chloro-
2-methyl phenol and lesser amounts of o-cresol and 4-chloro-2-formyl-
phenol (Soderquist and Crosby, 1975).
92
2,4,5-T [2,4,5-Trichlorophenoxyacetic acid]
Bovine serum albumin bound 2,4,5-T extensively. Palmitic acid reduced
the binding (Kolberg et al . , 1973). The binding site properties
resembled those the amino acid sequency adjoining the tryptophan
residue of human serum albumin. There was evidence, too, of the
presence of tryptophan at the high affinity binding site of bovine
serum albumin (Mason, 1975).
Human male volunteers ingested a single dose of 5 mg/kg. Excretion
of 2,4,5-T was essentially in unchanged form. Clearance from the plasma
and excretion both followed first-order kinetics with a half-life of
23.10 and 23.06 h, respectively (Gehring et al . , 1973).
[1-UC]2,4,5-T was administered by stomach tube to pregnant and non-
pregnant rats. The rate of elimination was the same for both groups.
Urinalysis revealed that 90-95% of the label excreted was in the
form of unchanged 2,4,5-T. Two non-polar and one water soluble
metabolite were observed. Acid hydrolysis of the latter produced
2,4,5-T. The biological half-life in the various organs was essentially
the same but differed between adult and newborn rats: 3.4 h vs. 97 h,
respectively (Fang et al . , 1973). The plasma and elimination half-
lives for Sprague-Dawley rats was 4.7 and 13.6 h, respectively, when
a 5 mg/kg dose was administered (Piper et al . , 1973).
When adult beagle dogs were administered 5 mg/kg doses, the half-life
for plasma clearance and elimination was 77.0 and 86.6 h, respectively.
Three unidentified metabolites were detected in the urine (Piper et al . ,
1973).
Photolytic decomposition of 2,4,5-T by sunlight in distilled water at
pH 8 was studied. The principal reaction was ether cleavage and replace-
ment of ring chlorines by hydroxyl and hydrogen. The products identified
were: 2,4,5-trichlorophenol > lactone of 4,5-dichloro-2-hydroxyphenoxy-
acetic acid > 2,5-dichlorophenol , 4-chlororesorcinol and 4,6-dichloro-
resorcinol. Unidentified and polymer material accounted for as much
as all metabolites combined except the 2,4,5-trichlorophenol (Crosby
and Wong, 1973).
93
DBNPA (2,2-Dibromo-3-nitrilopropionamide) [2,2-Dibromo-2-cyanoacetamide]
The rate of hydrolysis of DBNPA at various pH levels was determined
at 25C and the hydrolysis products determined.
PH
ti/2> h
3.9
2140 (2:
6.0
155
6.7
37
7.3
8.8
7.7
5.8
8.0
2.0
8.9
0.34
9.7
0.11
As DBNPA decreased, dibromoacetonitrile increased. Dibromoacetamide
formed by hydrolysis of the latter. Dibromoacetic acid and C02 formed
under more stringent conditions and hydrolysis of the acid yielded
bromide ions and glyoxylic acid. Two unexpected compounds were iden-
tified as tribromoacetonitrile and tribromoacetamide. These must have
arisen via a bimolecular reaction and hydrolysis. These latter products
occurred because of the high (12000-15000 ppm) concentrations used in
these studies. At use levels of 1-10 ppm, these should not occur.
When a solution of DBNP was mixed with sodium bisulfite, cyanoacetic
acid was obtained. DBNPA was also exposed, in water and in a quartz
tube, to a G.E. sunlamp for 3 days. A residual oil was obtained which
contained cyanoacetic acid, malonic acid amide, malonic acid and
oxalic acid. IR and mass spectral analyses were employed for identi-
fication (Exner et al . , 1973).
94
DCB [Dichlorobenzene]
When dichlorobenzenes were fed to rabbits, the compounds were slowly
metabolized over a 3-6-day period.
o-DCB
The o- isomer yielded glucuronides (48%), sulfates (21%), mercapturic
acid (5%) and catechols (4%). The major metabolites were 3,4- and
2,3-dichlorophenol conjugates (2:1, respectively). 4,5-Dichloro-
catechol and traces of 3,4-dichlorocatechol comprised the major
portion of the catechol fraction and 3,4-dichloro phenylmercapturic
acid was the probable mercapturic acid (Azouz et al . , 1954).
m-DCB
When fed to rabbits, the m-DCB yielded glucuronides (31%), sulfates
(11%), mercapturic acid (9%) and catechols (4%). The major product
was 2,4-dichlorophenol . Traces of 3,5-, but no 2,6-, dichlorophenol
were observed. 2,4-Dichlorophenylmercapturic acid and 3,5-dichloro-
catechol were also observed (Azouz et al . , 1954).
p-DCB
Rabbits fed ^-dichlorobenzene excreted glucuronides (37%) and sulfates
(27%). No mercapturic acid or catechols were observed. 2,5-Dichloro-
phenol and a quinol, probably 2,5-dichloroquinol , were observed (Azouz
et al., 1954).
95
DDOD (Dichlozoline) [3-(3,5-Dichlorophenyl )-5,5-dimethyloxazolidine-
2,4-dione]
Labeled DDOD was administered orally to 200g male Wistar rats. Urine
and feces were collected and analyzed. Approximately equal amounts of
radioactivity appeared in urine and feces. Most of the radioactivity
in feces was unchanged DDOD. About 85% of the radioactivity was
extractable from urine with ether and contained eight metabolites.
Five were identified:
N-(3,5-dichloro-4-hydroxy)-5,5-dimethyloxazolidine-2,4-dione
N-(3,5-dichloro-4-hydroxyphenyl )-a-hydroxyisobutyramide
N-(3,5-dichloro-4-hydroxyphenyl )-N-(a-hydroxyisobutyryl)carbamic acid
N-(3,5-dichlorophenyl ) -N-( a- hydroxy isobutyryl )carbamic acid
N-(3,5-dichloro-4-hydroxyphenyl )lactamide
Two fractions treated with glucuronide or sulfatase released compounds,
one of which was identified as N^(3,5-dichloro-4-hydroxyphenyl )lactamide
(Sumida et al . , 1973a).
Bean plants were treated with labeled DDOD. After root treatment,
DHCA and HDA were observed. Neither compound was observed when DDOD
was injected into the bean plant. Other unidentified metabolites were
observed. After injection of DDOD into grape plants, analysis of the
leaves showed the presence of DMDOD, HDA and unidentified material.
In soil, DDOD degraded to DHCA, HDA, DCA and unidentified material.
No TCAB was found (Sumida et al . , 1973b).
96
E 10 i-
10 •— o
11 II II
z: o. uo
i. a;
O ■!->
C ••->
O c
J- o
3 O
97
DDT and RELATED COMPOUNDS
DDT [2,2-Bis(]D-chlorophenyl )-1 ,1 ,1-trichloroethane]
DDD (TDE, Rhothane) [2,2-Bis(£-chlorophenyl )-l ,1-dichloroethane]
Kel thane (Dicofol) [2,2-Bis(])-ch1oropheny1 )-l ,1 ,1-trichloroethanol]
DDE [2,2-Bis(£-chlorophenyl )-l ,1-dichloroethylene]
98
Studies with human serum has shown that p^p^-DDE can be bound to
proteins. This binding increased with aged serum (Schoor, 1973).
When ring-labeled 1I+C-DDT was incubated with human embryonic lung
cells, reductive dechlorination produced DDD. The only other meta-
bolite found was DDA (North, 1972; North and Menzer, 1972). Binding
of p^p^-DDA with human and bovine serum has also been observed (Ross
and Biros, 1975).
Syrian golden hamsters were fed p_,p} -DDT in their diet for 4 months.
Urine and feces were collected. Autoradiography of thin-layer plates
on which urine had been spotted indicated the presence of at least
10 radioactive bands. The major metabolite (80%) apparently was DDA,
free and as the glucuronide. Other bands were identified as the DDA
conjugates of glycine and alanine. DDD was observed in urine and
feces (Wall cave et al . , 1974).
After Swiss albino mice were fed £,£1-DDT, analysis of urine revealed
the presence of DDE and DDA as the glucuronide, alanine and glycine
conjugates. DDD was found in the feces (Wall cave et al . , 1974).
In other studies with mammals, oral dosing of mice with metabolites
of fj.p^-DDT indicated that DDE is not an intermediate in DDT metabolism
to DDA. Administration of p^p^-DDD produced increased levels of d_>E.1-
DDA. However, DDMU led to a decrease in DDA production in the urine
over that found from DDD administration. This would not be expected if
DDMU was a metabolite of DDT or DDD leading to production of DDA.
When administered intraperitoneally, jd^-DDT dosing led to a decrease
in DDA production and indicated that the intestines may play a major
role in DDT degradation to DDA (Apple, 1969). Other studies with
hepatic microsomes also indicate that the pathway for DDT in birds
may differ from that in mammals. A pathway involving DDMU to a highly
active liver inducer may be involved (Bunyan and Page, 1973).
Oral dosing of mammals with p^p^-DDT gave rise to o.p^-DDA. No fJ.j).1-
isomer was observed (Apple, 1969).
14C-Labeled o^-DDD was administered orally to Sprague-Dawley rats.
Urine and feces were collected at 6, 12 and 24 h and then at 24 h
intervals. Rats were sacrificed at 15 days. Urine contained: o,^.1-
DDA and its 3-hydroxy, 4-hydroxy and 3, 4-di hydroxy analogs; the serine
and glycine conjugates of DDA; monomethyoxy- and dimethoxy-o^-DDD
(Reif and Sinsheimer, 1975).
After mice were administered DDT, urine and feces were collected and
analyzed. In addition to DDE, DDT, DDMS, DDD, DBP, DDA and kelthane,
five unidentified metabolites and some conjugates were observed (Kapoor
et al . , 1972). In other studies, DDT was incubated with ovine (Ovis
aries) rumen fluid. DDD, DDE and DDMU were observed (Sink et al . , 1972)
99
After mule deer fawns, Odocoileus hemionus, were fed jD.p^-DDT, DDD
was found in the serum and in feces^ p_,£!-DDE was found in fecal
matter but not in serum (Watson et al . , 1975).
Studies with a worker exposed to DDT indicated that the human liver
excretes DDT into the bile (Paschal et al . , 1974).
A common loon (Gavia immes), found in a moribund state in a soybean
field, was autopsied and tissue was analyzed. In addition to p_>P1-
DDE, p^-DDD, jd.j^-DDMU, p^-DCBP, jj.^-DDMS, 0,^-DDD, and o.fP-DDE
another compound was observed and identified by synthesis and mass
spectrum as 1 ,l-bis(]3-chlorophenyl )-2,2-dichloroethanol (Prouty et al .
1975).
Chickens, modified surgically to facilitate collection of urine and
feces were administered single oral doses of ring-^C-labeled o,^1-
DDT. Feces contained o^-DDT and o.p^-DDD, predominantly. The
following metabolites were also observed:
S-hydroxy^^-DDD
4-hydroxy-2, 41-DDD
4-hydroxy-3-methoxy-2,41-DDD
o,£} -DDE
3-hydroxy-2,4!-DDE
4-hydroxy-2,41-DDE
4-hydroxy-3-methoxy-2 ,4! -DDE
3-hydroxy-2,41-DDT
4-hydroxy-3-methoxy-2,41-DDT
0,^-DDA
3-hvdroxy-2,41-DDA
o,jr-DDA methyl ester
Methyl ester of a methoxy o^p^-DDA (probably 3-isomer)
4-hydroxy-3-methoxy-2,41-DDA
(Feil et al., 1974 and 1975)
12,000xg Liver preparations, to which NADPH and riboflavin had been
added, were incubated with DDT. Percentage conversion of DDT to
DDD was in order: hamster > mouse > pigeon > Wistar rat > quail >
cockerel; after heating and then supplementing: Wistar rat > mouse
> quail > hamster > cockerel > pigeon (Hassall, 1975). In other
studies, incubation of pigeon liver preparations with DDT and DDD
gave rise to analogs showing loss of one chlorine (Hassall and
Manning, 1972).
When pooled fat extracts from tissues of guillemots and grey seals
were analyzed, two hydroxylated DDE analogs were observed. The 4,4*-
dichlorobenzophenone and 2-bis(p_-chlorophenyl ) acetic acid were also
present in some samples (Jansson et al . , 1975). The hydroxylated DDE
100
analogs were identified by mass spectra and synthesis as: 1 ,1-dichloro-
2-(4-chloro-3-hydroxyphenyl )-2-(4-chlorophenyl )ethylene; 1 ,1-dichloro-
2-(3-chloro-4-hydroxyphenyl )-2-(4-chlorophenyl jethylene. When rats
were fed p_,p_i-DDE, these two and a third compound identified as the
2-(4-chloro-2-hydroxyphenyl ) analog were isolated (Jansson et al . ,
1975; Sundstrom et al . , 1975).
When tadpoles of the common frog (Rana temporaria) were exposed to £,£1-
DDT, no DDE was detected. The only metabolite observed was DDD and
post-mortem breakdown was suspected (Cooke, 1970).
In the environment, conversion of DDT to DDD has been observed in a
wide variety of biological systems, living and dead. The mechanism
has not been clearly established but existing data indicates the
involvement of reduced porphyrins. A series of studies demonstrated
that the DDT to DDD conversion was affected whenever DDT and reduced
porphyrins were brought together in solution (Zoro et al., 1974).
Agricultural loam soils were treated with DDT in 1954 and sampled
periodically. Analyses in 1970 showed the presence of DDD, DDE and
dicofol (Lichtenstein et al . , 1971).
In flooded soil, p.p^DDT was dechlorinated to p.p^DDD. Some DDE
was also observed (Bhulya, 1969). When DDT was added to an Everglades
muck, the amount of degradation was related to the changes in redox
potential. Under aerobic or flooded anaerobic conditions in substrate-
amended muck, where the redox potential dropped to +350 and +180 mV,
respectively, little DDT degradation occurred. Where the redox poten-
tial dropped to 0 and -250 mV, considerable degradation occurred (Parr
and Smith, 1974).
E_. col i , B. subtil is and S. aureus degraded DDT to DDD and DDE in
trypticase soy broth (Collins, 1969). Anaerobiosis was found to be
an environmental factor in the degradation of DDT to DDD. The ability
to make this conversion was demonstrated by 27 bacterial species from
the following genera: Achromobacteria, Aerobacter, Agrobacterium,
Bacillus, Clostridium, Erwinia, Kurtha, Pseudomonas and Xanthomonas
(Johnson, 1969). Reductive dechlorination of £,p_1-DDT to DDD has
been observed under both aerobic and anaerobic conditions (French,
1969). Bacillus megaterium converted a small amount of DDT to DDD
(Hicks, Jr., and Corner, 1973). When DDT was added to raw sewage,
DDD, DDE and DBP were produced. Addition of glucose enhanced the
rate of DDD formation but reduced DBP formation. Addition of di phenyl -
methane reduced formation of DDD and DBP (Pfaender and Alexander, 1973).
Membrane-bound enzymes from Hydrogenomonas sp. appeared to mediate
initial anaerobic degradation of DDT to DDD. Soluble cell fractions
and flavin enzymes stimulated the reaction. Enzyme preparations from
Hydrogenomonas sp. were capable of degrading DDT to DDD, DDMS, DBP.
Addition of fresh cells to the anaerobically incubated extract and
101
aerobic incubation of the mixture produced p_-chloropheny1acetic acid
(PCPA). An isolated Arthrobacter sp., that could use PCPA as a sole
carbon source, produced p_-ch1orophenyl glycol aldehyde during growth
on PCPA (Pfaender, 1972).
In studies with adult catfish (Heteropneustes fossil is) exposed to
DDT, only DDE was observed (Agarwal and Gupta, 1974). The thorny
skate (Raja radiata) metabolized ^C-p^p^-DDT to DDD and DDE (Darrow
and Addison, 1973).
Ring-labeled p^p^-DDT- 3H was force-fed to mature brook trout (Salvelinas
fontinal is) one dose each week for five weeks. The eggs were collected,
fertilized and incubated. Analyses of the eggs and fry indicated
metabolism to £,p_1-DDD and p_,p_1-DDE. Distribution of the three compounds
was determined from the day of fertilization until 80 days post-
fertilization:
p_,p>DDT 92.4 to 61.7%
£,£1-DDD 0.4 to 5.1%
p^-DDE 7.2 to 33.2%
(Atchison and Johnson, 1975)
When 14C-labeled DDT was given orally to common soles [Solea solea
(L.)]» there was a characteristic distribution pattern of accumulated
DDT that was independent of dosage. Brain, liver and gastro-intestinal
tract ranked highest. More than 80% of the accumulated DDT remained
unchanged and DDE, DDD and a polar compound occurred as metabolites
(Ernst and Goerke, 1974).
After oral application of yg-amounts of DDT to the polychaete Nereis
diversicolor, analysis indicated that most of the DDT (51 to 67% of
the initial dose) was stored unchanged. There was only slight
metabolism, probably to DDA (Ernst, 1969).
Studies with the freshwater planarian Phaqocata velata indicated that
it was capable of metabolizing DDT to DDD and DDE (Phillips et al . ,
1974).
All algae tested converted DDT to DDE. No other metabolites were
observed. Algae used included:
Chlorella vulgaris
Ankistrodesmus braunii
Anacystis nidulans
Nostoc muscorum
Synechococcus elongatus
Synechococcus cedrorum
Anabaena variabilis
102
Anabaena flos-aquae
Calothrix parieatina
Phormidium luridum var. olivacea
Skeletonema costatum
Cyclotella nana
Isochrysis galbana
Olisthodiscus luteus
Amphidinium carteri
Tetraselmis chuii
(Rice, 1972; Rice and Sikka, 1973)
In other studies with the unicellular freshwater alga (Ankistrodesmus
amalloides), after exposure to ll+C-DDT for 30 days, both DDE and DDD
were recovered. When daphnids (Daphnia pulex) were exposed for 24 h,
DDE was recovered (Neudorf and Khan, 1975).
Collembola, Folsomia Candida, was fed brewer's yeast spiked with
100,000 ppm DDT. These were then released into fenced plots in a
beech-maple forest. Arthropod fauna were sampled at intervals.
Reductive dechlorination of DDT gave DDD and dehydrochlorination
gave DDE (Klee, 1972).
Vitamin B12 has been suggested as having a role in the degradation of
DDT. To study this possibility, macrocyclic alkyl -cobalt complexes
were synthesized and reacted with DDT. In one of these studies, the
Co(II) complex was prepared, reduced to Co(I) species, and allowed to
react with DDT. A maroon powder was isolated. Infrared spectra
indicated that the complex contained a carboxyl group. After a few
days in sunlight, a solution of the material was extracted. Mass
spectrum analysis indicated that the white material obtained was
bis(p-chlorophenyl ) ketone (Prince and Stotter, 1974; Prince et al . ,
1974).
Gamma-radiation of DDT induced loss of chlorine but DDD and DDE were
absent. It seems, therefore, that dechlorination proceeds with simul-
taneous loss of all three chlorine atoms from the CCl3-group (Woods
and Akhtar, 1974).
In a laboratory model ecosystem, DDE was extremely stable in the
tissues of the living organisms. Analysis of body and feces of the
salt marsh caterpillar showed over 95% unchanged DDE. The remainder
appeared as unidentified polar metabolites (Metcalf et al . , 1975b).
Under laboratory conditions, DDT, DDE, DDD and DDA were chroma to-
graphed on silica gel G on glass plates. The studies indicated
that degradation of DDT occurred when the spotted plates were exposed
to UV. In addition to DDD and DDE, there appeared to be four other
components (Ernst, 1972).
103
DDT decomposed when irradiated, whether as a pure solid or in hexane
solution, by UV (2537A). In hexane solution, DDD and HC1 were identi-
fied. When irradiated in the solid form, DDD, DDE and DBP were formed
(Mosier et al . , 1969).
When DDT and DDE in pyrex tubes were exposed to UV-irradiation (A>290nm)
as solids in an oxygen stream, mineralization products (C02 and HC1 )
were observed in small amounts after 7 days. DDE yielded dichloroben-
zophenone and trichlorobenzophenone. No photoproducts from DDT were
detected (Gab et al . , 1975).
Kel thane residues on apple pomace were subjected to UV irradiation
filtered through pyrex glass (A>290nm). Analyses indicated that only
DBP was formed from Kel thane (Archer, 1974).
After oral administration of Kelthane to rats, analyses of tissues,
urine and feces showed the presence of DDE, DBP and 4,41-dichlorobenz-
hydrol (Brown et al . , 1969).
Recent studies have indicated that colored complexes can form between
montmorillonite clay and p.p^-DDT, o.p^-DDT, p^p^-DDE, £,p_1-DDD,
js.p^-DDA, dicofol, or 4,4*"-dichlorobenzophenone (Haque and Hansen, 1975).
In other studies, larvae of the bollworm H_. zea and tobacco budworm
H_. virescens were exposed to DDT. Analyses indicated rapid accumulation
of DDE and only small amounts of metabolites more polar than DDT in
H_. zea. In H_. virescens, there was only minor accumulation of DDE but
rapid accumulation of more polar metabolites (Plapp, 1973).
104
DESTUN (Perfluoridone) [1 ,1 ,l-Trifluoro-N-[2-methyl-4-(phenylsulfonyl )
phenyl ]methanesul fonamide]
In sandy loam soil, destun was degraded to 3-methyl-4-[[(l ,1 ,1-
trifluoromethyl )sulfonyl]amino]benzenesulfonic acid (II) (Bandal
et al., 1974).
Peanut seedlings were root treated with ^C-labeled destun. Young
developing lateral branches contained the highest concentrations of
lkC in foliar tissue. TLC of aqueous extracts of roots gave eight
radioactive zones. Hydrolysis of one of the zones yielded destun
and a metabolite tentatively identified as 1 ,1 ,l-trifluoro-N-[2-methyl-
4-(3-hydroxyphenylsulfonyl )phenyl]methanesul fonamide (III). The most
abundant metabolite, not identified, yielded 2 moles of glucose and
one of compound II upon acid hydrolysis, but one mole of II and no
glucose when treated with B-glucosidase (Lamoureux and Stafford, 1974)
*-r\\ /,
CH3
II
\
Glucoside
III
105
DEXON [p_-Dimethylaminobenzenediazo sodium sulfonate]
Pseudomonas fragi metabolizes dexon by a co-metabolic process. One
of several compounds that is formed was identified as N,N^-dimethyl-p_-
phenylenediamine (DMPDA). The enzyme, a reductase, was found in the
soluble fraction and required dithioerythreitol as reductant. When
dexon was applied to soil, DMPDA was also found (Karanth et al . ,
1974).
106
DIANISYLNEOPENTANE [1 ,l-Bis(£-methoxyphenyl )-2,2-dimethylpropane]
In an effort to find a more selective and biodegradable replacement
for DDT, analogs of DDT were studied. Metabolic studies were con-
ducted with an analog, dianisylneopentane, and the DDT-resistant
housefly R5P, the salt marsh caterpillar Estigmene acrea (Drury),
female Swiss white mice, and mouse liver microsomes (see Table 1).
Additionally a model ecosystem was used to study biodegradation
(see Table 2). In the model ecosystem, this compound accumulated
in fish to about the same level as has been found in studies with
methoxychlor; and the neopentyl group exhibited about the same
stability as the trichloromethyl group (Coats et al . , 1974).
Table 1
Radioactivity recovered
Compound
Housefly
Caterp
ill
ar
Mouse
Liver homogenate
I
++++
+++++
+++
++
II
+++
+++
+
III
++
++
+++
IV
++
+
+
V
+
+
VI
+
+
VII
+
+
+
+
Conjugates S
aci
ds
+++
+
+++
+
Unknown A
+
B
++
+
+
107
Table 2
Metabolites found in the model ecosystem
Alga
Snail
Fish
Compound
H 0
(Oedogonium)
(Physa)
(Gambusia)
I
+
+
+
+
II
+
+
+
III
+
+
+
IV
+
+
V
+
+
VI
+
+
+
VII
+
+
+
+
Conjugates &
acids
+
+
+
+
Unknown A
+
+
+
+
B
+
+
+
+
CH
■0?-0H
/
H,C-C-CH,
CH,
Dianlsylneopentane (I)
I
(v)
H3qtH3
CH3 X
3C0-^C-C-^~^>CH3
H2C CH3
(VII)
(IV)
108
DIAZINON [0,0-Diethyl 0-(2-isopropyl-4-methylpyrimidin-6-yl )
phosphorothioate]
In the beagle dog, metabolism of diazinon proceeded rapidly. Analyses
of urine indicated the presence of two metabolites identified as:
4-hydroxy-2-isopropyl-6-methylpyrimidine (III) and 4-hydroxy-2-
isopropanol-6-methylpyrimidine (Vila) (Iverson et al . , 1975).
Three diazinon metabolites were isolated from sheep dosed by stomach
tube. Identification was made by mass spectra: from urine, the 2-
isopropanol diazinon (VI); 4-methanol diazinon (XI); primarily from
fat, the isopropenyl analog (VIII) (Janes et al . , 1973; Machin, 1973).
Liver microsomes rapidly degraded diazinon to diethyl phosphorothioic
and diethyl phosphoric acids. Diazinon was degraded by hydrolases
in mitochondrial, microsomal and soluble fractions of rat liver
(Yang et al . , 1969; Yang, 1971).
Houseflies, susceptible and resistant, degraded diazinon and diazoxon.
The major metabolites were diethyl phosphorothioic and/or diethyl
phosphoric acids. In addition to the MFO system which was responsible
for the foregoing, there is another soluble system in the housefly which
used reduced glutathione. The major metabolites were the same (Yang,
1971).
Degradation of diazoxon by homogenates of Hokota strain (diazinon-
resistant) and NAIDM strain (diazinon-susceptible) houseflies produced
diethyl phosphate. Optimal pH was ca. 7.0. Resistant flies degraded
more diazoxon than susceptible flies. The homogenate supernate
degraded diazinon in the presence of reduced glutathione with no
significant difference between rates by the supernatant of Hokota
and NAIDM strains. The main degradation products were diethyl phos-
phorothioic acid and 5[-(2-isopropyl-4-methyl-6-pyrimidinyl ) glutathione.
Optimal pH was 8.5. Microsomal MFO plus NADPH metabolized diazinon to
diazoxon and diethyl phosphorothioic acid (Shono, 1973, 1974 a and b).
Metabolism of diazinon by gypsy moth larvae (Porthetria dispar L.)
was qualitatively the same whether after ingestion or topical appli-
cation. The major products were 2-isopropyl-4-methyl-6-pyrimidinol ;
diazoxon; hydroxydiazinon; 2-(2-hydroxy-2-propyl )-4-methyl-6-pyrimidinol .
Formation of these metabolites was reduced by the synergists 2,6-
dichlorobenzyl-2-propynyl ether and piperonyl butoxide (Ahmad and
Forgash, 1975).
From submerged soild and rice paddies, microorganisms capable of
decomposing diazinon have been obtained. These fall into three
categories:
109
c
o
00
u
o
2
o
01
a
e
PL,
I
•A
no
1. Sole carbon source - flavobacterium sp.
2. Synergism - Arthrobacter sp. plus Streptomyces sp.
3. Co -metabolism
Arthrobacter "sp.
Corynebacterium sp. , Pseudomonas melophthora, Streptomyces sp.
Trichoderma viride
Microorganisms accelerated hydrolysis of diazinon and subsequent
mineralization of 2-isopropyl-6-methyl-4-pyrimidinol to C02
(Sethunathan, 1972).
The inhibition of MFC1 by pesticide synergists was investigated.
Piperonyl butoxide and NIA 16824 (O-isobutyl-0-propargyl phenyl phos-
phonate) inhibited all oxidative reactions to the same extent. However,
l-(2-isopropyl phenyl )imidazole inhibited conversion of thiophosphate
to phosphate and oxidative de-arylation. There was no significant
effect on hydroxylation of ring side chain (Smith et al., 1974).
Ultraviolet irradiation of diazinon gives a mixture of products. One
has been identified as 0,0-diethyl 0-(2-acetyl-6-methylpyrimidin-4-yl )
phosphorothioate (Machin and Quick, 1971).
Ill
DICAMBA (Banvel; 3,6-dichloro-o-anisic acid) [2-Methoxy-3,6-dichloro-
benzoic acid]
DISUGRAN (Racuza; methyl 3,6-dichloro-o-anisate) [Methyl 2-methoxy-
3,6-dichlorobenzoate]
Breakdown of dicamba in bracken litter occurred rapidly. At 25C,
of the initial dose (1.25 lb/acre) was lost in 4 days at pH 4. Raising
the pH to 7.4 reduced the loss rate (Parker and Hodgson, 1966).
Dicamba degraded rapidly in prairie soils when applied at rate of
1.1 kg/ha. At 25C over 50% dissipated in 2 weeks. In other studies
over half was lost within 4 weeks and only 1UC02 and 3,6-dichloro-
salicylic acid were detected (Smith 1973a and b, 1974b).
Incubation of disugran with rumen fluid of ewes produced seven meta-
bolites. Four were not identified. However, the three identified
metabolites comprised about 95% of the total metabolites. Degradation
proceeded primarily via ether cleavage and then ester hydrolysis. The
third metabolite was 3,6-dichloro-o-anisic acid (Ivie et al . , 1974a).
A radiochemical analytical procedure was used to monitor dicamba break-
down in soil. At -5 ± 1C breakdown was not observed but was observed
at 5 ± 1C. At temperatures above 15 ± 1C, over 80% of the dicamba was
dissipated in 8 days. When heavy clay and sandy loam were used, 14
days and temperatures above 20 ± 1C were needed to degrade similar
amounts of the herbicide (Smith and Cullimore, 1973).
112
DICHLOBENIL [2,6-Dichlorobenzonitrile]
The fate of dichlobenil in alligator weed and parrot feather (Myriophyllum
brasiliense) was investigated. In the latter, the major metabolite was
the 3-hydroxy analog. Small amounts of the benzamide and benzoic acid
analogs of dichlobenil were also observed as was 3-hydroxy-2,6-dichloro-
benzamide. Conjugates of the 3-hydroxy compounds also occurred. There
was other material not identified (Sikka et al . , 1974).
In soil, degradation of dichlobenil was determined at 6.7 and 26.7C. At
6.7C, the half-life was 28 weeks after a ten-week lag; 19 weeks at 26. 7C.
Only 2,6-dichlorobenzamide was detected (Montgomery et al . , 1972).
In a farm pond treated with dichlobenil at 10 lb a.i. per surface acre,
the concentrations in water and hydrosoil had decreased by 85 and 87%,
respectively, after 7 weeks (Rice et al . , 1974). In other studies with
pond water, more than 75% of the added dichlobenil disappeared because
of volatilization. Some dichlobenil was metabolized microbiological ly
to 2,6-dichlorobenzamide and other unidentified metabolites. A cell
suspension of Arthrobacter sp. metabolized up to 71% of added dichlobenil
in 6 days to dichlorobenzamide and small amounts of other compounds not
identified. Evolution of lt+C02 from labeled dichlobenil indicated that
some of this herbicide could be completely degraded in the environment
(Miyazaki et al., 1975).
113
DICHLOROPROPENE (Component of DD) [Trans- and cis-dichloropropene]
At 15 to 20C in sandy soils, 1 ,3-dichloropropenes exhibited an average
half -life of 24 days and disappeared at the rate of 2 to 3.5% per day
with no marked isomer difference. Some chloride was released but
this slowed to about 3% after an initial rapid release. Chloroallyl
alcohols are assumed to arise from dichloropropenes in soil. The
trans- isomer {th = <one day) degrades more rapidly than the c is- isomer
(th= ca. 2 days) (Van Dijk, 1974).
114
DICHLORVOS (DDVP, Vapona, Nuvan, Mafu) [2,2-Dichlorovinyl dimethyl
phosphate]
Dichlorvos was rapidly metabolized by mice, hamsters, rats and man.
Urine of rat, mouse and hamster contained compounds tentatively identi-
fied as hippuric acid, desmethyl dichlorvos, urea and dichloroethanol
glucuronide. The latter was also found in urine of man (Hutson and
Hoadley, 1972).
In pigs, after one dose of dichlorvos-1I+C in slow release PVC, lkC
in the tissues was in the form of C-l and C-2 fragments from the vinyl
moiety of dichlorvos and incorporated into normal tissue constituents
such as glycine, serine, creatine, glucose, glycogen, fatty acids,
cholesterol, choline, lecithin and ribonucleic acid (Page et al . , 1972;
Potter et al . , 1973a and b).
In vitro studies were conducted with isolated nucleic acids and in
cells of £. coli and the human tumor cell line HeLa. DNA and RNA
were methylated (Lawley et al., 1974).
Stored soybeans were treated with an aqueous emulsion of dichlorvos at
the rate of 20 ppm. Within 24 h post-treatment, 77% of the calculated
deposit had disappeared. During processing, most of the residue was
removed with the hull. Further processing, including refining of crude
oil and toasting the defatted meal, removed the remaining residue.
Degradation of dichlorvos in the stored crude soybean oil was slow
(0.36 ppm after 12 weeks) but was rapid on the hulls (<0.02 ppm after
12 weeks) (La Hue et al . , 1975).
115
DICROTOPHOS (Bidrin, Carbicron, Ektafos, SD 3562, C709) [Cis-N,N-
dimethyl -3- (dimethyl phosphate) crotonamide]
Mouse liver fractions were incubated with [ll*C] 0-methyl dicrotophos.
When phenobarbital and dieldrin were present, oxidative as well as
hydrolytic metabolism was induced. In the presence of the whole
homogenate, different metabolism patterns were noted in contrast to
that observed with supernatant. Des-N-methyl dicrotophos and N-hydroxy-
methyl dicrotophos were detected. Other metabolites were not identified
(Tseng and Menzer, 1974).
116
DICRYL [N-(3,4-Dichlorophenyl)methacrylamide]
Dicryl was incubated in a culture medium with the fungus Rhizopus
japonicus. After extraction of the culture medium and purification
by TLC, a metabolite was identified as l^-(3,4-dichlorophenyl )-2-
methyl-2,3-dihydroxypropionamide (Wallnofer et al . , 1973b).
117
DIMETHOATE [0,0-Dimethyl S- (N-methyl carbamoyl )methyl phosphorodithioate]
An amidase was prepared from sheep liver microsomes. The optimum pH
was 9 and it had a molecular weight of 230,000 to 250,000. The amidase
was able to hydrolyze the N-alkyl and various 0,0-dialkyl analogs of
dimethoate (Chen, 1972).
Elution patterns of N-hydroxymethyl analogs of dimethoate and dimethoxon
indicated that these compounds were converted to their corresponding
de-N-methyl derivatives by heat on the GLC column (Steller and Brand,
1974).
When a surfactant was added to a dimethoate wettable powder, initial
penetration of citrus leaves was greater than when no surfactant was
used. Without surfactant, there was no significant penetration for
1 day as against 2 h with a surfactant. Residues of dimethoxon in
grapefruit pulp, following a dimethoate-wettable powder treatment was
less than 0.05 ppm. Residues of dimethoate averaged 0.09 ppm after
2 days and 0.03 ppm after 14 days (Woodham et al . , 1974).
After dimethoate was applied to soils, dimethoate carboxylic acid and
dimethoxon were found. Identification was by co-chroma tography. Other
compounds were observed but could not be identified (Duff and Menzer,
1973).
[14C]Carbonyl -dimethoate was incubated with mouse liver fractions.
The oxon analog and other metabolites were observed. When the homo-
genate was pretreated with phenobarbital or dieldrin, dimethoxon
concentration was increased by more than fourfold. Similar results
were observed in vivo with mice (Tseng and Menzer, 1974).
118
DINITRO COMPOUNDS
N-sec-Butyl-4-tert-butyl-2,6-dinitroaniline
In methanol , 75% of this compound was decomposed after 8 h exposure
to sunlight. A major product of decomposition in methanol or water
was the nitrosoaniline (III). Some dim' troani line (II) was also
observed. Mass spectrometric analysis of minor products indicated
that two pathways may be simultaneously operative (Plimmer and
Klingebiel, 1974).
CH3
CH-CH
h
H3C-C-CH3
LH3
•NO:
III
119
DINITRO COMPOUNDS
DNBP (Dinoseb) [2- (1 -methyl -n-propyl )-4,6-dinitrophenol]
DINOBUTON [2- (1 -methyl -n-propyl )-4,6-dinitrophenol isopropyl carbonate]
In rats and rabbits DNBP was metabolized to the 2-amino analog and then
converted to the glucuronic acid conjugate. A propionic acid analog
and another compound, thought to be hydroxylated on the side chain,
were observed (Ernst, 1969).
After application of dinobuton to bean leaves, dinoseb (DNBP) and
other unidentified compounds were observed (Matsuo and Casida, 1970).
Dinobuton was slowly hydrolyzed to dinoseb after application to apple
trees. Subsequent degradation occurred to produce the 2-amino and
butyric acid analogs. Other unidentified polar compounds were also
observed (Hawkins and Saggers, 1974).
Twenty-eight days after topical application of dinobuton or dinoseb
to apple fruits, about 75 and 72% of these materials, respectively,
was lost. Analyses of peel indicated the presence of two polar
metabolites which chromatographed on TLC similar to 2-amino-6-sec-
butyl-4-nitrophenol and 3-(3,5-dinitro-2-hydroxyphenyl )butyric acid.
Other polar material, not identified, was also present. The same
compounds were found in the apple flesh also (Hawkins and Saggers,
1974).
O
120
DINITRO COMPOUNDS
DINITRAMINE (Cobex, Cobeko, USB-3584, Diethamine) [N3,N3-Diethyl-2,4-
dini tro-6-tri f 1 uoromethyl -m-phenyl enediami ne]
Soil fungi used were identified as Aspergillus fumigatus Fres.,
Fusarium oxysporum Schlecht and Paecilomyces sp. When these organisms
were exposed in culture to dinitramine, all three degraded the herbicide.
Quantitative differences were observed. Four metabolites were identi-
fied as the mono- (II) and di- (III) dealkylated dinitramine, the ethyl -
benzimidazole (IV), and the dealkylated benzimidazole (V). Crude cell
extracts of A. fumigatus also dealkylated dinitramine (Laanio et al . ,
1973).
Radioactive dinitramine (lt+CF3 and 1!*C-ring-labeled) was incorporated
into Anaheim silty loam soil. Analyses over an eight-month period
revealed the presence of compounds II, IV and VI. Perhaps as many
as ten other unidentified metabolites were also formed (Smith et al . ,
1973).
Dinitramine underwent rapid photolytic decomposition in methanol and
water with a 10 min half -life. Mass spectrum analyses were used to
identify the products as compounds IV, V, VI and VII (Newsom and
Woods, 1973).
121
HN-C2H5
122
DINITRO COMPOUNDS
ISOPROPALIN (2,6-Dinitro-N,N-dipropy1cumidine) [2,6-Dinitro-N,N-
di propyl -4- i sopropyl benzene]
Isopropalin (I) was incorporated in soil, and tomato and pepper seeds
were planted in some of the plots. Tobacco transplants were placed
in other plots. After all were harvested, wheat was sown and harvested
the following year. Analyses of soil and plants involved TLC, column
chromatography, GC-MS and thin-layer radioautography. In soil, in
addition to bound and unidentified compounds, nine metabolites were
identified in addition to unchanged isorpopalin:
II. 2,6-dinitro-N-propylcumidine
III. 2,6-dinitro-cumidine
IV . 2-ami no-N ,N-di propyl ami no-6-ni trocumi di ne
V. 2-ami no-6-nitro-N-propylcumi dine
VI. 2-ethyl -5- i sopropyl -7-nitro-l -propyl benzi mi dazole
VII. 2-ethyl -5- i sopropyl -7-nitrobenzimi dazole
VIII. 4 ' -i sopropyl -2 ' ,6 ' -di ni tro-N-propyl propionani 1 ide
IX. 4 ' -i sopropyl -2 ' ,6'-dinitropropionanil ide
X. a,a-dimethyl-3,5-dinitro-4-dipropylaminobenzyl alcohol
Negligible amounts of isopropalin or its degradation products were
found in the plants grown on treated soil (Golab and Althaus, 1975).
123
DINITRO COMPOUNDS
N-(l-Methyl-n-propy1)-4-tert-butyl-2,6-dinitroaniline
In soil, compound I was dealkylated to produce 4-tert-butyl-2,6-
dinitroaniline (II). A soil fungus Paecilomyces sp. produced 3-
(4-tert-buty1-2,6-dinitroaniline)-2-butanol (Kearney et al . , 1974).
In methanol, 75% of this compound was decomposed after 8 h in sunlight.
A major product of decomposition in methanol or water was 4-tert-butyl-
2-nitro-6-nitrosoaniline (III). Some 4- tert-butyl -2 ,6-di ni troani 1 i ne
(II) was also observed. Mass spectrometric analysis of minor products
indicated that two pathways may be simultaneously operative (Plimmer
and Klingebiel, 1974).
124
DIPHENAMID (Dymid, Enide, L-34314) [N,N-Dimethyl-2,2-diphenylacetamide]
Tomato plants (Lycopersicon esculentum Mill., var. Sheyenne), 27 to
35 days old, were fumigated with ozone prior to exposing their roots
to ll*C-diphenamid in nutrient solution. Some differences were observed:
1. fumigated plants absorbed 70 to 100% as much diphenamid as did
controls
2. fumigated plants contained less radioactivity in the CHC1 3-
soluble fraction than did controls
3. fumigated plants generally contained more radioactivity in the
water-soluble and insoluble fractions than did controls.
Fumigated and control plants contained N-methyl di phenyl acetamide (MDA),
2,2-diphenylacetamide and an unidentified compound. There were two
additional compounds. When hydrolyzed, one gave MDA plus glucose and
the other gave MDA plus moieties positive to sugar reagents (Hodgson,
1971).
Diphenamid metabolism in tomato plants was altered by ozone fumigation.
There was little effect on root absorption, translocation or conversion
to water-soluble conjugates; but the proportions of conjugates were
altered. There was a marked shift toward more polar material and
increased production of methanol-insoluble residues. The predominant
compounds formed, in both fumigated and non-fumigated plants, were the
6-glucoside (MDAG) and the 6-gentiobioside (MDAGB) of N-hydroxymethyl-
N-methyl -2,2-diphenylacetamide (MODA). The latter is a postulated
intermediate in the formation of the glucoside and gentiobioside
(Hodgson et al . , 1973). The primary metabolites of diphenamid metabolism
in tomato plants included MODA, N-methyl -2,2-diphenylacetamide and 2,2-
diphenylacetamide. In addition to MDAG and MDAGB, soluble polar products
were also obtained (Hodgson et al . , 1974).
The metabolism of diphenamid in the corn root was studied with carbonyl-
lkC labeling. The only compound identified was N-methyl -2,2-diphenyl-
acetamide (Yaklich, 1970).
ll+C-Diphenamid accumulated in foliage of tobacco seedlings (Nicotiana
tobacum L. Kentucky) when incubated in nutrient solutions. The amount
of radioactivity in the roots remained minimal. The N-methyl-2,2-
diphenylacetamide and traces of 2,2-diphenylacetamide were found in
the foliage. In the roots, only traces of N-methyl -2,2-diphenyl-
acetamide was observed (Long et al . , 1974).
125
DIQUAT [l,r-Ethylene-2,2'-bipyridylium dibromide]
PARAQUAT (Gramoxone) [1 ,r-Dimethyl-4,4'-bipyridylium dichloride]
Adsorption studies were conducted with diquat and paraquat. Adsorption
for both compounds was increased in the order:
Mg+2 > Ca+2 > H+ > Mn+2 > Co+2 > Zn+2 > Ni+2 > Cu+2 > Fe+3 > Al+3
(Khan, 1974)
In studies with sandy loam, paraquat was degraded only slightly, if
at all, over a seven-year period (Fryer et al . , 1975).
126
DISYSTON [0,0-Diethyl-S-(2-ethylthio ethyl )phosphorodithioate]
Disyston was rapidly converted to its oxidative metabolites in
soils. Conversion in soil was predominantly by side chain
oxidation of the sulfur. The oxygen analogs form in small amounts
only. Oxidation in flooded conditions was at a much faster rate
than in upland soils (Takase et al . , 1972).
127
DITHIOCARBAMATES
Under acid conditions, dithiocarbamates may form significant amounts of
carcinogenic nitrosamines. In the presence of sodium nitrite and ziram,
the carcinogen dimethyl nitrosamine formed in small amounts at pH 1.5 to
2.0 (Eisenbrand et al . , 1974).
MANEB [Manganese ethyl enebisdithiocarbamate]
After treatment of beans and tomatoes with maneb, residues were measured
at intervals until 14 days post treatment. Residues on beans were
higher than on tomatoes for unchanged maneb as well as ETU, ETM and EDA.
Residues of these three metabolites were also found in soil 15 days
after treatment (Newsome et al., 1975).
Maneb was suspended in buffer pH=6 and aerated. Degradation products
identified by TLC included ETM, ETU, EDA, CS2 and sulfur (Hylin, 1973).
ZINEB [Zinc ethylenebisdithiocarbamate]
When fruits and vegetables containing zineb were boiled, ETU was formed
(Newsome and Laver, 1973).
Maneb and Zineb formulations were studied under laboratory conditions of
controlled heat and humidity. At elevated temperatures, zineb was less
stable than maneb. The zinc-manganese coordination products, however,
were considerably more stable than either zineb or maneb (Bontoyan and
Looker, 1973).
ETU [Ethylenethiourea)
Although not a pesticide, there is considerable interest in its occurrence
as a breakdown product of a group of ethylenebisdithiocarbamate fungicides
very widely used. There is considerable interest too in its fate in the
environment.
128
ll+C-ETU was injected into corn, lettuce, pepper and tomato seedlings.
Some ETU was present after 14 days. Some 1UC02 was formed but the major
degradation product in all plant tissues was identified as ethyleneurea
(EU) (Hoagland and Frear, 1976).
When ETU was administered to rats and guinea pigs, elimination was rapid.
About 50% was eliminated within 24 h in urine. Elimination in feces
was negligible (Newsome, 1974).
Photolysis of ETU (x>285 nm) on a solid substrate produced 2-imidazolidone
as the major product, bis (imidazolin-2-yl ) sulfide and an unidentified
product. Aqueous solutions of ETU undergo slow photolysis but are stable
to hydrolysis in the pH range 5.0 to 9.0 at 90C (Cruickshank and Jarrow,
1973). Although aqueous solutions of ETU were stable to sunlight, in
the presence of dissolved oxygen and sensitizers, ETU was rapidly degraded.
When less than 5% of the ETU remained, a compound was indentified as
glycine sulfate. When the reaction was stopped while there was more
than 50% of the ETU remaining, 2-imidazolidone was obtained (Ross and
Crosby, 1973).
129
DS-15647 (Thiofanox) [3,3-Dimethyl-l-methylthio-2-butanone
0- (methyl carbamoyl ) oxime]
Fully expanded leaves of cotton plants grown in the field were
treated individually with 35S-labeled DS-15647. The sulfone and
sulfoxide were formed. Metabolism to the sulfoxide was essentially
complete in 4 days. Polar compounds not identified, the oxime and
the oxime sulfoxide, also formed. Similar results were obtained
with excised cotton leaves. Seedlings grown from treated seed
gave the same results as those obtained in mature plants and in
soil. The rate of the initial reaction was more rapid than that
of the second, particularly in plants (Whitten and Bull, 1974a).
130
DYFONATE [O-Ethyl S-phenyl ethyl phosphonodithioate]
The degradation of dyfonate was studied with a series of fungi:
Aspergillus flavus, Aspergillus fumigatus, Fusarium oxysporum,
Trichoderma viride , Aspergillus niger, Mucor alternans, Rhizopus
arrhizus and Mucor plumbeus. All species degraded dyfonate to
some extent. Degradation by P. notatum was slowest; M. alternans,
R^ arrhizus and M. plumbeus were the most active species in producing
water-soluble metabolites. In addition to dyfonate, the extracts
contained dyfoxon, thiophenol , diphenyl disulfide, MPSO2 (methyl
phenyl sulfone), ethylethoxyphosphonic acid (EOP) and ethylethoxy-
phosphonothioic acid (ETP) and methyl phenyl sulfoxide (MPSO)
(Flashinski and Lichtenstein, 1974a and b).
Factors affecting the ability of soil fungi to degrade dyfonate
included nturient supply, temperature, pH and incubation time. The
studies indicated that the mycelium absorbed dyfonate and that meta-
bolism of dyfonate occurred in the mycelium. Degradation apparently
involved formation of the ethyl acetate-soluble metabolites: ethyl-
ethoxyphosphonic acid, ethylethoxyphosphonothioic acid, methyl
phenyl sulfoxide and methy phenyl sulfone. These were then metabolized
to water-soluble compounds. For R. arrhizus, the optimum was at
15-25C and pH 6.0 to 7.0 (Flashinski and Lichtenstein, 1975).
When plants were grown in nitrogen deficient nutrient solutions,
concentrations of dyfoxon in greens were reduced due to deficiencies
of all elements (potassium, calcium, and magnesium) except nitrogen
(Talekar and Lichtenstein, 1973).
Dyfonate was incorporated into soil at the rate of 5.6 and 11.2 kg/ha
as granules or emulsifiable concentrate; and its persistence and
absorption by plants was observed. Four months after application,
33-35% of the granular application and 38-41% of the emulsifiable
concentrate application (both 5.6 kg/ha) remained in the soil. No
dyfoxon was detected in soil. Potatoes, beets, and rutabagas had
little or no detectable residue at either application rate. Wheat
had 0.01-0.07 ppm dyfonate but little or none in the mature plant
or in the grain. Carrots grown in soil treated at the lower rate
had 0.35 and 0.04 ppm dyfonate and dyfoxon, respectively (Saha et al . ,
1974).
131
EDB [Ethylene dibromide]
In vitro studies of the enzyme catalyzed reaction between EDB and
conducted. Chromatography and comparison with
indicated the Dresence of S-(B-hydroxyethyl )
le main product (93%) and S^S^-bisCglutathione)
[n vivo studies indicated that the reaction occurs
(B-hydroxyethyl glutathione,
glutathione were
synthetic samples
glutathione as th
ethylene (7%). I
primarily in the
S- ( B-hydroxyethyl
Later degradation
ethyl ) mercapturi
liver with formation of S; ,
glutathione sulfoxide and J[,S_ -bis(glutathione)ethylene.
occurs primarily in the kidneys to yield ^-(B-hydroxy-
c acid and its sulfoxide (Nachtomi, 1970).
Br-CH2-CH2-Br + 6SH >- GS-CH2-CH2-Br + Br" + HH
GSH.
HOH
GS-CH2-CH2-SG
GS-CH2-CH2-0H + H+ + Br'
Mercap-CH2-CH20H
GS-CH2-CH2-0H
132
ENDOSULFAN (Thiodan) [6,7,8,9,10,10-Hexachloro-l ,5,5a,6,9,9a-hexahydro-
6,9-methano-2,4,3-benzo[e]dioxathiepin-3-oxide]
Endosulfan residues on alfalfa were exposed to ultraviolet light and
to sunlight while drying for 10 days. A third lot was dried in the
dark. Residue analyses showed the presence of endosulfan isomers I
and II, endosulfan diol (XI), endosulfan ether (VII), endosulfan
a-hydroxy ether (XIV) and endosulfan sulfate (IX). No lactone was
observed (<0.1%). In all three groups, the sulfate percentage of the
total residue increased but the increase was most dramatic in the dark
drying lot (Archer, 1973).
In temperature stressed rats orally dosed with endosulfan I or II,
endosulfan sulfate was the metabolite most commonly recovered from
tissues, organs and feces regardless of temperature stress. The diol,
a-hydroxy ether and lactone (X) were found in most urine and feces
samples. Studies with the diol showed this to be converted to the
a-hydroxy ether and that both diol and a-hydroxy ether were metabolized
to the lactone in small amount (Whitacre, 1970).
Degradation of endosulfan by a soil microorganism of the family
Pseudomonad was studied. The alcohol was the main metabolite from
either isomer. The 6- isomer also yielded small amounts of the endo-
sulfan ether as well as i somen zed to the more stable a-isomer
(Perscheid et al . , 1973).
Endosulfan isomers (a and 3.) were incubated with Aspergillus niger.
Endosulfan alcohol was formed from both isomers (El Zorgani and Omer,
1974). These same authors refer to studies by Domsch and coworkers
in which endosulfan sulfate was also observed after exposure of
microbes and fungi to endosulfan.
After incorporation of endosulfan into soil, analyses indicated a half-
life for the a-isomer of about 60 days and about 800 days for the
B-isomer. Endosulfan sulfate formed in amounts equivalent to the
endosulfan that decomposed. Potato tubers grown in the treated soil
contained residues of both isomers and the sulfate (Stewart and
Cairns, 1974).
UV irradiation of endosulfan isomers gave a variety of products,
depending on the medium used. a-Endosulfan (I) yielded compound III
in n-hexane; compound IV in dioxane-water; and compounds VII to XIII
in gas phase. e-Endosulfan (II) gave compound V and VI in dioxane-
water and compound V in n-hexane-acetone (Schumacher et al . , 1973).
133
VIII /
' If xiv
/ Endosulfan
H
/ Hydroxy
— ch2oh Ether
XIII
XII
XI
E'ndosulfandiol
134
ENDOTHALL [7-Oxabicyclo(2.1 .1 )heptane-2,3-dicarboxyl ic acid]
Aquatic microorganisms readily degrade endothall . One species of
Arthrobacter, isolated from lake water and sediment, utilized endo-
thall as a sole source of carbon for cell growth. When luC-endothall
labeled in the oxabicyclo ring was used, the 14C was found in cellular
amino acids, proteins, nucleic acids and lipids. Citric, aspartic,
alanine and glutamic acid were labeled as well as C02 (Sikka and
Saxena, 1973).
When exposed to luC-endothall in tap water, bluegill absorbed the
labeled material but only unchanged herbicide was found in the alcohol
extractable fraction of the fish (Sikka et al . , 1975).
135
ETHION (Diethion) [S,S-Methylene bis(0,0-diethyl phosphorodithioate)]
When sediment samples from a saline lagoon were incubated with ethion
for 20 days, ethion degradation was slow. Analyses indicated the
formation of sulfide from ethion. In these studies, ethion was the
sole sulfur source (Sherman et al . , 1974).
136
Ethylene oxide (EO, ETO)
When wheat is fumigated with ethylene oxide, S5% of the bound EO was
converted to water soluble compounds. The EO residue concentration
in the wheat was between 14 and 37.5 ppm and was distributed among
water-soluble and water-insoluble proteins, organic acids, mono-oligo-
saccharides, lipids, lipoproteins, starch, and bran (Pfeil sticker and
Rasmussen, 1974).
137
FENAZAFLOR (Lovozal) [Phenyl 5,6-dichloro-2-trifluoromethylbenzimidazole-
1-carboxylate]
NC-2983 [5,6-Dichloro-2-trifluoromethylbenzimidazole]
A major degradation product of the acaricide fenazaflor was found to
be 5,6-dichloro-2-trifluoromethylbenzimidazole (NC-2983). After
application of NC-2983 to field plots, soil analyses indicated no
significant disappearance in fall, winter or early spring but a rapid
decline during the summer. About 85% of an NC-2983 application in
summer disappeared within 135 days. When applied in the autumn,
disappearance of a comparable amount required about one year (Ercegovich
et al., 1972).
138
FENSULFOTHION (Dasanit, Terracur P) [0,0-Diethyl 0-(p_-methylsulfinyl )
phenyl phosphorothioateT
After application to a sandy loam soil, fensulfothion degraded rapidly
to the corresponding sulfone. Traces of the sulfone were found in
rutabagas grown in fensulfothion-treated soil. It was also found in
carrots, in which it persisted during a 4-year storage period when the
carrots were frozen (Chisholm, 1974).
139
FLUENETHYL (Fluenetil, Flu, Lambrol ) [2-Fluoroethyl 2-(4-biphenylyl )
acetate]
FLUOROACETIC ACID (1080) [2-Fluoroacetic acid]
Studies with mice, houseflies and the two spotted spider mite clearly
indicate that the toxicity of Flu depends on the release of monofluor-
ethanol by ester cleavage of fluenethyl and subsequent oxidation to
the monofluoroacetic acid. The latter is converted to fluorocitrate
which inhibits aconitase (Johannsen and Knowles, 1974).
Seeds of Acacia georginae, peanut (Arachis hypogaea L.) and bean
(Phaseolus vulgaris L. var. Pinto) were treated with 1I+C-sodium
fluoroacetate. Labeling was found in the lipids and in the water-
soluble fractions. lltC02 also evolved (Preuss et al . , 1968).
When lettuce plants were incubated with labeled fluoroacetate, a
labeled material was obtained and identified as S-carboxymethyl-
glutathione (Ward and Huskisson, 1972).
140
FLUORODIFEN (C-6989, Preforan) [2,41-dinitro-4-trifluoromethyl
di phenyl ether]
Rats, given a single oral dose of lltCF3-fluorodifen, excreted 48% of
the dose in 48 h in urine; 23% in feces. Most (83%) of the urinary
radioactivity in the 24-h sample was 2-nitro-4-trifluoromethyl phenyl -
mercapturic acid. In vitro studies with rat liver homogenates indicated
the formation of S-T2-nitro-4-trifluoromethyl phenyl )gluthathione after
cleavage of fluorodifen (Lamoureux and Davison, 1974).
From epicotyl tissues of pea seedlings, a soluble glutathione S-transferase
was obtained. The enzyme, capable of cleaving the ether, had a pH
optimum of 9.3-9.5. With labeled substrates, the cleavage products were
separated and identified as p_-nitrophenol and S_-(2-nitro-4-trifluoro-
methyl phenyl )gluthathi one (Frear and Swanson, 1973). This glutathione
conjugate was also formed by peanut (Arachis hypogaea L.). O-Conjugates
of p-nitrophenol and traces of the 2-amino analog of fluorodifen also
formed. Other unidentified metabolites were observed (Shimabukuro et al . ,
1973a). In other studies with peanut seedlings, metabolites identified
included 2-ami no-4-trifluoromethyl phenol , 2-amino-fluorodifen and traces
of p_-aminofluorodifen and 2,41-diaminofluorodifen. The major product
was not identified (Eastin, 1971a and c). Cucumber seedlings were also
exposed to labeled fluorodifen. Leaves, stem, cotyledons and root were
analyzed. Metabolites identified included p_-nitrophenol , 2-aminofluorodifen,
p_-aminophenol , 2,41-diaminofluorodifen and p_-aminofluorodifen (Eastin,
1971b).
141
FLURECOL (Flurenol, EMD-IT 3233) [9-Hydroxyfluorene-9-carboxylic acid]
FLURECOL-n-BUTYL ESTER (IT-3233, Am' ten, Florencol, Flurenol -n-butyl
ester) [r^-Butyl 9-hydroxyfluorene-9-carboxylate]
14C-labeled fluorecol -n-butyl ester was applied to leaves of Phaseolus
vulgaris. Five metabolites were observed: two isomeric e-glucosides
and three amino acid conjugates. The aglycone moieties were identified
as 21- and 31 -hydroxy analogs of flurecol-ivbutyl ester (Wotschokowsky,
1972).
142
FORMETANATE [m-{ (Dimethylaminomethylene)amino}phenyl N-methyl carbamate]
About 84% of formetanate injected into houseflies was metabolized in
4 h. The major metabolite was 3'-hydroxyformanilide. Microsomes from
housefly abdomen plus NADH resulted in only 10% metabolism of formetanate.
Incubation of labeled formetanate with alkaline soil resulted in a 50%
decomposition in less than two days. The major products were 3-formamido-
phenyl methyl carbamate, 3'-hydroxyformanilide and m-aminophenol .
Irradiation of formetanate with UV (254 my) produced 3'-hydroxyformanilide
(the main product), 3-formamidophenyl methyl carbamate and m-{ (dimethyl -
aminomethylene)amino}phenol . N^-Demethylation of formetanate was of
minor importance photochemical ly (Arurkar, 1971).
143
FRESCON (Trifenmorph, WL 8008) [N-Trityl morpholine]
Rats eliminated 97% of a single dose within 96 h. Within the gut,
frescon was probably hydrolyzed prior to absorption. The morpholine
was excreted largely unchanged. Tri phenyl carbi no! was metabolized
to a glucuronide in part and also hydroxylated (mainly para). The
latter was conjugated with glucuronic acid (Beynon, 1971).
When fish were exposed to frescon at 0.2 ppm, the only residue observed
in fish after 30 min was unchanged frescon (Beynon, 1971).
Rice plants grown in treated water contained residues of triphenyl-
carbinol and hydroxytriphenylcarbinols (o-, m-, and p_-) and their
glycosides. In water frescon hydrolyzes to tri phenyl carbi nol . Mud
and sediment gradually adsorb frescon and the carbinol. In soil,
within a few weeks frescon is aerobically converted to the carbinol
which undergoes slow hydroxylation (Beynon, 1971).
Hydrolysis t^ at 0.05 ppm
PH
6.5
7.1
7.4
8.0
9.0
time
in hours
3
10
28
ca.
100
ca.
1000
144
GARDONA [Dimethyl 2-chloro-l-(2' ,4' ,5'-trichlorophenyl )vinyl phosphate]
Exposure of gypsy moth larvae to gardona produced metabolites, both
free and bound, identified as 2,4,5-trichloroacetophenone, l-(2',4',5'-
trichlorophenyl )ethan-l-ol , 2,4,5-trichlorophenacyl chloride and l-(2\
4' ,5'-trichlorophenyl)-2-chloroethan-l-ol (Tomlin, 1972).
145
GLYPHOSATE [N-(Phosphonomethyl )glycine]
When applied to clay loam or muck soil, 56 kg/ha of glyphosate was
rapidly inactivated. This inactivation was probably the result of
reversible adsorption to clay and organic matter (Sprankle et al . ,
1975a). Iron and aluminum clays and organic matter adsorbed more
glyphosate than sodium or calcium clays and was readily bound to
kaolinite, illite, bentonite, charcoal and muck but not to ethyl
cellulose. ll4C-Labeled glyphosate was degraded in soil and 11+C02
was released (Sprankle et al . , 1975b).
146
GRISEOFULVIN (Fulvicin) [7-Ch1oro-4,6-dimethoxycoumaran-3-one-2-spiro-
1 - ( 2 ' -methoxy-6-methyl cycl ohex-2 ' -en-4 ' -one ) ]
Liver homogenates prepared from Charles River male mice and rats were
incubated with griseofulvin. Analyses showed the presence of 4-desmethyl
griseofulvin and 6-desmethyl griseofulvin (Chang et al . , 1973). Pre-
treatment with phenobarbital increased both 4- and 6-desmethylation of
griseofulvin whereas 3-methylcholanthrene increased only 6-demethylation
in rats (Lin et al . , 1973).
147
HCB [Hexachlorobenzene]
Single doses of 10 ppm of hexachlorobenzene were administered to rats
and several Rhesus monkeys. In rat feces and liver, pentachlorobenzene
(PCB) and unchanged HCB were identified by GLC-MS. Pentachlorophenol
(PCP) and PCB were identified in urine and feces by GLC-MS. Tetra-
chlorobenzene (TCB) was identified by GLC in rats and monkeys (Rozman
et al., 1975).
In other studies, after administration of a single oral dose of 14C-HCB
to adult male rats, primary excretion was via feces (16%). No metabolites
appeared to be present. In urine, less than 1% of HCB was excreted
but analyses indicated the presence of PCB, TCB, PCP and 2,4,5-trichloro-
phenol . Homogenates of liver, lung, kidney and small intestines were
incubated with HCB. Trace amounts of chlorobenzenes were produced.
Liver microsomal preparations with added NADPH produced chlorophenols.
Pentachlorophenol probably formed a glucuronide or other conjugate.
The studies also indicated the formation of glutathione conjugates
(Mehendale et al . , 1975).
Hexachlorobenzene was slowly decomposed by a mold that was capable of
decomposing lindane. The only metabolite detected after 52 days was
pentachlorobenzene. When pentachlorobenzene was added to a culture of
the mold, degradation produced the following metabolites: pentachloro-
phenol; 2,3,4,5- and 2,3,4,6-tetrachlorophenol ; 1 ,2,3,4-tetrachloro-
benzene; 1,2,4,5- and/or 1 ,2,3,5-tetrachlorobenzene; 2,3,4-, 2,4,6- and
3,4,5-trichlorophenol ; and 1 ,3,5-trichlorobenzene (Engst et al . , 1975).
Irradiation of HCB by UV (A>290nm) in quartz produced C02, HC1 and
CI 2 (Gab et al . , 1975a).
When sheep were dosed with HCB, residues in omental fat were approx-
imately proportional to dose rates. Although about 1000 times lower
in HCB concentration, blood also reflected the residue in fat.
Similarly, tissue levels in pigs and chickens reflected feeding levels
of HCB. The half-life for HCB in sheep, chickens and pigs was 10 to
18 weeks, 8 to 14 weeks and 10 to 12 weeks, respectively (Avrahami ,
1975; Avrahami and Steele, 1972a and b).
148
HINOSAN (Edifenphos) [O-Ethyl S,S-diphenyl phosphorodithiolate]
Hinosan was incorporated in fodder and fed to female goats for 10 days.
Several goats were also administered hinosan orally via gelatin capsules.
Urine, feces and milk were collected for analyses. At a dose level of
1 mg/kg, no hinosan appeared in the milk. At 10 mg/kg, residues
appeared at extremely low levels but disappeared rapidly after 3 days.
Low residue levels also appeared in tissues after 4 days. Analyses of
urine, after administration of 10 mg/kg of hinosan, showed the presence
of 13 metabolites but no hinosan was observed. The following metabolites
were identified in urine by co-chroma tography by TLC and GLC:
0-ethyl S-phenyl hydrogen phosphorothiolate (ESP) (V)
S_,S-di phenyl hydrogen phosphorodithiolate (SSP) (VII)
0-ethyl S-phenyl hydrogen phosphorodithiolate (ESSP (XII)
0-ethyl di hydrogen phosphate (EP) (X)
S-phenyl di hydrogen phosphorothiolate (SP) (VI)
phosphoric acid (PA) (XI)
diphenyl disulfide (DPDS) (IV)
methyl phenyl sulfide (MPS) (XIII)
methyl phenyl sulfoxide MPSO) (XIV)
methyl phenyl sulfone (MPS02) (XV)
m- and p_-(hydroxyphenyl )methyl sulfoxide (m- and p-(OH)-MPSO) (XVII)
m- and p_-(hydroxyphenyl (methyl sulfone (m- and p_-(0H)-MPS02) (XVIII)
Since some of the metabolites were not determined without acid hydrolysis,
they were probably conjugated. In feces, only MPS02 and some unchanged
hinosan were observed (Ueyama and Takase, 1975).
When administered to a rat and dog, hinosan was rapidly metabolized.
Diphenyl disulfide was found in urine but benzenethiol was not observed.
The 0-conjugate of hydroxyphenyl methyl sulfone was also present (Eben
and Kimmerle, unpubl . , 1972).
When applied to rice plants (Oryza sativa L. v. hatsukinode and v.
jukkoku), hinosan persisted somewhat longer than many phosphorus
insecticides. The half-life on rice leaves was about 4 days (Ishizuka
et al . , 1973). Degradation of hinosan was primarily by cleavage of
the P-S bond. 35S- and 32P-labeled hinosan was used to elucidate the
metabolic pattern. Co -chroma tography indicated the presence of 0,0-
diethyl S-phenyl phosphorothiolate (I), triphenyl phosphorotrithiolate
(II), diphenyl disulfide (IV), S_-phenyl dihydrogen phosphorothiolate (VI),
0-ethyl S-phenyl hydrogen phosphorothiolate (V), S,S-diphenyl hydrogen
phosphorodithiolate (VII), benzenethiol (III), benzenesulfonic acid
(VIII), sulfuric acid (IX) and phosphate (XI) (Ueyama et al . , 1973).
In other studies ethyl phosphate (X) was also observed (Takase et al . ,
1973).
149
(H) :2Ht®
IV
t
0-sh
DPDS
III
PSH
, y S03H
VIII
t
H2S0.,
IX
X
v>4
Hinosan
/
MX9
O-f-s-G
■SH
C2H5
ESSP
XII
II
0
C2H50-P-SQ
ESP OH
V
0
HO-P
1
S
6 +
SSP
VII
8
C2H50-P-0H
OH
EP
G>-sh
PSH III
HO-P-sQ
OH
VI SP
H3PO„
m-/p-
HO'
PA XI "J^^-S-CH3 -*"
je OH-f*
m-/p-H0^S-C
XVI
-MPS
O-5-
, MPS
|XIII
"CHq
j/ OH-MPSO
m-/p-H0-Qi-CH3 -e~~
0H-MPS02
XVIII
XVII
OS_ch3
XV MPSO,
-S-CH.
v/-j-CH3
MPSO XIV
150
IMIDAN [0,0-Dimethyl S-phthalimidomethyl phosphorodithioate]
In diethyl ether, photolysis of imidan produced N-methylphthalimide
(II) and N-methoxy methyl phthal imide (III). Further irradiation of
N-methylphthalimide produced approximately another six compounds,
three of which were identified as 3-hydroxy-2-methyl phthal imidine
(IV) and the two isomers of 3-(l ' -ethoxyethyl )-3-hydroxy-2-methyl-
phthal imidine (V). The latter appear to arise from the reaction of
product IV and the ether solvent (Tanabe et al . , 1974).
S
II
-CH2-S-P-0CH3
iCH3
J-CH2-0CH3
HC ^OH
H3d\)-CH9-
Va
H OH
151
IRGASAN DP 300 [5-Chloro-2-(2,4-Dichlorophenoxy)phenol ]
Technical formulations of tri-, tetra-, and penta-chlorophenols contain
dimeric impurities. The main constituent of these impurities are
2-phenoxyphenols with 4-9 chlorine atoms. The bactericide known as
Irgasan DP 300 contained 2,3,4-trichloro-6-(2,4-dichlorophenoxy)phenol .
This compound undergoes ring closure with application of heat or when
irradiated with UV (xmax = 290-430 nm). When Irgasan was subjected
to heat and irradiation, only heat produced 2,7-dichlorodioxin (Nilsson
et al., 1974).
CI
A1C1
OH CI
Irgasan DP 300
or UV
2,7-Dichlorodioxin
1 ,2,3,7-Tetrachlorodioxin
152
ISOXATHION (Karphos) [0,0-Diethyl 0-(5-phenyl-3-isoxazolyl )phosphoro-
" thioate]
Isoxathion-ll+C was administered to Wistar strain rats. Radioactivity
was eliminated rapidly mainly in the urine. Four major and seven
minor metabolies were detected. Because of the small amounts available,
the minor products were not identified. The major metabolites were
identified as:
(III) 3-hydroxy-5-phenyl i soxazol e ;
(XIV) 5-phenyl-3-isoxazolyl sulfate;
(XV) 3-(B-D-glucopyranuronosyloxy)-5-phenylisoxazole; and
(XVI) hippuric acid.
Compounds III, XIV and XV were also found in the tissues (Ando et al . ,
1975).
Persistence of isoxathion in soil was influenced by soil type and
moisture content with an approximate half-life of 15 to 40 days in
nonflooded soils and a much faster disappearance in flooded soil.
In addition to C02, biochemical degradation produced: 3-hydroxy-5-
phenyli soxazol e (HPI) (III); the rearrangement product, 5-phenyl-4-
oxazolin-2-one (VII); benzoylacetamide (X); and benzoic acid (XII).
Six non-persistent metabolites were tentatively identified as:
isoxathion oxon (II); 3-methoxy-5-phenyli soxazol e (V); 2-methyl-5-
phenyl-4-i soxazol in-3-one (VI); 2-acetyl-5-phenyl-4-i soxazol in-3-one
(IV); 2,5-diphenylpyrazine (IX); and acetophenone (XI). There were
strong indications also of conjugated material. Hydrolysis with
boiling 6N HC1 for six h released HPI, benzoic acid and a-aminoaceto-
phenone. The latter arises from 5-phenyl-4-oxazolin-2-one and its
metabolites or degradation products (Nakagawa et al . , 1975).
HPI (III) was stable when exposed to sunlight. When exposed to UV,
HPI decomposed to yield primarily 5-phenyl-4-oxazolin-2-one (VII).
Benzoic acid (XII) and benzoylacetamide (X) were also produced
(Nakagawa et al . , 1974).
153
154
KEPONE [Decachloropentacyclo[5.3.0.02>6.03>9.01+'8]decan-5-one]
MIREX [Dodecachloropentacyclo[5.3.0.02'6.03'9.04>8]decane]
KELEVAN [Decachloropentacyclo[5.3.0.02>6.03>9.04'8]decan-5-ol-5-
levulinic acid]
Kepone hydrate was irradiated in cyclohexane with ultraviolet. There
were two major products identified as compounds XI and XIa (Alley
et al., 1974a).
Mirex was absorbed more rapidly from digestive tract of female quail
than of the males and was rapidly excreted. Male quail excreted more
via feces than did female quail. No metabolism of mirex was observed
(Ivie et al . , 1974c). In other studies, after administration of 14C-
mirex, the half-life in fat of female and male quail was about 20 and
30 days, respectively, and in whole body of fish, 130 days. In fat of
female rats, 10 months after being returned to a "clean" diet, residues
of mirex had declined by only 40% (Ivie et al . , 1974d). In studies
with young leghorn roosters, the amount fed correlated well with
amount accumulated over a 20-week period.
If: X = ppm in feed
Y = ppm in fat
Then: Y = a+bX and
Y intercept a = 1.0508
slope b = +73.7628
correlation coefficient r = +0.9999767
(Medley et al . , 1974)
When mallard duck eggs containing mirex were irradiated with UV and
y irradiation, seven and eight products were formed, respectively.
Two were identified and tentative identification of two other products
was made (Lane et al . , 1976).
Cows were fed rations containing mirex. Analyses of fat and milk
were then conducted. Residue levels over a 31-week feeding period
did not exceed 0.08 ppm in milk and 1.87 in omental fat when mirex
was fed at 1.00 ppm (Bond et al . , 1975). In eggs of hens fed 1.06 ppm
mirex, the residue level reached 2.03 ppm at 28 weeks and then began
declining (Woodham et al . , 1975).
Anaerobic incubation of sewage sludge with mirex gave indications of
degradation. After two months incubation in the dark at 30C, the
sludge was centrifuged and the supernatants were extracted. Gas
chromatography in three columns, chromatography in two solvent systems
155
isf1"
11
i
11
ii
n
in
IV
10
Kepone f gem-D1ol
V vi
OH
10
CI
J -A >rJ> ^
"-C1.
■-C1.
(trans) V^ (cis)
XX ' XXI
> 17'
•*fch *^fZ7--Cl8,H
/xxiv yw
R=CH2-C-CH2-CH2-C-0CH,-CH
i2-on3
156
on silica gel thin layer plates, and mass spectra were used to identify
the metabolite as the 10-monohydro analog of mirex (Andrade and Wheeler,
1974a; Andrade et al . , 1975). Other studies with soil microorganisms
were conducted with nine aerobic soils and four anaerobic lake sediments
No mirex degradation occurred (Jones and Hodges, 1974).
Photolytic degradation of mirex in cyclohexane or isooctane produced
two compounds. The monohydro was narrowed to III or IV; the di hydro
is believed to be one of four compounds XII, XIII, XIV or XV (Alley
et al . , 1973). In other studies, the monohydro photoproduct was
identified as compound III (Alley et al., 1974a).
When mirex in tri ethyl amine was irradiated with UV, the major photo-
product was compound II. A second compound was identified as III. A
mixture of dihydro photoproducts formed was believed to be XX or XXI
(Alley et al., 1974b).
Pyrolysis of mirex produced hexachlorobenzene as the major product
and hexachlorocyclopentadiene in small amounts. The vapor phase
contained CO, C02, HC1 , Cl2, CC1 ^ and C0C12 (Holloman et al., 1975).
Mirex was exposed on silica gel thin-layer chroma topi ates to sunlight
or ultraviolet light. Slow degradation occurred. The major photo-
product was identified as the monohydro derivative III. Another
compound more polar than mirex was identified as kepone hydrate (VI).
A compound appearing in small amounts was identified as the monohydro-
kepone hydrate XI. Exposure of compound III to artificial light
resulted in conversion to compound VII (Ivie et al . , 1974b).
Irradiation (x>300nm) of kelevan in n-hexane produced compounds XXII,
XXIII and V. Identification was made by chromatography, IR and mass
spectra. When kelevan was irradiated in methanol, compounds XXIII
and the methyl esters of kelevan and XXII were observed. In acetone,
XXII was formed. When quartz filter was used, XXIV and XXV were
formed. After prolonged {Sh h) irradiation of kelevan, mirex and
kepone were found in 15 and 28% yield (Begum et al . , 1973).
In other studies, kelevan was applied to potato leaves and to soil.
Analysis after 11 weeks indicated the same metabolites were present
in both. In addition to unchanged kelevan, kelevan acid, kepone and
kepone acetic acid and some unextractable material were present.
Similar results were obtained when the soil was analyzed one year
later. GC/MS was used for identification (Sandrock et al . , 1974).
157
HO
CI
0 0
ii n
H2-C-CH2-CH2-C-0CH2-CH3
Kelevan
CH2-C-CH2-CH2-COpH
CH2-C00H
Kelevan acid
Kepone acetic acid
CI
10-
/
Kepone
158
KITAZIN P [0,0-Diisopropyl S-benzyl phosphorothiolate]
32P and 35S-labeled Kitazin P was applied to rice plants. When applied
as a spray, Kitazin P disappeared fairly rapidly. When applied to the
water, the disappearance rate increased. The water-soluble metabolites
were separated into five fractions. Products identified were: 0,0-
diisopropyl hydrogen phosphorothioate (V); phosphoric acid (IX);
isopropyl di hydrogen phosphate (VIII); diisopropyl hydrogen phosphate
(VI); 0-isopropyl S-benzyl hydrogen phosphorothiolate (VII); and dimethyl
sulfate. When the toluene-soluble fractions were chromatographed, eight
metabolites were observed on TLC. 0,0-Diisopropyl 0-benzyl phosphoro-
thionate (IV) and dibenzyl disulfide Jill) were identified by GLC
(Yamamoto et al . , 1973).
159
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160
LANDRIN [3,4,5- and 2,3,5-Trimethylphenyl N-methyl carbamate]
The persistence of landrin in eight soils was studied. The half-life
varied between <4 to >40 days. As pH increased above pH 7, the break-
down rate increased. Although microorganisms played a role in the
breakdown, alkaline hydrolysis was a major cause of landrin degradation
(Asai et al . , 1974).
Photolysis of landrin in ethanol or cyclohexane produced 3,4,5-tri-
methyl phenol (Addison et al . , 1974).
161
N-Lauryl-L-valine
Many organisms could utilize the sodium salt of this compound as
carbon and nitrogen sources for growth. Pseudomonas aeruginosa
AJ 2116 apparently cleaved the N-acyl linkage with release of 1 auric
acid. Gas chromatography also produced two peaks corresponding to
caprylic and capric acids. When 1LtC-labeled ^-lauryl-L-valine sodium
salt was used, 11+C02 was also observed (Shida et al . , 1973).
162
LEPTOPHOS (VCS-506, Phosvel , Abar) [0-(4-Bromo-2,5-dichlorophenyl )■
6-methyl phenyl phosphonothioate]
After application of leptophos to tomato plants, initially degradation
was very slow but accelerated three weeks after treatment. The phenol
metabolite increased in fruit and leaves during the initial three weeks
but then decreased. The oxon analog was detected in leaves but not
fruit. In grapes, results were similar. The phenol increased during
the first three weeks and then decreased (Aharonson and Ben-Aziz, 1974)
163
LUPROSIL [Propionic acid]
Luprosil breaks down completely in the citric acid cycle. Successive
reactions involving CoA, methyl ma lonyl CoA and succinyl CoA bring the
luprosil into the cycle (Anon., BASF, 1974).
164
MALATHION [0,0-Dimethyl S-(l ,2-dicarbethoxy)ethyl phosphorodithioate]
After topical application of 32P-malathion to adult larva of the
cotton leaf worm (Spodoptrea littoral is), 32P-activity was distributed
between hemolymph, gut and fat. About 23% of the applied dose was
metabolized in 24 h. A major site of enzymatic attack occurred at
the P-0-alkyl bond and then hydrolysis of the P-S bond to give thio-
phosphoric acid. Oxidation of P=S to P=0 produced malaoxon. Hydrolysis
of the esters gave mono- and di- acid derivatives. 0,0-Dimethyl phos-
phorodithioic acid was isolated in small amount. Oxidation of this
could give rise to the 0,0-dimethylphosphorothioic acid found. Dimethyl
phosphate was also found. The latter gave rise to monomethyl phosphate
and inorganic phosphate (Zayed et al . , 1973).
With resistant and non-resistant housefly strains, in vitro studies
showed that resistant strains degraded malaoxon oxidatively at a rate
lOx higher than that of the susceptible strain. The oxidation product
was malaoxon 3-monocarboxylic acid when a susceptible strain was used.
The resistant strain produced some 3-monoacid but the malaoxon a-
monoacid was probably the main metabolite. Positive identification,
however, was not made (Welling et al . , 1974).
Studies with an Arthrobacter sp. showed that this organism was capable
of degrading malathion. Laboratory studies identified the metabolites
as malathion half ester, the dicarboxylic acid, dimethyl phosphoro-
dithioate and dimethyl phosphorothioate. O-Demethyl malathion was also
observed but was non-biological in origin. Identification by TLC was
confirmed by infrared spectroscopy (Walker, 1972).
When larval homogenates of a malathion-resistant and malathion-susceptible
strain of the Indian meal moth (Plodia interpunctella Hubner) were tested
for esterase activity, the resistant strain had greater a-napthyl acetate
esterase than the susceptible strain; less carboxyl esterase and butyryl-
cholinesterase; and similar acetylcholinesterase activity (Zettler, 1974).
A heterogeneous bacterial population was isolated from river water and
incubated with malathion as a sole carbon source. About 1% of the
malathion was converted to the dicarboxylic acid, diethyl maleate, and
0,0-dimethyl phosphorothioic acid. The major metabolite was the 3-
monoacid. The bacteria present were identified as Flavobacterium
meningosepticum, Xanthomonas sp., Comamonas terrigeri , and Pseudomonas
cepacia (Paris et al . , 1975).
165
■ CH3°\il J>
p-s-ch— cr
ch or N)c h
H5C2^H 25 '»
CH Csj
CH30>"SH S
CH3°J ^ ^*-
CHj0;p-S-(jH-C>OC2H5 +
Malathion
ch3oJ 0_
/ CHa-^C2H5
o-Malath1on monoadd N.
/ 6-Malath1on monoadd
kc
N-i
CH33C^-SH * \JHH"^°H
H5C2cf
r ch3oJ Ji
CH3(r"S~fH~'C;OH
CH2"S)H
Malathion dladd
/
CH3oJ
CH3O>-0H +
V
HS-CH— C^qH
CH2-C^H
"5 -1 -1
4.8 x 10 M sec
T pH
67 4.0
S
kb
1 yr
ka+b
5.5 + 0.3
27 8.0
36 h
kc+d
3.1 + 0.2
27 8.0
24 d
ke
1.8 ± 0.2
27 8.0
1 yr
(Wolfe et al., 1975)
166
MALEIC HYDRAZIDE (MH) [1 ,2-Dihydropyridazine-3,6-dione]
Activated carbon delayed decomposition of maleic hydrazide in soil.
Degradation followed first order kinetics. The Freundlich k determined
for adsorption on activated carbon was 2300 yg/g (Helweg, 1975).
167
MATACIL [4-Dimethyl ami no-3-tolyl -N-methyl carbamate]
Matacil was added to an ascorbic acid system containing L-ascorbic
acid, ferrous ions, EDTA and dissolved oxygen. After 2 h at 37C,
the mixture was extracted and analyzed. Isolated compounds were
identified by co-chroma tography and/or IR and MS. About 12 compounds
formed. Seven of 12 products could not be identified. One was iden-
tified as 4-amino-3-tolyl -N-methyl carbamate. Tentative identification
was made for two compounds: hydroxy matacil and the N-hydroxymethyl
matacil. Another compound co-chroma tographed with 4-monodemethylamino
matacil. IR and mass spectrometry confirmed its identity. Another
compound was identified as 4-N_-dimethyl ami no-3-methyl phenol (Balba and
Saha, 1974).
The major photoproduct from matacil irradiation (x>300nm) in ethanol
or cyclohexane was 4-dimethylamino-3-methyl phenol (Addison et al . , 1974)
168
MEOBAL [3,4-Xylyl-N-methyl carbamate]
Photolysis of meobal in cyclohexane produced only phenol and some
polymer. In ethanol , in addition to the 3,4-dimethyl phenol , three
other compounds were identified:
4,5-dimethyl-2-hydroxy-N-methylbenzamide;
2,3-dimethyl-6-hydroxy-N-methylbenzamide; and
o- xylene (Kumar et al., 1974).
H 0
H3C-A-C
169
MERCURY COMPOUNDS
In studies with 48 patients who had ingested seeds treated with
mercurials, methyl mercury was determined and its biological half-
life in man was calculated to vary from 35 to 189 days with an
average of 72 days (Al-Shahristani and Shihab, 1974).
In the squirrel monkey, four days after administration of a single
dose of methyl mercury chloride, blood and brain concentrations
came into equilibrium. The biological half-time was found to be
about 49 days and 134 days, respectively, in blood and whole body.
Biotransformation of the methyl mercury produced inorganic mercury.
In the liver, 20% of the total mercury was inorganic; in the kidney,
50%; in the bile, 30% to 85%; but in the brain less than 5% of the
mercury was inorganic (Berlin et al . , 1975).
Biotransformation of methyl mercury in the guinea pig produced a
high mercuric level in the kidney and a low liver level (50% and
5%, respectively) (Iverson and Hierlihy, 1974).
After exposure of bovine erythrocytes to methyl mercury chloride,
rapid and almost complete uptake of mercury occurred. Over 90%
of the mercury penetrated the bovine cell membrane and associated
with intracellular hemoglobin. Various sulfhydryl agents elicited
release from cells. Cysteine alone induced a transient release of
methyl mercury from erythrocytes but did not facilitate equilibrium
with albumin. Rat red cells released much less methyl mercury to
albumin than human red cells (White and Rothstein, 1973).
Single doses of 203Hg-methyl mercury chloride were administered into
the rumen of a milk goat and a milk cow. Less than 20% of the dose
appeared in the feces within 72 hours and no radioactivity was
detected in the cow's milk. The half-time retention of the 203Hg
from methyl mercury chloride was 22 days in goats (Sell and Davison,
1975).
Methyl mercury chloride was incubated with intact and ghost erythro-
cytes and reticulocytes of adult New Zealand white rabbits. Within
5 min these cells accumulated almost all of the available mercury
(Garrett and Garrett, 1974).
In cats administered a single oral dose of 203Hg-labeled methyl
mercury chloride, the half-period of methyl mercury for whole body
was 117.7 t 1.4 days including hair and 76.2 t 1.6 days excluding
the hair (Hoi 1 ins et al . , 1975).
170
After injection of 203Hg-methyl mercuric chloride into adult Wistar
rats, 3% to 6% of the total brain mercury was present in the inorganic
form. This was more than from an equal dose of mercuric chloride.
Myelin and mitochondrial fractions accumulated more inorganic mercury
than other fractions (Syversen, 1974). When x ttCH3203HgCl was force
fed to rats, the amount of C-Hg bond cleavage was calculated to be
between 5.1% and 10.6% in blood fractions. Highest concentration
of mercury was in the hemoglobin one day after force-feeding (Garcia
et al., 1974a). In milk of lactating Sprague-Dawley rats which
had been force fed labeled methyl mercury chloride, there was an
average of 4.5% bond breakage in the milk; 6.2% in the cerebrum;
6.2% in the liver; 8.0% in the kidney (Garcia et al . , 1974b).
Brains of Wistar rats, given CH3HgCl intraperitoneal ly ewery second
day from 5 to 27 days of age, were analyzed. The myelin fraction
contained a larger proportion of inorganic mercury than found in
other fractions (Syversen, 1974). In rat bile, the principal methyl
mercuric compound observed was methyl mercuric glutathione. This
compound also formed in vitro with bile. A small amount of methyl
mercuric cysteine also occurred in the bile. This increased with
storage of the bile (Refsvik and Norseth, 1975). When ^-acetyl-
homocysteine was intravenously administered, after methyl mercury
chloride, urinary excretion of mercury increased. The corresponding
thiol actone turned out to be more effective in removing mercury from
the body (Aaseth, 1975). Administration of methyl mercuric chloride
in the presence of selenium greatly increased the concentration of
the mercury in the brain of rats and reduced uptake by kidneys
(Chen et al . , 1975).
Methyl mercury-203 was orally administered to Jersey cows. About
59% was absorbed. Tissue concentrations were kidney > liver >
skeletal muscles > heart > smooth muscle > spleen > lung > brain >
ovaries > pancreas. Of the total mercury body burden, 72% was in
muscle and 7% in liver and only 0.17% appeared in milk in 14 days
(Neathery et al . , 1974).
Aspergillus niger and Penicillum notatum were able to grow and
reproduce in limited amounts of methyl mercury chloride. Twenty-
five and 20 ug Hg per gm fungal tissue was absorbed (Hardcastle
and Mavichakana, 1974).
Bacteria were obtained from river bottom sediments in an area
highly polluted with inorganic mercury. When incubated with methyl
mercury chloride, mineralization of the mercurial occurred (Billan
et al . , 1974). Some enteric bacteria were capable of causing
volatilization of 203Hg-methyl mercuric chloride (Schottel et al . ,
1974). When methyl mercuric chloride was anaerobically incubated
with human feces, Ch3Hg+ disappeared at a constant rate during a
7-day test. Methane was not observed (Edwards and McBride, 1975).
171
In studies with plasmalogens, methyl mercury chloride was soluble
in this phospholipid. The methyl mercuric ion catalyzed rapid
hydration and hydrolysis of the vinyl ether linkage to give a mixture
of palmitic and stearic aldehydes plus the linolenic monoglyceride
product (Segal 1 and Wood, 1974).
Guppies accumulated methylmercury from solution but converted very
little to inorganic mercury. When the guppy (Labistes resticulatus)
and coontail (Ceratophyllum demersum) were exposed to water containing
203Hg-ethyl -mercuric chloride (EMC), the uptake of EMC was related
to exposure time and concentration. Internal organs of the guppy
contained the highest concentration of 203Hg and the half-life of
203Hg was about 20 to 23 days. The guppy and coontail were both
capable of converting EMC to inorganic mercury (Fang, 1974).
After a single oral dose to rats, methylmercury dicyandiamide was
slowly excreted in feces and urine, primarily i-n organic form.
Methylmercury dicyandiamide slowly broke down in kidneys and liver
to inorganic mercury. Methylmercury dicyandiamide was rapidly
absorbed into circulation and bound by the tissues, particularly
by blood cells (Rusiecki and Osicka, 1972).
Methylmercury hydroxide was shown to have a lower affinity than
Cd++ or Hg++ for thionein.
When Hg(0Ac)2 was intravenously injected into laying quail, the
mercury was bound to lipovitellin and transported into ovarian
follicles (Nishimura and Urakawa, 1972). A microorganism, found
in activated sludge and identified as Pseudomonas oval is, tolerated
mercury acetate (Tomoyeda et al . , 1973~T In other studies, R-
factor systems in enteric bacteria were able to reduce Hg+ from
Hg(0Ac)2 to elemental mercury (Schottel et al . , 1974). When
solutions of mercuric acetate were irradiated with a 20 watt black-
light having the spectral distribution of sunlight, methylmercurlc
compound formed. In this reaction mercuric oxide can replace
mercuric acetate. The studies indicated that mercuric acetate
was hydrolyzed to mercuric oxide and acetic acid in water. The
mercuric oxide stimulated the light-induced methylation of inorganic
mercury (Akagi and Takabatake, 1973).
A metallic mercury-releasing enzyme (MMR-Enz), which catalyzes the
reduction of mercurials to metallic mercury, was induced when
Pseudomonas sp. were incubated with PMA, PCMB, merzonin, mercuric
chloride, and metallic mercury (Furukawa and Tonomura, 1972).
In a study of organisms capable of degrading methyl mercury, 207
organisms from sediments and fish were screened with methyl mercury
bromide. Thirty isolates were capable of degrading methylmercury
with volatilization of labeled mercury (Spangler et al . , 1973a).
In addition to Hg°, methane also formed (Spangler et al . , 1973b).
172
Liver preparations from rat, mouse, and guinea pig degraded methoxy-
ethyl mercury chloride (MEMC) with formation of ethylene. No evidence
of Hg° formation was observed. Preparations from rat brain and
kidneys of rat, guinea pig, ferret, and chicken also degraded MEMC
(Lefevre and Daniel, 1973).
When phenyl mercuryacetate (PMA) was incubated with liver preparations
from rat, mouse, guinea pig, ferret, and chicken, benzene was formed.
Brain preparations from rat, guinea pig, and ferret and kidney
preparations of rat, guinea pig, ferret, and chicken also degraded
PMA (Lefevre and Daniel, 1973). A number of bacterial isolates were
tolerant of PMA (Tomoyeda et al . , 1973) or capable of volatilizing
203Hg-PMA (Schottel et al . , 1974). In addition to Pseudomonas sp.,
Arthrobacter sp., Citrobacter sp., Enterobacter sp., Vibrio sp., and
Flavobacterium sp. also degraded PMA. Elemental mercury vapor and
benzene were observed products of degradation (Nelson et al.. 1973).
When guppies, snails, elodea, and coontail were exposed to 2(53Hg-PMA
in water, PMA was readily taken up and converted mainly to inorganic
mercury. Small amounts of ethylmercuric chloride (EMC) were also
formed. The biological half-life of 203Hg in guppies, coontail,
and elodea was between 43 and 56 days but was dependent on the
initial concentration. At higher concentrations the half-life
was between 7 and 11 days. In snails, the biological half-life was
about 10.8 days (Fang, 1973). When river sediments were incubated
with PMA, some methylmercury formed. More was formed under more
acidic conditions (Jacobs and Keeney, 1974).
Phenyl mercuric salts were converted to diphenylmercury as the main
product. Simultaneously, phenylmercuric chloride was produced in
amounts related to the amount of chloride contaminations (Dressman,
1972).
Incubation of liver preparations of rat, mouse, guinea pig, ferret,
and chicken with £-chloromercury benzoate (PCMB) produced benzoic
acid. Rat brain and rat, guinea pig, and chicken kidney preparations
also degraded PCMB (Lefevre and Daniel, 1973).
Photolytic half-lives of phenyl mercurials are summarized:
Compound ti/2, hrs.
Diphenyl mercury 8.5 ± 1.8
PMA 16.0+2.0
PMN 20.0 + 1 .0
Phenyl mercury B03 14.0 + 2.0
Phenyl mercury hydroxide 16.0 t 2.0
(Zepp et al., 1973).
173
The mechanism of mercury elimination in waste water was studied.
Mercury removal rates were over 99.8% when waste water containing
mercuric chloride was treated with acclimated sludge. It was found
that the added mercuric chloride was removed rapidly by volatilization
after reduction to metallic mercury. Optimum pH and temperature were
8 to 9 and 42 to 43C, respectively (Nakamura et al . , 1974a,b). In
other studies, the mercury-resistant bacterium Pseudomonas K62 strain
was incubated in culture medium for 6 h with various mercurials.
Results are summarized in the following table.
Mercury removal by Pseudomonas K62 (6x1 08 cells/ml)
Hg-Compound
Concentration
(ppm)
% Removal added
mercury
Added
Without Ps.
K62
With
Ps. K62
HgCl2
30
11
65
Hg(CN)2
30
0
72
Hg(N03)2
30
0
47
Hg(0Ac)2
30
15
45
HgSO^
30
25
73
Hg(SCN)2
30
9
55
Hgl2
30
14
69
HgO
15
29
69
PMA
100
0
80
Uptake of mercury in these studies was severely inhibited by sodium
chloride, sodium nitrate, KH2P0it and K2HP04 (Suzuki et al . , 1968).
Mature specimens of dungeness crabs, Cancer magister, were exposed
to dissolved inorganic mercury in aquarium water, returned to unpolluted
sea water, and then analyzed for total mercury. Experimental data
indicated that inorganic mercury has a biological half-life of 20-25
days in the dungeness crab (Sloan et al . , 1974). In the mollusc,
Tapes decussatus, the half-life was 5-10 days (Unlii et al . , 1972).
When elemental mercury was incubated with pure culture of micro-
organisms, oxidation and accumulation of mercury occurred. Six
cultures were tested:
P_. aeruginosa |_. coli
P_. fluorescens B_. subtil is
Citrobacter sp. B_. mega teri urn
Concentration factors calculated for E_. coli , P_. fluorescens, and
Citrobacter sp. were 196, 1202 and 222, respectively. The distribution
of mercury in aquatic biota from a stream receiving a continuous input
of Hg++ was also determined. Dragonfly nymphs (Neurocordulina
alabamensis) and damselfly nymphs (Argia sp.) exhibited highest total
174
mercury levels. Methyl mercury was highest in mosquito fish (Gambusia
affinis) , predaceous diving beetles (Dytiscidae) and water boatmen
(Hesperocorixa sp.). No methylmercury was found in algae, fungi and
bacteria (Holm and Cox, 1974).
Studies with bovine serum albumin indicated that mercury (II) was
bound at sites in addition to the carboxyl and thiol groups (Katz and
Samitz, 1973). Within 5 min after exposure to mercuric chloride,
intact and ghost erythrocytes and reticulocytes accumulated approxi-
mately 30% (intact) and 50% (ghost) of the available mercury (Garrett
and Garrett, 1974). Kinetic studies of mercuric chloride indicated
that mercury was contained in three compartments of short, medium, and
long retention time within the rat. Kidneys were the largest compart-
ment for mercury and kidney retention probably accounted for the long-
term compartment. The biological half-life was about 30-33.5 days
(Phillips, 1972).
When a goat was given 203HgCl2, less than 30% of the dose was absorbed.
Excretion of 203Hg in milk accounted for 0.22% of the dose. Half-time
of retention by goats of 203Hg given 203HgCl2 was 78 days (Sell and
Davison, 1975).
Suspensions of rat caecal and small intestinal contents were incubated
with HgCl2. Analyses indicated that these materials were able to
synthesize methylmercury (Rowland et al . , 1975).
The ability of algae to grow in media containing HgCl2 was studied.
Lag periods of 3 or more days were observed. The growth rate was
then similar to that of controls without Hg. The rate of decrease
of mercury content was not dependent on initial Hg concentrations
except at the lowest concentration (2 pM) (Ben-Bassat and Mayer,
1975).
In the presence of sublethal amounts of HgCl2, small amounts of methyl-
mercury were produced during 7 days aerobic growth by the following
bacteria:
Pseudomonas fluorescens Aerobacter aerogenes
Mycobacterium phlei Bacillus megaterium
Escherichia coli
and by mycelium of the fungi:
Aspergillus niger
Scopulariopsis brevicaul is
Saccharomyces cerevisiae
175
A yeast, isolated from a stream and identified as Cryptococcus sp.,
was grown in media containing HgCl 2. Analyses indicated the presence
of high levels of mercury in viable cells. The form of the mercury
was not determined but is believed to be elemental (Brunker and Bott,
1974).
When 203HgCl2 was incubated anaerobically with human feces, methyl-
mercury was produced in amounts directly related to the amount of
Hg+2 added. The disappearance of methylmercury occurred at a constant
rate during the 7-day test. lhCHh was not observed (Edwards and
McBride, 1975).
One mercury resistant strain of E_. coli converted 95% of 10" 5 M Hg+2
(HgCl2) to metallic mercury at a rate of 4 to 5 n moles Hg+2/min/108
cells. Metallic mercury was eliminated as a vapor (Summers and Silver,
1972). In addition to the E_. col i , S_. aureua and P_. aeruginosa were
also capable of carrying out these reactions (Summers and Lewis, 1973).
Methylation activity is higher in tuna liver than in other fishes.
Fractionation studies with tuna liver strongly suggested that the
factor was methyl cobal ami n, a known methyl donor in many biological
systems (Pan et al . , 1973).
Studies have shown that Hg+2 may be non-enzymatically reduced to
elemental mercury by humic acid (Alberts et al . , 1974) or by reducing
agents such as ethylene and acetylene (DeFilippis and Pallaghy, 1975).
In the presence of sulfur, inorganic mercury may be alkylated in
aquatic environments. Sulfur photooxidation to sulfate couples with
reduction of mercuric ions. A basic mercuric sulfate formed and was
an effective photosensitizer for the methylation (Akagi et al . , 1974).
The possibility that sediment materials might cause symmetrization
and conversions of monomethyl mercurials into dimethyl mercury was inves-
tigated. Results of this study indicated that alkylmercuric halides
are not symmetrized under the test conditions although arylmercuric
halides were. The procedure used consisted of placement of the
mercurial halide on a basic Al 203 column and eluting with a hydro-
carbon solvent (Cross, 1973).
Studies were conducted to determine the kinetics of microbially
mediated methylation of mercury in aerobic and anaerobic aquatic
environments. From these studies the following was concluded:
1. Methylation can occur under aerobic or anaerobic conditions.
2. Methylation under both conditions is dependent on growth rate
or metabolic activity of the methyl ating organisms, mercuric ion
concentration, and availability of mercuric ions.
176
3. At neutral pH, monomethyl mercury is the main product but dimethyl -
mercury forms in small amounts.
4. The rate of formation of the mono- and dimethyl mercury can be
described by
NSMR = YBn(Hgtotal)n where
NSMR = net specific methylation rate
y = coefficient of microbial activity
3 = coefficient of mercuric ion availability
n = reaction order
5. The average reaction order value (n) is 0.15 and 0.28 for anaerobic
and aerobic systems, respectively.
6. Methylation is temperature dependent only to the extent that it
affects microbial activity.
7. Large amounts of Hg° are formed and removed from the aqueous
phase when a gas is forced through the system.
(Bisogni and Lawrence, 1975).
177
MESUROL [4-Methylthio-3,5-xylyl-N-methyl carbamate]
Photodecomposition of mesurol produced only the compound 4-methylthio-
3,5-dimethyl phenol . This is the same product obtained by basic
hydrolysis of mesurol (Kumar et al . , 1974).
In alkaline soils, mesurol was rapidly hydrolyzed and CO2 evolved.
Hydrolysis in acid soil was shown. The half-life varied between 4
days at pH 7.6 to more than 56 days at pH 4.1. While hydrolysis
the main route of degradation in alkaline soil, in acid soil the
primary route appeared to be oxidation to the sulfoxide prior to
hydrolysis to the phenol (Starr and Cunningham, 1974b).
0=C-N-CH3
0 M
was
H,C
alkaline
soil
-CH3
Mesurol
Lacid soil
H,C
0=S-CH3
0=S-CH3
178
METHAZOLE (Oxydiazol , Probe, VCS-438) [2-(3,4-Dichlorophenyl )-4-methyl
1 ,2,4-oxadiazol idine-3,5-dione]
Wheat plants and Bermuda onions were placed in water containing lkC-
methazole for 24 h and then removed and analyzed after being washed.
Radioautography and ultraviolet light were used to visualize the
materials on silica gel. With TLC, about seven compounds were resolved:
two metabolites were not identified- however, acid hydrolysis (HC1 for
1 h at 90C) released methazole-methylurea (III) and methazole-urea (IV).
In onions, metabolite II was in greater concentration than I; in wheat,
metabolite I was in greater concentration. Acid hydrolysis of I gave
predominantly methazole-urea and small amounts of methazole-methylurea.
With metabolite II, the reverse was true. Two metabolites were not
identified but did chromatograph similar to 6,7-dichloro-l-methyl-2-
benzimidazolinone (VI) and the 5,6-dichloro analog (VII). Other conju-
gates were present as evidenced by acid treatment of plant solids after
methanol treatment and the release of metabolites I, III and IV. In
wheat, 50 to 60% of the dose was accounted for by metabolites III and
IV. In onions, methazole-methylurea was the predominant metabolite and
methazole-urea (IV) was present only at low concentrations. Treatment
of wheat seedlings with methazole-3-ll+C and methazole-phenyl-ll4C gave
similar results. This showed that methazole was metabolized in wheat
to form 11+C02 and the methyl urea metabolite (III). Some methoxymethyl-
urea was also detected in extracts of wheat and onions (Dorough, 1974).
Beans and cotton were treated with labeled methazole. Quantitative
rather than qualitative differences were indicated. From cotton, 1-
(3,4-dichlorophenyl )-3-methylurea (III) and 3,4-dichlorophenylurea
(IV) were obtained. The latter was the major metabolite. In addition
to these compounds, the hydroxymethyl derivative and three conjugates
were observed (Dorough et al . , 1973). In other studies with cotton
and prickly sida (Sida spinosa L. ) , compounds III and IV were also
observed (Butts and Foy, 1974).
After application of VCS-438 to cotton (Gossypium hirsutum L. 'Acala
4-42-77'), foliar penetration occurred within 3 h and increased with
time. Cotton tissue readily metabolized VCS-438 to l-(3,4-dichloro-
phenyl)-3-methylurea (DCPMU) and l-(3,4-dichlorophenyl jurea (DCPU).
When plants were treated through the roots with VCS-438, DCPMU, DCPU
and unidentified polar material formed. Digestion of plant residues
with the proteolytic enzyme pronase indicated that some of the unex-
tractable lkC may be complexes of DCPMU and DCPU with proteins (Jones,
1972).
When metabolites I and II were fed to rats, nearly 50% of a single
dose was excreted in the urine and 11% in feces within i day after
treatment; 65 and 21%, respectively, in 6 days (Dorough et al . , 1973).
179
Water solutions of methazole-phenyl-^C were exposed to sunlight for
7 days. Analyses indicated that compounds III, VI and VII were present.
In methanol, compounds VI, VII and VIII were observed (Dorough et al . ,
1973). In other studies, irradiation of methazole in water also formed
VI, VII and III and compound VIII in methanol (Ivie et al . , 1973).
180
CI
VII
V"
VI
ci-^ — 'o=c: c=o
ch3
Methazole
Compounds I & II
CI _y . VjJ-C-fi-CH -OCH
c^_y 8
VIII
ci-J — ' o
IV
4^V ^1
^ \ii-C-l5-CH3 +C02
i-c-3
CIA' o
I
N-Con jugate
III
N-Conjugate
-(\ /Vn-C-N-CHjOH —^O-Con Jugate
ci ^_^
v >», J=\ 8
CI-/. . Vn-c-n-ch ^och 3
P1-" ' '
VIII
181
METHIDATHION (Supracide, GS 13005) [S-(2-Methoxy-5-oxo-A2-l ,3,4-
thiadiazolin-4-yl )methyl 6,0-dimethyl phosphorodithioate]
Methidathion was irradiated with UV of A = 254 my. TLC, IR, mass
spectra and synthesis were used to isolate and identify nine products.
The proposed breakdown scheme is indicated (Dejonckheere and Kips,
1974).
182
Methidathion was fed to a cow as a residue in forage. No intact
methidathion was found in the milk and was found to be stable in rumen
fluid for 24 h. Incubation with beef liver 10,000xg supernatant
fraction degraded methidathion 74-86% within 30 min. Urinalyses showed
the presence of dimethyl dithiophosphate and dimethyl thiophosphate
(St. John, Jr., and Lisk, 1974).
183
METHOHYL (Lannate, DuPont 1179) [S-Methyl N- (methyl carbamoyl oxy)
thioacetamidate]
Charles River-CD rats were administered labeled methomyl . lltC02 and
acetonitrile were observed. Urine metabolites were not identified
(Harvey et al . , 1973).
Radiolabeled methomyl was applied to tobacco, corn and cabbage. Rapid
degradation occurred to produce CO2 and acetonitrile with a methomyl
half-life of 3 to 6 days. Labeled lipids, Krebs cycle acids, sugars
and other materials were also present (Harvey and Reiser, 1973). The
half-life on cotton was found to be between 2 and 4 days (Bull, 1974).
Radiolabeled methomyl was injected into 5th-instar cabbage loopers
[Trichoplusia ni (Hubner)]. Unidentified water soluble metabolites
were formed. Acetonitrile and other volatiles also probably formed
(Kuhr, 1973).
In soil, labeled methomyl was degraded to ll|C02 and other materials,
some of which were reincorporated into normal components of soil
organic matter (Harvey and Pease, 1973).
184
METHOXYCHLOR [2,2-Bis(p_-methoxyphenyl )-l ,1 ,1-trichloroethane]
ETHOXYCHLOR [2,2-Bis(p_-ethoxyphenyl )-l ,1 ,1-trichloroethane]
When 11+C-ring-labeled methoxychlor was incubated with a sheep liver
microsomal preparation for 30 min at 39C, two products were identified:
2-(p_-hydroxyphenyl )-2-(p_-methoxyphenyl )-l ,1 ,1-trichloroethane (8.13%)
and 2, 2-bis(p-hydroxyphenyl )-l ,1 ,1-trichloroethane (3.44%) (Hirwe
et al., 1975).
Chemical decomposition of methoxychlor was slow in water. The half-
live at pH 5 to 9 and 27C was 100 days. The photolytic half-life in
distilled water was 37 days. In some river waters, methoxychlor
photolysis in sunlight was rapid with a half-life of 2 to 5 h. The
ethylene analog (DMDE) was formed in each case (Zepp et al . , 1975).
Methoxychlor was administered orally to mice in olive oil and topically
in acetone to flies. Excrement was collected. Identification of
metabolites was by thin-layer chromatography. O-Demethylation was
observed with both species and the monohydroxy and dihydroxy metabolites
were observed. Similar results were obtained with mouse liver and
housefly microsomes (Hansen et al., 1974).
CH30-Q-|hQ-0CH,
■CH.0-
1
cfS0H X
CH3O-Q-C-0.
0CH3
CH30^|- <Q>0CH3-^ CH30^C-Q-0CH;
•13
Methoxychlor
H0-Oi-<O0H
■o&>
h°-<CH-O-0h
185
After exposure of the housefly (Rsp) and saltmarsh caterpillar (Estigmine
acrea) to ethoxychlor, excrement was collected and analyzed. In addition
to unidentified conjugates, six metabolites were observed. Studies
with microsomal preparations of these two species gave similar results.
When mice were used, only conjugates and the O-monodealkylated analog
were observed (Table 1) (Kapoor et al . , 1972). In another study with
mouse liver microsomes, metabolite III was observed (Hansen et al . ,
1974).
Studies with a model ecosystem are summarized in Table 2. Ethoxychlor
was concentrated in the higher trophic levels. In fish, this was 1500
and in snails, 98,000 times that in water. The
a factor of 35,000 for DDT and 120,000 for methoxy-
1972).
times that in water;
latter compares with
chlor (Kapoor et al
Table 1
Test Species
Saltmarsh
Mi
ce
Metabolite
Ho
usefly
Caterpillar
In vivo
In vitro
II
+
+
+
III
+
+
IV
+
+
+
+
V
+
+
VI
+
+
VII
+
+
Conjugates
+
+
+
+
Table 2
Ethoxychlor distribution
Algae
Snail
Mosquito
Fish
Metabolite
H20
(Oedogonium)
(Physa
1) (Culex)
(Gambusia)
II
+
+
+
+
+
III
+
+
IV
+
+
+
+
+
V
+
+
+
+
VI
+
+
+
VII
+
+
+
Unknown I
+
+
Conjugates
+
+
+
+
+
Polar Cmpds.
+
(Kapoor et al .
, 1972)
186
C2H50
■<Q> t<Q),0C2H5
(I)
Ethoxychlor
< '
C2H50-
mo
0CH2 CH2 OH
OCoH
2n5
(ID
C2H50
\j)t<^)-™
(ni)
h°-<Q^-<Q>-°h
ci2
(VI)
(IV)
ho-<G^t<C^)"oh
ci3
(V)
ho-OtQ
■OH
(VII)
187
METHYLCHLOR [2, 2-Bis(p_-methyl phenyl )-l ,1 ,1-trichloroethane]
In the search for biodegradable DDT analogs, methylchlor was studied.
Experiments were conducted with houseflies (R$p), salt marsh caterpillar
(Estigmine acrea) and mouse, and microsomal preparations from each
(Table 1 ), as well as with a model ecosystem (Table 2). Methylchlor
was found to concentrate in fish 1400 times over that in water and in
snails by a factor of 120,000. The latter compares with a factor of
3500 for DDT and 120,000 for methoxychlor (Kapoor et al . , 1972).
Table 1
Specie
Mouse
Metabolite Housefly Caterpillar In vitro In vivo
II +
III + + + +
IV + +
V + + +
VI
VII + + + +
VIII
Unknown I + + +
II + +
III +
IV +
Conjugates + + + +
H3C-OlO~CH3 ■* H3c-0"<fO"CH3
(ID ?l3 (i)3
H3C-O"^"O"C00H * h3c-<GtO"CH2°h
h3 ft,
(iv) V^ (in)
t
J^C-OfQ"00"-*- H0H.C- Q-^-Q-CH,
OH
H00C-^-?-<^-C00H (VI> (V)
CI.
:ia
(VII)
188
Table 2
Methyl chl or distribution in model ecosystem
Compound
H20
Algae
Snail
Mosquito
Fish
II
III
IV
V
VI
VII
+
+
+
+
+
+
Unknown I
II
III
IV
V
+
+
+
+
+
+
Conjugates
Polar metabol
ites
+
+
+
+
+
+
189
METHYLENEDIOXYPHENYL COMPOUNDS
PIPERONYLIC ACID
Pseudomonas fluorescens strain PM 3 was used to prepare a soluble
fraction containing oxidative activity. When this was incubated with
piperonylic acid, oxidative attack produced protocatechuate and formate.
One mole of 0? was consumed per mole piperonylate and NADH or NADPH
was required (Buswell and Cain, 1973).
190
MOBAM [4-Benzo[b]thienyl N-methyl carbamate]
Resistant and susceptible strains houseflies rapidly metabolized mobam.
Differences were quantitative rather than qualitative. Of the five
to six metabolites produced, one was identified as 4-hydroxybenzothio-
phene (Morallo, 1970).
191
MOCAP (Ethoprop) [O-Ethyl S,S-di propyl phosphorodithioate]
When mocap was administered to rats, the urine contained despropyl
mocap, 0-ethyl phosphoric acid, S-propyl phosphorothiolic acid and
desethyl mocap. Rat and rabbit liver supernatant enzymes de-ethyl ated
mocap in the presence of glutathione and formed S-ethyl glutathione.
Despropyl mocap was also isolated from liver microsomes and supernatant
and from plants, ^-propyl phosphorothiolic acid was also present in
plants. Methylene chloride extracts of bean and corn plants, grown in
mocap-treated soil, contained ethyl propyl sulfide, ethyl propyl
sulfoxide, ethyl propyl sulfone and propyl disulfide. Traces of S^
methylation products and subsequent oxidation were observed: methyl
propyl sulfide, methyl propyl sulfoxide and methyl propyl sulfone
(Iqbal, 1971).
192
MONITOR (Methamidophos, acephate-met, Tamaron, Ortho 9006) [0,S-Di methyl
phosphoramidothioate]
ORTHENE (Acephate) [0,S_-Dimethyl N-acetyl phosphoramidothioate]
Within 1 h, 130 day-old loblolly pine seedlings absorbed and distributed
ll*C-orthene from nutrient solution. Metabolites were separated by TLC.
Cochromatography and GLC were used to identify the main metabolite as
0,S_-di methyl phosphoramidothioate (Monitor) and another unidentified
compound (Werner, 1974).
In plant tissue, orthene is partially metabolized to 0,S-dimethyl
phosphoramidothioate, the active ingredient in the insecticide monitor
(Leary, 1974).
The alkaline hydrolysis of monitor was investigated. P-0 bond cleavage
occurred in aqueous potassium hydroxide. In the methanol and acetone
solutions, P-S bond cleavage occurred. In the aqueous solution, S-
methyl phosphoramidothioate formed; in the less polar methanol and
acetone, 0-methyl phosphoramidate. The potassium salt of 0-ethyl and
0-propyl phosphoramidate were the main products formed in ethanolic
and propanolic potassium hydroxide. Dimethyl sulfide also formed.
The second order rate constants for P-0 and P-S cleavage were determined
in potassium hydroxide at 27C for monitor and two closely related analogs
k, M"1 rnin"1
0,S-dimethyl phosphoramidate
0,S-dimethyl t^-methyl phosphoramidate
0,S-dimethyl M,N-dimethyl phosphoramidate
P-0
P-S
8.4
1.0 x 10"3
0.6
4.4 x 10-2
1.5 x 10"1*
(Fahmy et al . , 1972)
193
NAA [a-Naphthaleneacetic acid]
Conjugation of NAA in plant tissue studied. Eleven to 14-day-
old cowpea plants (Vigna sinensis, Endl . , cultivar Black Eye,
Early Ramshaw) were used. Leaves, floating on a-NAA-buffer solution,
quickly formed NA-glucose. The formation of NAA-aspartate followed
a 2 to 4 h lag (Goren and Bukovac, 1973).
When Kinnow mandarin fruits were dipped in aqueous solutions of
NAA, four metabolites were formed. Two of these were in small
amounts and were not identified. The other two, in larger amounts,
were identified as the a-NAA-aspartate and a-naphthylacetyl-e-D-
glucose (NA-glucose) (Shindy et al . , 1973).
194
NEMACUR (Bay 68138) [O-Ethyl 0-(4-methylthio-m-tolyl ) N-isopropyl
phosphoramidate]
After application to turf grass, nemacur was oxidized to its
sulfoxide and sulfone (Bowman, 1972).
195
NEODECANOIC ACID (NDA) [Mixture of di-a-branched decanoic acids]
14
C-Carboxy labeled neodecanoic acid was applied to onions to dry the
tops. Some C02 was formed during the first 12 days. Thereafter ll+C02
formation was negligible. When onion foil age containing 1UC-NDA was
applied to muck soil, 11+C02 was formed over a 30-day period with little
change in the rate of evolution. (Gilbert et al . , 1974).
196
NIAGARA 10637 [Ethyl propyl phosphonate]
When pea seedlings were treated with ethyl propyl phosphonate,
ethylene was apparently produced. In ancillary studies, ethylene
and propylene were produced when this phosphonate was exposed to
oxygen in combination with a reduced metal. Of the three systems
studied, the cuprous system was most effective; ferrous system,
least; and metallic copper intermediate (Dollwet and Kumamoto, 1970)
197
N-SERVE (Nitrapyrin) [2-Chloro-6-trichoromethylpyridine]
N-Serve was incubated at 20C and IOC in three soils. The half-life
at 20C for the three soils was 9, 15 and 16 days for coarse sandy
loam, loamy sand and loam, respectively; and 43, 77 and 43 days,
respectively, at IOC (Herlihy and Quirke, 1975).
Carboxy-labeled 6-chloropicolinic acid(6-CPA), administered to a
rat, was rapidly eliminated. Urine collected during the first
8 h showed the presence of 6-CPA and the N-(6-CPA) glycine
conjugate. The half-life of 6-CPA in the rat was 2.4 h (Ramsey
et al., 1974).
C-Cl
Cl-^N^S
COOH
CI
6-CPA
N-6-CPA Glycine
IN|-CH2-C00H
H
198
ORYZEMATE [3-Allyloxy-l ,2-benzisothiazole-l ,1-dioxide]
When applied to rice plants, oryzemate was preferentially accumulated
in plant leaves. Acetomitrile extracts of rice shoots showed the
formation of products which were identified as: ally o-Sulfamoylbenzoate,
saccharin and its N^g-D-glucopyranosyl conjugate (Uchiyame et al . ,
1973).
-CH2 -CH=Cn2
Oryzemate
C-0-CH2-CH=CH2
-NH:
Conjugate
199
OXADIAZON [2-tert-Butyl-4-(2,4-dichloro-5-isopropoxypheny1-A2-
1 ,3,4-oxadiazol in-5-one]
11+C-Oxadiazon was applied to submerged soil in which rice plants
(Oryza sativa L. v. kimmaze or v. nihombare) were grown. Once
taken into root tissue, oxadiazon was translocated to shoots and
leaves. Metabolism of oxadiazon in plants involved the side
chain primarily and produced dealkylated metabolites, an alcholol,
and an acid in shoots of seedlings and straws of plants at harvesting.
Most of the radioactivity in the roots, shoots or straws, however,
was unchanged oxadiazon. The metabolites were identified as the
following derivatives:
-4-(2,4-dichloro-5-methoxyphenyl )- (III)
-4-(2,4-dichloro-5-hydroxyphenyl )- (IV)
-4-(2,4-dichloro-5-ethoxyphenyl )- (II)
2-[2-(2-methyl propanoic acid)]-4-(2,4-dichloro-5-hydroxyphenyl )- (V)
2-(2-methylisopropanol)- (I)
A sixth metabolite, wherein the nitrogen ring had been opened, was
also found and identified as l-(2,4-dichloro-5-isopropoxyphenyl )-l-
methoxycarbonyl-2,2-dimethylpropanoylhydrazine (VI) (Hirata and
Ishizuka, 1975; Ishizuka et al . , 1975).
200
CH3
I R2 ■ C-CH20H
CH,
II R1 - C2H50-
III R] - CH30
IV R1 - -OH
V R,
VI
-OH
m3
■C-COOH
\
CH,
H
CH,-C-CH,
3 i 3
Cl-fVfUc'-fcHj
^( H CH,
CI
201
PARATHION [0,0-Diethyl 0-p_-nitrophenyl phosphorothioate]
Mixed function oxidase enzymes metabolized parathion to phosphate and
diethyl phosphorothioate. Desethyl parathion was identified (Wolcott,
1971).
When 35S-parathion was incubated with rabbit and rat hepatic microsomes,
a good portion of the released sulfur in paraoxon formation became bound
to microsomal macromolecules. This was decreased by Cu2+ which is known
to inhibit MFO (Poore and Neal , 1972).
Over 90% of the radioactivity administered to rats as 14C-ethyl parathion
was eliminated within 72 h. In urine, the principal radioactive meta-
bolites of paraoxon were diethyl phosphoric acid and desethyl paraoxon.
Some bound p_-nitrophenol in urine was indicated. In vitro studies with
microsomal enzymes degraded li+C-paraoxon to desethyl paraoxon, diethyl
phosphoric acid, monoethyl phosphoric acid and an amino acid conjugate
of paraoxon. Ethanol and acetaldehyde were also found in small amounts.
When rats were pretreated with microsome inducers, the microsomes
prepared from these rats produced ethanol from the paraoxon. When NADPH
was added to the incubation mixture, paraoxon degrading activity was
greater than without NADPH or with NADH (Ku and Dahm, 1973).
In other studies with rat liver cells, data indicated that the soluble
fractions obtained at 105000xg and 500000xg were primarily responsible
for the degradation of parathion to water-soluble metabolites. Analyses
indicated that aminoparathion was the primary metabolite produced by
soluble cell fractions, followed by paraoxon. Small amounts of p_-nitro-
phenol were also detected. Parathion was reduced to aminoparathion and
oxidized at the same time to paraoxon. The data indicated that paraoxon
was more readily degraded than parathion. It appeared that parathion
and paraoxon were degraded to water-soluble materials primarily by
soluble fractions. Enzymes in the soluble fraction reduced parathion
to aminoparathion. Some oxidation to paraoxon was also affected.
Paraoxon was degraded mostly by particulate-associated enzymes through
hydrolysis to p_-nitrophenol . The largest amounts of water-soluble
metabolites were produced by the soluble fractions which also reduced
paraoxon to aminoparaoxon (Lichtenstein et al . , 1973).
The nature of the serum enzyme catalyzing paraoxon hydrolysis was
partly characterized. The enzyme, paraoxonase, apparently has a single
binding site (Lenz et al . , 1973).
Weanling Holtzman rats, male and female, were injected with parathion.
Cochromatography was used to identify tissue residues as consisting
of diethyl phosphorate (DEPA), diethyl phosphorothioate (DEPTA), paraoxon
and parathion. Whereas liver, kidney, skeletal muscle and plasma
contained residues of all four compounds, only parathion and paraoxon
202
were found in brain and fat tissues. DEPA and DEPTA occurred as the
major metabolites in urine with parathion and paraoxon present as traces
only. Higher paraoxon levels were present in plasma and brain of
weanlings than of adult rats. In vitro studies with liver homogenates
showed that adult male rats possess higher activity than weanlings or
adult females for both the oxidative and hydrolytic metabolic pathways
of parathion (Gagne and Brodeur, 1972).
The comparative metabolism of parathion to p_-nitrophenol in rats and
lobsters was measured j_n vitro. The rate was considerably greater in
rats than in lobsters. No paraoxon could be detected (Carlson, 1973).
Oxidative activation of methyl parathion and ethyl parathion in vitro
by NADP-glucose-6-phosphate-fortified mouse and liver homogenates were
measured. Fish liver homogenates did not differ in their ability to
cleave both parathions to p_-nitrophenol and the respective dialkyl
phosphorothioates. In these studies, enzymatic hydrolysis of the oxygen
analogs was negligible. Fish liver homogenates without added cofactors
degraded less than 10% of methyl parathion and no ethyl parathion.
Addition of GSH increased methyl parathion degradation but did not
enhance ethyl parathion degradation (Benke et al . , 1974). Dearylation
of parathion occurred predominantly via microsomal MFO. In resistant
fish, highest MFO levels correlated with highest parathion tolerance
(Chambers and Yarbrough, 1973).
Parathion was applied to peach trees. Residue analyses showed the
presence of S-ethyl parathion and paraoxon as well as parathion.
Degradation of S-ethyl parathion was very rapid with EC, WP and encap-
sulated parathion formulations (Winterlin et al . , 1975).
After application of parathion to cotton, analyses indicated a constant
increase in photoalteration products. Products found on the foliage
included S-ethyl parathion, S-phenyl parathion, paraoxon and p_-nitro-
phenol (Joiner and Baetcke, 1973).
When parathion was applied to spinach in the field, paraoxon, diethyl
phosphate and p_-nitrophenol residues increased. Aminoparathion, S-ethyl
parathion and ^-phenyl parathion did not increase in percentage of
harvest residues or were undetectable (Archer, 1974). In other studies,
parathion was incubated with spinach homogenate. TLC and gas chroma-
tography were used to demonstrate the presence of parathion, amino-
parathion, hydroxylaminoparathion, and nitrosoparathion. Non-enzymatic
reduction of nitrosoparathion by NADPH to hydroxylaminoparathion was
also demonstrated (Suzuki and Uchiyama, 1975).
In submerged soils, parathion degraded to aminoparathion. In upland
conditions, aminoparathion was not detected. Addition of Flavobacterium
sp. to the soil accelerated decomposition of parathion to p_-nitro-
phenol (Sethunathan and Yoshida, 1973). A bacterium obtained from
203
flooded alluvial soil was identified as a Pseudomonas sp. When this
organism was incubated with parathion, hydrolysis to p_-nitrophenol
occurred within 3 h. Release of nitrite from p_-nitrophenol occurred
within 24 h. A Bacillus sp., also obtained from flooded alluvial soil,
liberated nitrite from p_-nitrophenol but not from parathion (Sethunathan,
1973; Siddaramappa et al . , 1973).
When Rhizobium japonicum and R. meliloti were incubated with parathion,
95% of the parathion was not detectable after 50 h. Degradation
proceeded primarily via aminoparathion which accounted for about 85%
of the initial parathion. Diethyl phosphorothioic acid (DEPTA) accounted
for 10%. The remaining 5% was unreacted parathion. No paraoxon was
detected (Mick, 1969).
Microorganisms from Lake Tomahawk were incubated with parathion. Degra-
dation to aminoparathion occurred under aerobic and anaerobic conditions.
Aminoparathion underwent further degradation aerobically but not under
anaerobic conditions (Graetz, 1970). In some studies, after addition of
methyl parathion to soil, the oxon was identified (Baker and Applegate,
1970).
The persistence of parathion was partially dependent on soil type. In
some soils degradation was rapid and probably through a combination of
hydrolysis and strong microbial activity. In other soils, parathion
loss was slow and attributable to hydrolysis. In Madera sandy loam,
after parathion was added at 200 ppm, aminoparathion was not observed
although parathion residues declined after 10 days. However, with
parathion at 20 ppm in this soil and submerged under water, 3 ppm
aminoparathion was recovered after 7 days (Iwata et al . , 1973). At
exaggerated levels (30000 to 95000 ppm), parathion was applied to field
soil plots as an emulsifiable concentrate or wettable powder. Degrada-
tion was slower than anticipated and persisted at relatively high levels
for 5 years after gross topical contamination with parathion (Wolfe
et al., 1973).
Degradation of parathion proceeded via hydrolysis to p_-nitro phenol and
diethyl phosphorothioate when adsorbed on kaolinites. Ca-kaolinite was
most active (Saltzman et al . , 1974).
After exposure of parathion for 35 days to ultraviolet irradiation,
12 products were identified:
paraoxon
0,S-di ethyl 0-p_-nitrophenyl phosphate
0,0-di ethyl S-p_-nitrophenyl phosphate
p_-nitrophenol
p_-aminophenol
diethyl phenyl phosphate
204
0,0-diethyl O-phenyl phosphorothioate
0-ethyl 0 ,0-bi s (£-ni trophenyl )phosphorothioate
ethyl bis(p_-ni trophenyl phosphate)
diethyl phosphate, free acid
monoethyl phosphate, free acid
phosphate
(Joiner and Baetcke, 1974).
Parathion was dissolved in 80% aqueous ethanol or 80% aqueous tetra-
hydrofuran and irradiated at 2537a. Photolysis in either solvent
produced 0,0,S_- triethyl phosphorothioate as the major product and lesser
amounts of triethyl phosphate, paraoxon, ethanethiol , and p_-nitrophenol .
Photolysis of paraoxon under identical conditions yielded triethyl phosphate
(Grunwell and Erickson, 1973). In other studies, photolysis of parathion
produced 15 products of which 12 were identified and confirmed by infrared
spectroscopy: ethyl paraoxon, S-ethyl parathion, S-phenyl parathion,
p_-aminophenol , diethyl phenyl phosphate, diethyl phenyl phosphorothioate,
ethyl bis(£-ni trophenyl) phosphate, ethyl bis(p_-ni trophenyl )phosphorothioate,
diethyl phosphate and monoethyl phosphate. After application of 14C-
parathion to cotton plants exposed under different environmental conditions,
identification of photo-alteration products after extraction was by thin-
layer chromatography and liquid scintillation spectroscopy: paraoxon,
£-nitrophenol , S_-ethyl parathion and ^-phenyl parathion. As much as
15.4% of the applied ^C-parathion remained after 28 days (Joiner, 1972;
Joiner and Baetcke, 1973).
Sampling of air downwind from a parathion-treated prune orchard revealed
the presence of parathion and paraoxon as well as some p_-nitrophenol
(Woodrow et al . , 1975).
Methyl parathion was incubated with isolated bacteria strains from water
from the Vistula River (Poland) and from municipal sewage. These studies
indicated that degradation of this pesticide was due to Bacillus cereus
and to Bacillus sp. 8. The presence of other organic material apparently
accelerated the biodegradation. Most rapid degradation was observed when
serine, threonine, asparagine, and alanine were present (Maleszewska,
1974).
In other studies, p_-nitrophenol , a metabolite of parathion, in milk was
fed to houseflies. An observed conjugated metabolite behaved like
the glucose-6-phosphate analog of p-nitrophenol (Heenan and Smith, 1965).
205
PCB (Aroclor, Clophen, KC, Kanechlor, Phenoclor) [Polychlorinated
bi phenyl]
Following intravenous administration to rats of 4-chloro, 4,41-dichloro,
2,21,4,5,51-pentachloro- and 2,2i,4,41,5,5Lhexachlorobiphenyl , these
PCBs were initially rapidly removed from blood and stored in liver
and muscle primarily. Redistribution to skin and adipose tissue
followed. Half-lives were calculated for each compound:
Half-life,
h
Bi phenyl
Blood
Liver
Muscle
Skin
Adipose
Feces
4-chloro-
4.7
120.0
4.9
85.6
1.26
68.2
4.78
74.0
0.79
15.7
4,4!-dichloro-
5.25
39.6
6.1
99.2
0.131
35.2
11.4
87.4
5.46
50.6
22.2
2,21,4,5,51-
pentachloro-
0.53
27.7
256.7
0.25
2.8
40.1
193.0
2.23
613.4
43.0
613.0
51.3
389.0
39.2
211.0
2,21,4,41,5,51-
hexachloro-
3.77
27.1
1359.0
2.4
18.3
1308.0
49.0
642.0
Following administration of the PCBs, there was an initial very rapid
phase when part of the dose was removed from the tissue. This was
followed by a much slower rate of removal. The respective decay rates
are summarized (Matthews and Anderson, 1975b).
After intraperitoneal injection of 4-chlorobiphenyl in young male rats,
urine and feces were collected. A mono- and dihydroxychlorobi phenyl
was observed (Hutzinger et al . , 1972a).
When 4-chlorobiphenyl was fed to rats, 4-chloro-4i-hydroxybi phenyl was
obtained (Safe et al . , 1974). In subsequent studies, this metabolite
was administered intraperitoneal ly to rats. Urine and feces were
collected and analyzed. Mass and NMR spectroscopy identified the major
urinary compound as 4i-chloro-3,4-dihydroxybiphenyl . Two other dihydroxy
compounds were observed but could not be separated by chromatographic
procedures. However, demethylation of urinary chloromethoxy analogs
gave only one product, 4i-chloro-3,4-dihydroxybiphenyl . This indicated
that the two components were 4i-chloro-3-methoxy-4-hydroxybiphenyl and
4i-chloro-4-methoxy-3-hydroxybi phenyl . A fourth urinary compound was
identified as 4i-chloro-4-methoxy-3,5-dihydroxybiphenyl . No fecal
metabolites were observed (Safe et al., 1975a).
206
When 4-chlorobiphenyl was administered to rabbits, the compound was
metabolized to 41-chloro-4-hydroxybiphenyl and 41-chloro-3,4-dihydroxy-
biphenyl. The 4-hydroxy compound was metabolized by rabbits to the
3,4-dihydroxy analog and small amounts of 41-chloro-4-hydroxy-3-
methoxybi phenyl and 41-chloro-3-hydroxy-4-methoxybiphenyl . The results
of this study were consistent with the formation of an arene oxide
intermediate (Safe et al . , 1975c).
After intravenous injection of 4-chloro- and 4,41-dichlorobiphenyl
to goats and a cow, urine was collected. After extraction and cleanup
of the urine samples, mass spectrometry was used to identify the
metabolites of 4-chlorobiphenyl as 41-chloro-4-hydroxybiphenyl and
41-chloro-3,4-dihydroxybiphenyl . The 4-chlorobiphenyl was also identified
in urine of cow. Confirmation of metabolite structure identity was made
by NMR spectrometry and by comparison with samples of metabolites
identified in the rat and confirmed by synthesis (Safe et al . , 1975b).
4-Chlorobi phenyl was fed to male albino rabbits. Urine was collected
and analyzed. About 50% of the ingested dose was excreted as a gluco-
siduronic acid derivative. Free phenol accounted for 3% and sulfate
for 11%. No mercapturic acid derivatives were observed (Block and
Cornish, 1959).
When pigeons were fed 4-chlorobiphenyl, a monohydroxylated chloro-
bi phenyl was found. Trout excreted no detectable metabolites into
the water when exposed to 4-chlorobiphenyl (Hutzinger et al . , 1972b
and c).
Thorny skate (Raja radiata) and winter skate (Raja ocellata) were
intravenously administered 2-, 3-, and 4-chlorobiphenyl. The 3-isomer
cleared more readily from plasma than did the other two. Accumulation
varied considerably from fish to fish but was highest in muscle and
liver (Zinck and Addison, 1974).
li+C-Labeled 2,41-dichlorobiphenyl was administered intravenously to
4 female rhesus monkeys. Biological ti^l.l to 2.9 days. An average
of 73.5% of the administered dose was recovered within 14 days. About
70% of the recovered material appeared in urine and 30% in feces.
Blood levels were negligible after 14 days but about 7% of the dose
was in the fatty tissue (Greb et al . , 1973). Metabolites in urine
and feces were identical. About 17% of the metabolites were conjugated
as the sulfate or glucuronide. Three (of six) monohydroxy and three
dihydroxy dichlorobiphenyls formed (Greb et al . , 1975b).
When fed to rats, 4,41-dichlorobiphenyl yielded the 3-hydroxy analog
(Safe et al . , 1974). After intraperitoneal injection of an oil solution
of 4,41-dichlorobiphenyl into young male rats, a monohydroxylated
chlorobiphenyl was observed. Pigeons, when fed the 4,41-compound,
207
gave similar results. Trout did not excrete any metabolite into the
water when fed this material (Hutzinger et al . , 1972b and c). When
this 4,41-dichloro compound was intravenously injected into a goat
and a cow, the 3-hydroxy analog was found in the urine (Safe et al . ,
1975b).
Adult female rats (Swiss Webster strain) were treated with phenobarbital
for 3 days to increase MFO activity. On the fourth day, the animals
were killed and the livers removed and homogenized. The supernatant
from 10,000g centrifugation was centrifuged at 100,000q. The resultant
pellet was used to assay conversion of PCBs. When 2,2*-dichlorobiphenyl
was incubated with the liver enzyme system, four monohydroxy and four
dihydroxy dichlorobiphenyls were found. When 2,41-dichlorobiphenyl was
used, only 2 of 6 monohydroxy derivatives were found. Two dihydroxy-
dichlorobiphenyls also formed. When 2,21,5-trichlorobiphenyl was
incubated with the liver enzyme system, 3 monohydroxy (of seven possible)
and 2-dihydroxy trichlorobiphenyls were produced (Greb et al . , 1975a).
Within 14 days after 2,21,5-trichlorobiphenyl was intravenously admin-
istered to a rhesus monkey, about 82% of the dose was excreted. Urine
and feces contained about equal amounts of radioactivity. The t\, was
2.1 days (Greb et al . , 1973). Three monohydroxy, two dihydroxy and
one tri hydroxy derivative was formed (Greb et al . , 1975b).
2,21,5,51-Tetrachlorobiphenyl in oil was injected intraperitoneal^
into young male rats. A monohydroxy! ated chlorobi phenyl was observed.
A similar observation was made when the compound was fed to fish. Trout
did not metabolize this material (Hutzinger et al . , 1972b and c).
A 1% suspension of 2,4,31,41-tetrachlorobiphenyl in Tween 80-saline
(1:3) was intravenously injected into adult male Wistar King rats.
About 0.6% of the dose was excreted unchanged daily into the gastroin-
testinal tract through the wall of the small intestine (Yoshimura and
Yamamoto, 1975). After oral administration of this 2,4,31,41-isomer
to adult male Wistar strain rats, urine and feces were collected. At
least four phenolic compounds were excreted into feces in addition to
unchanged material. No evidence of conjugated metabolites was obtained.
About 43% of the administered dose was excreted within 12 days after
treatment. Synthesis and spectrophotometric analyses identified the
major metabolite as the 5-hydroxy derivative and the minor metabolite
as the 3-hydroxy derivative (Yamamoto and Yoshimura, 1973; Yoshimura
et al., 1973). '
Tritiated 2 ,5 ,22 ^-tetrachlorobiphenyl was administered to male infant
rhesus monkeys by gastric intubation. At 72 h, the animals were sacri-
ficed. Urine was collected and analyzed. Identification of metabolites
involved IR, GLC-MS and derivatization. Four metabolites were isolated
and identified as a monohydroxytetrachl orobi phenyl , a di hydroxy tetra-
chlorobiphenyl , trans-3,4-dihydro-3,4-dihydroxy-2,5,21 ^-tetrachloro-
biphenyl, and a hydroxylated derivative of the latter with the additional
hydroxy group on the aromatic ring (Hsu et al . , 1975a and b).
208
Sprague-Dawley rats were administered a single dose of 3H-2,5,21,51-
tetrachlorobi phenyl by gastric intubation. Of six metabolites observed,
one from feces was identified as the 3-hydroxy analog by mass and IR
spectra. Three other compounds had mass spectra indicative of mono-
hydroxy analogs also but were not further identified (Van Miller et al . ,
1975).
When rabbits were fed 2,5,21,51-tetrachlorobiphenyl , three hydroxylated
compounds were identified by gas chromatography, mass spectra and IR
spectra. Two compounds were identified as 3- and 4-hydroxy-2,5,21,51-
tetrachl orobi phenyl . The third compound was identified as trans-3,4-
dihydro-S^-dihydroxy-Z.S^^-tetrachlorobiphenyl (Gardner et al . ,
1973).
3,4,31,41-Tetrachlorobiphenyl was administered orally to male Wistar
rats every third day for 9 days. The fecal extract contained three
metabolites. One of these was isolated and identified as either 2- or
S-hydroxy-S^^^-tetrachlorobiphenyl (Yoshimura and Yamamoto, 1973).
Rats, mice and quail were administered 2,2* ,3,5! ,6-pentachlorobiphenyl .
Analyses of collected feces indicated differences in metabolism of this
compound between mammals and birds. Quail excreted the 41-hydroxy
analog as the major monophenol whereas with rats and mice, the major
monophenol excreted was the 5-hydroxy analog. In rat feces, 17 hydroxy-
lated derivatives were observed. Of these, eight were identified as
the following hydroxylated analogs of 2,2* ,3,5* ,6-pentachlorobiphenyl :
S^hydroxy- 31 ,4-dihydroxy-
41-hydroxy- S^-dihydroxy-
4-hydroxy- 4,41-dihydroxy-
5-hydroxy- 41 ,5-dihydroxy-
A resume of the metabolites found in rat feces in this study follows:
Description of bi phenyl No. derivatives
Monohydroxytetrachloro- 3
Monohydroxypentachloro- 7
Dihydroxytetrachloro- 1
Dihydroxypentachloro- 5
(Sundstrom and Jansson, 1975)
A phenolic metabolite of 2,2* ^^^-pentachlorobiphenyl was isolated
from feces of rats given this compound. Mass spectrum, synthesis,
elaborate chemical studies and chromatography showed that the metabo-
lite was the 3!-hydroxy analog (Sundstrom and Wachmeister, 1975).
209
In other studies with ll+C-label ing, single doses were administered
intravenously to rats. Most of the material was excreted in the form
of glucuronides, primarily a 3l-hydroxy or 3 l, 4 i-di hydroxy derivative.
More than 90% of the total dose was removed from the blood within 10 min.
Prior to translocation to skin and adipose tissues, the material was
initially deposited in the liver and muscle. Most of the radioactivity
was excreted in the bile and feces. Excretion in the urine accounted
for less than 7% of the dose and ceased after 8-9 days (Matthews and
Anderson, 1975).
Uniformly lltC-labeled 2,4,5,21,51-pentachlorobiphenyl was administered
intravenously and orally to mice. Autoradiography and scintillation
counting after intravenous administration showed that most radio-
activity left the circulation within 1 h. Peak concentrations were
highest in brown fat. Excretion of radioactivity occurred mainly via
bile with a half-time of six days. During the first 20 min after
injection, in addition to appearing in the fat, radioactivity also
appeared mainly in liver and kidneys. Analyses after oral administration
indicated that the major metabolite was an unidentified monohydroxylated
compound, which occurred free and conjugated (Berlin et al . , 1975).
For five weeks 50 pg of 2,4,6,21,41-pentachlorobiphenyl was adminis-
tered daily to four male and female rats. Urine and feces were collected
daily. Two compounds were isolated but not identified. Mass spectra
indicated a hydroxy and a methoxy derivative (Lay et al . , 1975). In
other studies when labeled material was fed to rats, most of the radio-
activity was found in the feces. The metabolites found in the urine
were conjugated. Monohydroxylation predominated and all three meta-
hydroxy compounds formed. Mo 2- or 4-hydroxybi phenyl was observed
(Goto et al., 1975).
When labeled 2,4,6,21,61-pentachlorobiphenyl was fed to rats, most of
the label appeared in the feces. Metabolites found in the urine were
conjugated. Two m-hydroxy derivatives were found and identified by
mass spectra and gas chromatography. No 2- or 4-hydroxy analogs were
observed. A dihydroxy compound was identified as the 31 ^-dihydroxy
derivative. The main conjugate was identified as the 3-glucuronide
by incubation with g-glucuronidase (Goto et al . , 1975).
Feeding of 2,4,6,31,41-pentachlorobiphenyl to rats yielded the 3-
hydroxy derivative. The Si-analog was not definitely known to be
present (Goto et al . , 1975).
When 2,4,6,3! ^-pentachlorobiphenyl was fed to rats, a trace of the
3-hydroxy derivative was observed (Goto et al . , 1975).
No excreted hydroxylated metabolites were observed after intraperitoneal
injection of 2,21,4,41 ^^-hexachlorobiphenyl in rats, feeding of
pigeons or feeding of trout (Hutzinger et al . , 1972b and c). When this
210
compound was fed to rats, a hydroxy metabolite was found in the feces
but not in urine. Mass spectra data favored the 3-hydroxy structure
(Jensen and Sundstrom, 1974). After feeding this hexachloro compound
to rabbits for 7 days, collected urine was analyzed. Three metabolites
were observed and corresponded to hydroxylation, hydroxylation and mono-
dechlorination, and a monodechlorinated analog that contained a hydroxy
and a methoxy group (Hutzinger et al . , 1974).
Feeding of labeled 2,4,6,21 ,4i,6i-hexachlorobiphenyl to rats yielded
the meta-hydroxy derivative (Goto et al . , 1975).
When fed to rats, decachlorobiphenyl remained unchanged (Goto et al . ,
1975).
Studies of extracts of human fat and animal material indicated that
many PCBs were metabolized (indicated by + in the following table).
Many of the individual PCBs have been identified. In this study,
the products were not identified (Schulte and Acker, 1974).
2,5,2i,5i- +
2,3,4,21
,51
2,3,6,2^
,51
2,4,5,21
,51
2,4,5,21
,31
2,3,4,21
,31
2,3,4,21
,41
2,3,4,5
21,
2,3,5,6
21,
2,3,6,21
,31
2,3,6,21
,41
2,4,5,21
,41
2,3,4,5
21,
2,3,4,5
,21,
2,3,4,5
,21,
2,3,4,5
,6,2
2,3,5,6
,2i,
2,3,4,5
,21,
2,3,5,6
.21,
2,3,4,5
,21,
+
+
+
+
+
+
+
+
+
+
Neg.
Neg.
(+)
Neg.
(+)
Neg.
Neg.
Neg.
Neg.
When rats were fed Aroclor 1016 and 1242, measurable residues were
still present five and six months, respectively, after exposure was
discontinued (Burse et al . , 1974). Studies also indicated that components
of Aroclor 1254 were metabolized at different rates (Grant et al . , 1971).
Twenty-seven PCBs in Aroclors 1221, 1242, and 1254 were separated and
identified by GLC and IR comparison with known prepared compounds
(Webb and McCall , 1972).
,41-
,51-
51-
51-
,61-
,51-
,5i-
3i,4i-
31,61-
41,51
i,5i-
41,51
3i,4i
,51
31,51
,61
3i,5i
,61
211
The main components of Kanechlor-400 (KC-400) were identified as
2,4,31,41-, 2,5,3m1-, 2,3,4,41-, and 3,4,31,41-tetrachlorobiphenyl
and 2,3,4,31,41-pentachlorobiphenyl (Saeki et al . , 1971). Single
doses of KC-400 were orally administered to female DDD strain mice.
The results indicated that each component was almost equally absorbed
and distributed in tissues. Skin concentration of chlorobiphenyls
one day after injection was about twice as high as that of liver and
kidneys; and chlorobiphenyls were retained longer in the skin than in
other tissues. While tetrachlorobi phenyls were almost completely
eliminated from liver and kidney in 3 to 4 weeks, the minor components
penta- and hexachlorobi phenyls were still retained in small amounts
after 9 to 10 weeks (Yoshimura and Oshima, 1971). In other studies
using rats and 3H-labeled KC-400, distribution and excretion radio-
activity was measured at 3, 28 and 56 days. Levels were higher in
skin, adipose tissue, liver, adrenal gland and GI tract than in plasma.
Skin and adipose tissues were highest. Although most of the radio-
activity was eliminated from the tissues after four weeks, a significant
amount was still present after eight weeks. During four weeks of obser-
vation, 2% of the dose was excreted via urine and 70% via feces
(Yoshimura et al . , 1971).
Cows were fed Aroclor 1254 for 60 days. PCB concentrations in milk
fat approached equilibrium after 40 days. After feeding stopped,
the PCB concentration in milk fat declined 50% within 15 days. The
average rate constant was 0.010 day-1 and varied from 0.005 to 0.016
day-1. The decline in body fat concentration of PCB paralleled that
in milk (Fries et al . , 1973).
C = 30.6e"°-32t + 32.3e°-010t
Studies with sheep and pigs yielded the following with Aroclor 1254:
(Blood Concentration) CA = Ae"at + Be-^t
Sheep Pig
a
B
B
VA
(Borchard et al . , 1974)
Aroclor 1254 was fed to bobwhite quail for 14 days. Absorption of
all components occurred at the same rate. Two peaks containing six
chlorines showed a distinct increase but a third peak declined. Some
0.616 ppm
0.465
1 .213 ppm
.537
0.115 ppm
0.047
.252 ppm
.046
284.54
65.60
212
dechlorination occurred but no products were identified (Bagley and
Cromartie, 1973).
Leghorn hens and a rooster were given 50 yg/ml of the PCB mixture
Aroclor 1254. Elimination of PCB isomers was studied. It was found
that 3,4,2! ,3l ^-pentachlorobiphenyl was eliminated more rapidly
than 3,4,21,41,51-pentachlorobiphenyl and 2,3,4,2! .41 ^-hexachloro-
biphenyl. Chlorination in the 4-position in penta- and hexachloro-
bi phenyls was associated with slow clearance of PCB isomers from hen,
embryo, and chick (Bush et al . , 1974).
Fish, exposed to Clophen A50, accumulated residues up to 70 ppm.
When transferred to fresh water, half of the PCB residues was eliminated
in 20 days (Hattula and Karlog, 1973).
Baltic herring (Clupea harengus) were shown to carry high PCB residue
levels. Since the guillemot (Uria algae) and the grey seal (Halichoerus
grypus) feed heavily on the Baltic herring, studies were undertaken to
determine PCB residues in droppings of the guillemot and seal. These
studies showed a difference in the metabolism of PCB and are summarized
in the following table. Compounds were identified by GC-MS (Jansson
et al., 1975).
Compou
inds found
in
the
phenol
ic
fraction
from
feces after me
thylation.
Compound
Number
• of :
Isomers
Seal
Gu-
illemot
Methoxytrichlorobi phenyl 2
Methoxytetrachlorobi phenyl 5 . 6
Methoxypentachlorobi phenyl 9 8
Methoxyhexachlorobi phenyl 7 7
Methoxyheptachlorobi phenyl 2 3
Dimethoxypentachlorobi phenyl - 1
Dimethoxyhexachlorobi phenyl 1 1
Grass shrimp (Palaemonetes pugio) , exposed for 3 months to sediments
contaminated with Aroclor 1254, concentrated the Aroclor to about the
level observed when exposed to 0.09 yg/1 in water for 2 weeks in the
laboratory (Nimmo et al . , 1974).
A laboratory ecosystem used to study the fate of ll+C-labeled PCBs
consisted of water, alga (Oedogonium cardiacum), snail (Physa),
plankton, water flea (Daphnia magna) , mosquito (Culex pipiens
quinquefasciatus) and fish (Gambusia affinis). After introduction
of 2,5,21-trichlorobiphenyl into the system, six compounds were observed:
in water, compounds I, II, IV, V, VI; in alga, compounds I, II, VI;
213
in snail, I through VI; in mosquito, I; and in fish, I and II. When
2,5,2* ^-tetrachlorobiphenyl was introduced, two compounds were observed
in all phases except fish, where only one was found. After introduction
of 2,5,21,41 ^-pentachlorobiphenyl , five compounds were observed in
the system. Compounds II, III, IV, and V in water; I, II, III and V in
alga; I, II and III in mosquito; I, II, III and V in fish; and all five
in snail. All three compounds were biomagnified in all components of
the system. All three compounds were also degraded by the salt marsh
caterpillar larva: five compounds from the trichloro-; three compounds
from the tetrachloro-; and three compounds from pentachlorobiphenyl .
None of the metabolites observed were identified (Metcalf et al . , 1975b).
Two plants, Ranunculus fluitans and Callitriche sp., which grow submerged
in water, were exposed to 2,21-dichlorobiphenyl . In the water where
the plants had been cultured; one di hydroxy compound free and conjugated,
and a dechlorinated product (Moza et al., 1974). 11+C-2,21-Dichloro-
biphenyl was also applied directly to leaves of Veronica beccabunga.
After 6 weeks, the plants were homogenized with methanol and extracted
for 48 h in a Soxhlet. Thin-layer chromatography indicated four
compounds, one of which was conjugated. Mass spectra indicated mono-
methylation of a phenol when it was reacted with diazomethane. A second
compound gave similar results, indicating a second monophenol . These
phenols were also observed after acid hydrolysis of the conjugated
fraction (Moza et al . , 1973).
The soil fungus Rhizopus japonicus was incubated in a medium containing
4-chlorobiphenyl , 56 Mg/30 ml culture medium. A compound having a
melting point of 145C was isolated. NMR and mass spectra were identical
with that of 4-chloro-4-hydroxybi phenyl (Wallnofer et al . , 1973).
4,41-Dichlorobiphenyl was hydroxylated by Rhizopus japonicus. The
metabolite was not identified (Wallnofer et al . , 1973
pomcus.
Two strains of Achromobacter were isolated from sewage effluents using
biphenyl and p_-chlorobi phenyl as sole carbon sources. Achromobacter
BP grew only on biphenyl but did co-metabolize the mono- and dichloro-
bi phenyls. Achromobacter pCB, grown on p_-chl orobi phenyl , grew better
on biphenyl than on £-chl orobi phenyl and co-metabolized meta- and ortho-
chlorobiphenyl and dichlorobiphenyls. Achromobacter pCB metabolized
p_-chl orobi phenyl to benzoic acid and p_-chlorobenzoic acids. The latter
probably arises also from jd^jd1 -dichl orobi phenyl . The two acids were
also produced by Achromobacter BP. Chloride was not produced by either
strain during degradation of the chlorobiphenyls. Washed cell suspensions
of both isolates oxidized biphenyl, o-phenyl phenol, phenyl pyruvate,
catechol, fj-chl orobi phenyl , m-chlorobi phenyl , o-chlorobiphenyl , o,^1- and
p^p^-dichlorobiphenyl (Ahmed and Focht, 1973b). Using resting cell
suspensions of Achromobacter pCB, they were first grown on p_-chl orobi phenyl
Except for 2,5,3* ^-tetrachlorobiphenyl which was not oxidized at all,
214
and S^-dichlorobiphenyl which was oxidized after a brief lag, all
other PCBs tested were oxidized without lag: 2,3-, 2,4-, 3,4- and
3,5-dichlorobiphenyl ; S^^-trichlorobiphenyl ; 2,3,21,31-tetrachloro-
biphenyl; 2,3,4,5,6-pentachlorobiphenyl . Products were not identified
(Ahmed and Focht, 1973a).
In studies with microorganisms, various PCBs were incubated with
Nocardia spp. (NCIB 10603) and Pseudomonas spp. (NCIB 10643) for
varying periods of 7 to 73 days. Nocardia spp. degraded at least 50%
of the following PCBs:
2,41-dichloro- 2,3,21-trichloro-
2,3-dichloro- 2,3,41-trichloro-
3,4-dichloro- S^^-trichloro-
When biphenyl was added to the incubation mixture, 2,5,41-trichloro-
biphenyl was also metabolized. Similarly, a mixture of 2,3,4,5,21,31-
hexachloro-, 2,3,21-trichloro-, and 2.31 ^-trichlorobiphenyl plus
biphenyl was metabolized. Mot metabolized with or without added biphenyl
were 2,4,6-trichloro-, 2,4,21,41-tetrachloro- and 2,4,6,21-tetrachloro-
biphenyl. Pseudomonas spp. metabolized only 2,41-dichloro-, 4,4*-
dichloro, and 2,5,4i-trichlorobiphenyl . Both strains also metabolized
85% or more of Aroclors 1016 and 1242 in 100 days (Baxter et al . , 1975).
Lake bacteria used Aroclor 1221 and 1242, but not 1254, as sole carbon
and energy sources for growth. Aroclor 1221 was completely degraded
into several low molecular weight compounds after one month. Of the
seven bacterial isolates capable of degrading Aroclors, five were
Achromobacter sp. and two were Pseudomonas sp. (Wong and Kaiser, 1975).
In other similar studies with bacteria from Hamilton Harbour, Ontario,
a solution containing 0.1% Aroclor 1242 was incubated at 20C for two
months. After extraction, the metabolites were isolated and identified
by gas chromatography and mass spectrometry. No phenols or chlorine-
containing metabolites were observed. Metabolites identified included:
iso-hexane, iso-octane, ethyl benzene, isobutyl benzene, n-butyl benzene
and iso-nonane (Kaiser and Wong, 1974).
Aroclor 1254 was added to a loam soil at the rate of 10 ppm. After
one year, 95% was recovered. In other soils, 25-50% of some of the
peaks were lost (Iwata et al . , 1973).
Unsymmetrical PCBs were irradiated in quartz with UV above 287 nm.
Mono- and di -dechlorination was observed.
215
Starting bi phenyl
2,4,5-trichloro-
2,4,6-trichloro-
21,3,4-trichloro-
2,3,4,5-tetrachloro-
2,3,5,6-tetrachloro-
Bi phenyl product
4-chloro-
3,4-dichloro-
4-chloro-
2,4-dichloro-
3,4-dichloro-
3,4-dichloro-
3,4,5-trichloro-
3,5-dichloro-
2,3,5-trichloro-
(Ruzo et al., 1975)
With irradiation of PCBs at 300 nm in cyclohexane, stepwise, dechlor-
ination occurred. Where ortho-chlorines were present, PCBs yielded
products arising from loss of the chlorines. The two main products
accounted for more than 98% of PCB reacted. Less than 1% of the
products arose from the loss of a meta-chlorine in the presence of
ortho-chlorine. Para-chlorines were not cleaved after 20 h of irradi-
ation. After more than 50 h of irradiation, S^^^-tetrachloro-
biphenyl yielded some 3,31,4-trichlorobiphenyl in addition to 3,4,4*-
trichlorobiphenyl . In methanol solution, dechlorination was the major
reaction; but some methoxylated products were also observed. In all
cases, these comprised less than 3% of the reacted PCB. Results have
been summarized in the following table (Ruzo et al . , 1972, 1974a and b)
Bi phenyl Products
Biphenyl used
4,41-C12
2,21,5,51-Cl^
2,2i,4,4!-CV
2,2i,3,3i-CV
Dechlorinated
4-C1-
2,3i,5-Cl3-
3,3i-Cl 2-(<l%)
3-C1
2,4,41-C13-
4,4i-Cl2-
4-C1- (<1%)
2,21,3-C13-(<1%)
2,3,31-C13-
S^i-C^
Methoxylated
CI3O Me-
C12(0 Me)2-(<1%)
CI 30 Me- (*)
Cl2 (0 Me)2-(<1%)
CI3O Me-
C12(0 Me)2-(<1«)
♦Main product was 2,4,41-C1 3-21-0CH3-biphenyl
216
3,3i,4,4i-CV 3.4t4*-Cl3- CI 30 Me-(<1%)
3,3i,4-Cl 3
4,4i-Cl2-
3,31,5,51-CK- 3,3i,5-Cl,-(<U)
2,2i,6,6i-Cl, 2,21,6-Clo- Cl30Me-
2,2i-Cl2-(<l%)
Photolysis of 4,41-dichlorobiphenyl with 3100A light in degased 2-
propanol and methanol yielded HC1 and 4-chlorobiphenyl . In other
solvents and in the presence of oxygen, a complex mixture containing
4-chlorobiphenyl was obtained (Nordblom and Miller, 1974).
After photolysis (x>286 nm) of 2,21,4,41,5,51-hexachlorobiphenyl in
methanol in sealed borosilicate tubes for 1 h, about 10% of the biphenyl
reacted to give 3.31 ,4,4 i-tetrachlorob1 phenyl (70%) and 2,31,4,41,5-
pentachlorobi phenyl (30%) (Ruzo and Zabik, 1975).
In other studies the 2,21,4,41,5,51-hexachloro- and 2,21,5,51-tetra-
chlorobi phenyls were adsorbed on silica gel and then exposed to UV
irradiation at x>290 nm. When quartz was used, mineralization occurred
with the hexachlorobiphenyl but not with the tetrachlorobiphenyl (Gab
et al., 1975a).
A sample of 2,21,4,41,6,61-hexachlorobiphenyl in hexane was irradiated
at max 3100a for 100 min. Thin-layer chromatography showed two bands
and gas liquid chromatography revealed 11 major peaks. Mass spectrum
analysis of one band indicated the presence of di-, tri-, tetra-, penta-
and hexa-chlorobiphenyls. Irradiation in methanol produced similar
results but also yielded some more polar material containing oxygenated
polychlorinated compounds (Safe and Hutzinger, 1971).
Chlorinated bi phenyls in a small volume of methanol were suspended
in distilled water. These were then irradiated for 15-26 days in
sunlight or 1-2 weeks in an aerated photoreactor (F40 BL lamp).
GC/MS analyses indicated the formation (about 0.2%) of 2-chloro-
dibenzofuran from 2,5-dichloro- and 2,21,5,51-tetrachlorobiphenyl
(Crosby and Moilanen, 1973).
Product
Test biphenyl
Reduced
2,4-Cl2
-
2,5-Cl2
+
3,4-Cl2
-
4,41-C12
+
2,4,5-CT3
2,21,3,3f-Cl4
-
+
2,21,4,41-C11+
-
Hydroxylated
+
+
+
+
217
PCB (not identified) in 2-propanol and sodium hydroxide was irradiated
with 100 W-high pressure mercury lamp under nitrogen and at about 30C.
PCB was dechlorinated about 80, 95 and 100% after 5, 10 and 15 min,
respectively. Biphenyl and sodium chloride were identified (Nishiwaki
et al., 1972).
The photolysis of chlorobiphenyls was studied under laboratory conditions
and in sunlight. Progressive dechlorination and polymerization occurred
in hexane. In hydroxylic solvents and at pH 9, irradiation of Aroclor
1254 produced compounds corresponding to the addition of water as well
as more polar carboxylic material. When thin films of Aroclors were
photolyzed in the presence of water, the major products were those
resulting from dechlorination and/or polymerization. Polar compounds
having little or no chlorine were also produced. 4,41-di-, 2,2*,5,51-
tetra-, 3,31,4,41-tetra, 2,21,4,41,5,51-hexa-, 2,21,3,31 AAK5,5l-oct<i-
and decachlorobiphenyl were studied (Hutzinger et al . , 1972a and d).
Aroclor 1254 was irradiated in hexane, water and benzene. Products
were not identified; but the increase in size of some peaks indicated
an increase in PCBs with lower molecular weights and shorter retention
times (Herring et al . , 1972).
UV irradiation of hexachlorobiphenyls in rnhexane, acetone, methanol,
or methanol -water produced photolytic products which had lost one to
six chlorine atoms (Hustert and Korte, 1972).
PCBs (KC 300, 400, 600) were chlorinated to decachlorobiphenyl by
reaction with A1C13, S02C12 and S2C12 at 65-70C for an hour (Nose,
1972). At 165C and 3 h and in the presence of antimony pentachloride,
decachlorobiphenyl was produced. If bromine is present, a monobromo-
nonachlorobi phenyl is produced (Huckins et al . , 1974).
Solubility of PCB isomers in water was determined after allowing the
solution to come to equilibrium. After 3 months, monthly measurements
produced reproducable values (Haque and Schmedding, 1975).
Biphenyl Solubility, ppb
2,41-C12
2,21,5-C13
2,21,5,51-Cli+
2,21,4,5,51-C15
2,21,4,41,5,51-C16 0.95 ± 0.01
Recent studies have also shown that PCBs form colored complexes with
montmorillonite clay (Haque and Hansen, 1974 and 1975).
637
+
7
248
+
4
26.
5
+
0.
8
10.
3
+
0.
,2
218
PCN [Chloronaphthalenes]
1-Chloronaphthalene in corn oil was administered by retrocarotid
injection in pigs. Analysis of urine samples showed the presence
of a monohydroxy compound, identified as 4-chloro-l-naphthol , and
a trace of a di hydroxy derivative (Ruzo et al . , 1975).
2-Chloronaphthalene in corn oil was administered by retrocarotid
injection in pigs. Analysis of urine samples showed the presence
of monohydroxy compound, identified as 3-chloro-2-naphthol (Ruzo
et al., 1975).
219
PCNB (Quintozene, Terraclor) [Pentachloronitrobenzene]
Soil samples were collected from greenhouses in which PCNB had
been regularly used. Analyses indicated the presence of:
Pentachloronitrobenzene (PCNB)
Pentachloroaniline (PCA)
Pentachlorothioanisole (PCTA)
Tetrachloronitrobenzene (TCNB)
Tetrachloroaniline (TCA)
Tetrachlorothioanisole (TCTA)
Hexachlorobenzene (HCB)
Pentachlorobenzene (QCB)
Tetrachloronitrobenzene and penta- and hexachlorobenzene occurred
as impurities in the technical PCNB. Analyses indicated the
presence of 2,3,5,6-TCNB. Others have indicated that it is the
2,3,4,5-TCNB isomer that is present as an impurity. However, no
pure 2,3,4,5-TCNB was available to check which isomer was actually
present. Analyses were conducted with GLC, EC-GLC and MS-GLC
(de Vos et al . , 1974).
220
PCP [Pentachlorophenol]
Sprague-Dawley rats and NMRI mice were administered PCP in olive oil
or propylene glycol. Most of the PCP was excreted unchanged. One
metabolite was identified as tetrachlorohydroquinone (TCH). Both
PCP and TCH were present in small amounts as conjugates (Ahlborg
et al., 1974).
The amount of PCP accumulated by goldfish (Carassius auratus) increased
with time. At 0.1 ppm, the concentration factor at 120 h was about
1000; at 0.2 ppm, about 580. Excretion was rapid with active elimination
with half eliminated after 10 h in PCP-free water. Most of the PCP
in the fish had not undergone decomposition. It appeared that most
of PCP transferred to the hepatopancreas was detoxified by sulfate
conjugation or by decomposition. Excretion of PCP was in the form of
a conjugate identified as pentachlorophenyl sulfate (Akitake and
Kobayashi, 1975; Kobayashi and Akitake, 1975a and b).
Photolysis of PCP produced octachlorodibenzo-p_-dioxin and a smaller
amount of the heptachloro analog (Plimmer and Klingebiel, 1973). In
other studies, photolysis of solid PCP in an oxygen stream produced some
C02 and HC1 (Gab et al . , 1975a).
221
PHENMEDIPHAM (Betanal) [Methyl 3- (m-tolyl carbamoyl oxy) phenyl carbamate]
In slightly acid soil of low humus content, phenmedipham decomposed
with a half-life of 28 to 55 days (Kossmann, 1970).
222
PHOSPHAMIDON (Dimecron) [2-Chloro-N,N-diethyl-3-(dimethyl phosphate)
crotonamide]
[11+C] Vinyl -carbonyl-phosphamidon was incubated with mouse liver
fractions. Microsomes and homogenate plus supernatant metabolized
phosphamidon into organosoluble metabolites. When there was pretreat-
ment with dieldrin or phenobarbital , increased conversion of phosphamidon
and its organosoluble metabolites into more polar substances was observed
(Tseng and Menzer, 1974).
223
PICLORAM [4-Amino-3,5,6-trichloropicolinic acid]
When wheat seedlings (Trichicum aestivum L.) were treated with picloram,
water-soluble conjugates not further identified were formed. Similar
results were obtained with rape (Brassica napus L. cv. Nilla) (Hallmen,
1974 and 1975; Hallmen and Eliasson, 1972).
In soil, microbial degradation of picloram underwent a series of reactions
that lead to CO2 and chloride ion. Only the 6-hydroxy analog of picloram
has been observed but it probably is not on the main degradative pathway.
Apparently decarboxylation of picloram is not involved in this degradation
either. A mechanism involving oxidation of the ring was proposed (Meikle
et al., 1974).
The yeast Rhodotorula glutinis (Fres.) Harrison decarboxylated more than
19% of added picloram in less than 28 days when some dextrose was present.
Aspergillus tamarii Kita and Trichoderma sp. also cometabolized picloram
(Rieck, 197077^
Photolysis of picloram followed pseudo first-order kinetics. The half-
life exhibited a straight line relationship vs solution depth (Hedlund
and Youngson, 1972). During photolysis, two chloride ions were produced
per molecule of picloram (Mosier and Guenzi , 1973).
224
IT
OOH
"TADH2 >"
CO.
V"2
V
HOOC ^ XC-C1
«2
N
s
-COOH
HOOC^ yr COOH
\r>
NH„
ci
HOOC
cC ,ci
ft
^
HN^
C-COOH
V
:-cooh
H20
HOO
I
COOH
SI
NH
CH2
"^CH
I
CHO
CO„
^7~
HOOC
CHO
HC1 + CO
225
PIRIMIPHOS-METHYL [0,0- Dimethyl 0-(2-dimethylamino-4-methylpyrimidin-
6-yl )phosphorothionate]
Pirmiphos-methyl was applied to a clean wooden plank upon which a new
cloth-wrapped cheese was placed. Very little pesticide was absorbed by
the cheese and TLC analyses indicated only traces of the oxon and
pyrimidinol derivatives in the wrapping (Thomas and Rowlands, 1975).
226
PROLAN [1 ,l-Bis(p_-chlorophenyl )-2-nitropropane]
14C-Prolan was administered in olive oil orally to mice. Urine and
feces were collected and analyzed. Results of these analyses are
tabulated.
1I+C-Labeled prolan was incubated with a preparation of sheep liver
microsomes. After 30 min incubation at 39C, 99% intact prolan was
recovered. In a comparative study with methoxychlor, about 88% remained
intact. When larva of the salt marsh caterpillar (Estigmene acrea)
ingested 11+C-prolan, 9% degraded to the 2-propanone and acetic acid
analogs. After topical application to the Sn/\idm female housefly
(Musca domestica) , 14C-prolan was degraded to polar compounds which
comprised 83% of the label in excreta and 75% in body homogenates.
In addition to prolan, the acetic acid and benzophenone analogs were
indicated. Conjugation was also indicated by the release of the 2-
amino analog after hydrochloric acid treatment of the polar material.
ite
Mou<
;e
Fly
Salt Marsh
Metabol
Urine
Feces
Caterpillar
I
+
+
+
+
II
+
+
+
III
+
+
+
IV
+
+
+
+
V
+
+
+
VI
+
+
+
+
VII
+
+
+
The degradation and accumulation of prolan in a model ecosystem was
also studied.
Oedo-
gonium
Daphnia
Physa
Culex
Gambusia
Compound
(alga)
(Waterflea)
(Snail)
(Mosquito)
(Fish)
I
+
+
+
+
+
II
+
+
+
+
III
+
+
+
IV
+
+
+
+
V
+
+
VI
+
+
+
VII
+
In all studies, polar conjugated materials were also observed as well
as several unidentified compounds (Hirwe et al . , 1975).
227
R= CI
W A
^CH-CH-N03
ft Eh 3
Prolan I
>CH-CH-NH2
*' in,
II
N
>- ^C=CH-CH3
III
[ pCH-(fH-CH3]
OH
V
COOH
VI
^CH-C-COOH
R/ II
K 0
l\
^CH-C-
CH,
IV
R
\
VII
c=o
228
PRONAMIDE (Kerb) [3,5-Dich1oro-N-(l ,1 -dimethyl -2-propynyl )benzamide]
The metabolism of pronamide in soil was studied with ^C-carbonyl labeling.
It was shown that formation of ll+C02 was biologically mediated. The
treated soils were extracted after 33 days and the extracts were chroma to-
graphed. No 3,5-dichlorobenzoic acid was detected/ In addition to
pronamide and two unidentified metabolites, five metabolites indentified
were compounds I, II, III, VII, and VIII (Fisher, 1974).
CHc
tttH,
-C^CH
Pronamide
I
R-C
IJ-C-CHo
I
1
H3C 0
r
R-C-N-C-C-CH
I - -3
H3
U\
CHq
,-i.
CH,
->-[R-C-N-C-
CH,
C^ 1
XN-C-
0-CH-CH20H
N-C-CH3
tH3
III
H3C OH
-C-N-C-C-CH,0H
VI
H3g o
ii
R-g-N-C-C-CH2OH *- R-C-N-C-C-COOH
0 H
CH
0 rt
:h3
IV
IX
->- R-C-N-C
C-N-C-CH2-CH2OH
{
H3
V
\
C\\:
■I
R-C-N-C-CH2-C00H
Fl
&
:h3
vii
I
H3C OH
->- R-fi-N-C-f H-COOH
Mh3
XII
■>• R-
CH3
•N-C-COOH
^CH3
VIII
R=
229
PROPANIL [3,4-Dichloropropionanilide]
In studies with propanil and 3,4-DCA (3,4-dichloroaniline) , it was
observed that in different soils there were differences in the amount
of tetrachloroazobenzene (TCAB) formed. Formation of TCAB did not
correlate with soil pH. With five soils of pH 4.5 to 5.5, TCAB was
formed from both compounds; pH 5.8 and 7.4, TCAB formed from 3,4-DCA
only; pH 3.4 and 6.4, no TCAB from either substrate (Hughes and Corke,
1974). In soil, the conversion of 3,4-DCA to TCAB increased with an
increase in peroxidase activity (Lay and Ilnicki, 1974).
Propanil was hydrolyzed by Corynebacterium pseudodi phtheri ti cum NCIB
10803 (Grant and Wilson, 1973). A strain of Fusarium solani used propanil
as a sole source of carbon and energy for growths and the primary product
of degradation was 3,4-DCA. This acylamidase did not catalyze hydrolysis
of dicryl , karsil, fenuron, monuron or IPC. It seems to be different
than acylamidases isolated from rice, rat liver and chick kidney (Lanzi-
lotta, 1969). Studies with rice have shown that diazinon and carbaryl ,
absorbed from soil and translocated, could inhibit propanil hydrolysis
(El-Refai and Mowafy, 1973).
230
PROXIMPHAM [0-(N-Phenyl carbamoyl )isopropyloxime]
Hydrolysis of proximpham in acid produced diphenylurea, aniline and
isopropoxime. In alkaline solution, the salt of carbanilic acid and
isopropoxime formed. Model tests of proximpham degradation in soil
indicated a half-life of 7-10 days. In soil, aniline was degraded
much more rapidly than proximpham and was not detected (Spengler and
Jumar, 1969).
231
PYRAZON (Pyramin) [5-Amino-4-chloro-2-phenyl-3(2H)-pyridazinone]
A photochemically controlled process was involved in the degradation
of pyrazon in the leaves of beets. No degradation occurs in the dark.
In sugar beets and red beets, pyrazon formed N-glucosylpyrazone (I).
In addition 5-amino-4-chloro-3(2H)-pyridazinone (II) and a strongly
hydrophilic compound were formed (Anon., BASF 1973; Stephenson et al . ,
1971).
In soil pyrazone is degraded by bacteria with formation of compound II
and is not detectable in soil after 20 weeks (Anon., BASF 1973).
A strain of Azotobacter sp., capable of using pyrazon as a sole source
of carbon, was used to study bacterial decomposition of pyrazon.
Incubation of the bacteria with pyrazon produced 5-amino-4-chloro-2-
(2,3-cis-dihydroxycyclohexa-4,6-diene-1-yl )-3(2H)-pyridazinone (III) ;
2-(5-amino-4-chloro-3-oxo-2,3-dihydro-2-pyridazino-cis,cis-muconic
acid (IV); 2-pyrone-6-carboxylic acid (VII); and 5-amino-4-chloro-
3(2H)-pyridazinone (V) (de Frenne et al . , 1973).
Analogs of pyrazon were co-metabolized by Azotobacter sp. When o-
methyl pyrazon was used, the 2-hydroxymethyl phenyl derivative was
formed and with m-methylparazon, the 3-hydroxymethyl phenyl derivative.
The p_-methyl pyrazon was not metabolized (de Frenne et al . , 1974).
232
Pyrazon
1
NH2
III
H Glucosyl
\ /
N
NH,
> J
CI
VII
233
PYRETHRINS
BIO-ALLETHRIN [3-Allyl-2-methyl-4-oxocyclopent-2-enyl (±)-trans-
chrysanthemate]
BIORESMETHRIN [(±)-trans-resmethrin]
FURAMETHRIN [5-Propargyl -2-furyl methyl (+)-trans-chrysanthemate]
PHENOTHRIN [3-Phenoxybenzyl (+)-trans-chrysanthemate]
RESMETHRIN [5-Benzyl -3-furyl methyl (±)-cis,trans-crysanthemate]
TETRAMETHRIN [3,4,5,6-Tetrahydrophthalimidomethyl (±)-trans-
chrysanthemate]
234
Mouse liver microsomal preparations were capable of hydrolyzing
the ester link of pyrethroids made with primary alcohols. The
enzyme system did not hydrolyze the esters formed with secondary
alcohols. Several relationships were observed.
1. Cleavage of (+)-trans chrysanthemate esters: rate decreased in
order of:
5-propargyl-2-furyl methyl
5-benzyl -3-furyl methyl
3-phenoxybenzyl
tetrahydrophthal imidomethyl
2. Hydrolysis rate of benzyl furyl methyl esters decreased in order
of:
(+)- or (-)-trans chrysanthemate
(+)-trans-ethanochrysanthemate
tetramethyl cycl opropanecarboxyl ate
(+)- or (-)-c is -chrysanthemate or (+)-cis-ethanochrysanthemate
3. Trans- isomers of the above were hydrolyzed up to 50-fold more
rapidly than the c is- isomers.
(Abernathy et al . , 1973)
In other studies, pyrethroids were decomposed in solution by tabu
powder. Decomposition was caused by the prophyrin ring in the
pheophytin in solution (Iguchi et al., 1974).
235
BIOALLETHRIN
Irradiation of a 0.15% solution of a diastereoisomeric mixture of
commercial bioallethrin in rv-hexane produced a single photoproduct in
up to 90% yield. Mass, NMR and IR spectral data were used to identify
the product as corresponding to a rearrangement in the prop-2-enyl
side chain of the alcohol moiety (Bullivant and Pattenden, 1973).
Bioallethrin was not cleaved by esterases in acetone powder preparation
from milkweed bugs, cockroaches (Blattella germanica L.), houseflies,
cabbage loopers (Trichoplusia ni Hubner), yellow meal worms (Tenebrio
molitor L.) or mouse liver (Jao and Casida, 1974).
-COO
236
FURAMETHRIN
Purified furamethrin (I) was heated at 120-140C for 10 h. Chyrsanthemic
acid (II) and an unidentified compound were formed in very small amounts,
At 150C for 8 h, about 0.5% pyrocin (III) and cis-dihydrochrysanthemo-
6-lactone (IV), chrysanthemic acid and an unidentified compound were
formed. At 200C for 7 h, in addition to four unidentified compounds,
chrysanthemic acid and two aldehydes (V and VI) were formed (Abe et al . ,
1974).
CH,-C=CH
->. Polymerization
C00H
II
III
/ \\
-CH0
R-<. J>-CH=CH-CH0
VI
237
PHENOTHRIN (S 2539)
11+C-Phenothrin, labeled at the hydroxymethyl group of the alcohol moiety,
was orally administered at the rate of 200 mg/kg to male Sprague-Dawley
rats. Absorption and elimination was rapid. About 60% of the radio-
activity was eliminated in urine and 40% in feces in 3 days. In addition
to phenothrin, 3-phenoxybenzyl alcohol and 3-phenoxybenzoic acid were
found in brain, liver, kidney and blood. Unidentified water and ether
solubles were also present. Urine contained low levels of 3-phenoxy-
benzoic acid and its glycine conjugate and some ether and water soluble
material. In addition to these, 3-(4'-hydroxyphenoxy)benzoic acid was
present and accounted for 42.3% of the radioactivity originally applied.
This compound was also the major metabolite in feces but accounted for
only 11.9% of the initially applied radioactivity. In addition to
unchanged phenothrin and unidentified water and ether solubles, feces
contained 3-phenoxybenzoic acid and the glycine- conjugate. 3-Phenoxy-
benzyl alcohol was not observed in urine or feces (Miyamoto et al . ,
1974).
238
RESMETHRIN
Mouse hepatic microsomal esterases cleaved the (+)-trans ester more
rapidly than the (+)-cis_- isomer (Abernathy and Casida, 1973). Acetone
powder preparations of milkweed bugs, cockroaches (Blatella germanica
L.), houseflies, cabbage loopers (Trichoplusia ni Hubner) and yellow
mealworms (Tenebrio molitor L.) also hydrolyzed both (+)-trans- and (+)-
cis-isomers. Of these, the (+)- trans- isomer was cleaved more rapidly
than the (+)-ci_s_- isomer (Jao and Casida, 1974). Other studies indicated
that microsomal esterases were important in hydrolyzing trans- but not
cis-isomers (Ueda et al . , 1975b).
Resmethrin isomers were metabolized in microsome-NADPH systems to the
extent of 95 to 98%. The extent to which trans- and cis-isomers were
metabolized differed. In the presence of NADPH, ester cleavage was
much greater with TEPP-treated microsomes. An oxidative ester cleavage
seemed to be most important with (-)-ci_s_- resmethrin. In the latter case,
alcohol moieties released include unstable compounds and protein-bound
metabolites. Seventeen percent of the initial radiocarbon appeared in
11 ester metabolites (not identified) of (+)-trans-resmethrin. These
were recovered only with TEPP-treated microsomes fortified with NADPH.
Oxidized chrysanthemic acid derivatives (VIII to XXII and XXVI) were
comparatively stable. The metabolites IV and VII were major products
only in the presence of NADPH and the supernatant fraction. Compounds
II, III, V and VI were not isolated (Ueda et al . , 1975b).
Six days after administration of ll+C-resmethrin to rats at a dose of
1 mg/kg, 53-73% was accounted for in urine and feces. Low residue
levels were observed in tissues. In urine, there were almost equal parts
of free and conjugated metabolites. Much of the conjugated material was
released after incubation at pH 5, in buffer, with or without glusulase.
When the aqueous phase was acidified to pH 2, more of the metabolites
were recovered. Differences were observed between the metabolism of
(+)-trans- and (+)-cis-resmethrin. When the alcohol was labeled,
compounds BFCA, a-OH-BFCA and 4'-0H-BFCA were found in urine after
administration of ( + )-trans_- isomer whereas only BFCA was observed after
the (+)-cj_s_- isomer. With the latter, all three compounds were released
by incubation with glusulase but only BFCA and 4'-0H-BFCA were released
when the (+)-trans-isomer was used. After administration of acid labeled
(+)-trans-resmethrin, tE-CDA and t-CA were found in urine. The t-CHA
found probably consisted of t-CHA from both (+)-trans- and (+)-cis-
resmethrin. The (+)-cj_s_- isomer yielded c-CA, cE-CHA, cE-CDA and cZ-CDA
when the acid moiety was labeled (Ueda et al., 1975a).
239
H3(
H3C. /CHs
C
=CH/\
N:H-CH2-c-d' N
CH2 CH-CH
N(K TH2
H3C CH
>QH/\ p
H3C nch-ch2-(;s
Ri
R2
R3
Ru
■CH3
■CH20H
■CHO
-C00H
Resmethrin
BFA- -CD Alcohol
BFA- -CD Aldehyde
BFA- -CD Acid
Ri
R2
R3
R4
-CH3
-CH20H
-CHO
-C00H
CA
CHA
CAA
CDA
HOOC
*J
a-keto BFCA
XXVIII
HOOC
jcxox
OHC-
ULfjO
HOOC-
HOCHf
a-OH-BFA
XXIII
oh
^
H0CH2-
BFA
XXII
OH BFCA
XXV
BFCA
XXVI
a-OH BF Aldehyde
XXIV
^-OH BFCA
XXVII
BFA-Z-CDA
VII
[VI]
[V]
BFA-E-CDA <
IV
t-CA
VIII
t-E-CHA
X
1 +
t-E-CAA -
XI
t-E-CDA
XII
[BFA-E-CD Aldehyde]<-[BFA-E-CD Alcohol ]«f(+)trans- & (+)cis-
Resmethrin (I)
c-E-CHA
XIII
■*- [c-E-CAA]
XIV
I
c-E-CDA
XV
c-CA
IX
I
c-Z-CHA
XVI
It
[c-Z-CAA] -^r
XVII
4
c-Z-CDA
XVIII
t-Z-CHA
XIX
If
-*«-{t-Z-CAA]
XX
I
[t-Z-CDA]
XXI
240
Observed
Acid derivatives J_n Vitro In Vivo
t-CA + +
c-CA + +
tE-CHA + +
tE-CAA + +
tE-CDA + +
cE-CHA + +
cE-CAA +
cE-CDA + +
cZ-CHA + +
cZ-CAA +
cZ-CDA + +
tZ-CHA +
tZ-CAA + ±
tZ-CDA + ±
Alcohol derivatives
BFA-E-CDA +
BFA-Z-CDA +
BFA +
a-OH-BFA +
BFCA + +
a-OH-BFCA +
4'-0H-BFCA +
Photodecomposition of (+)-cis-resmethrin produced cis-chrysanthemic
acid; benzaldehyde; phenylacetic acid; 5-benzyl-5-hydroxy-2-oxo-2,5-
dihydro-3-furylmethyl cis-chrysanthemate and 4-benzyl-5-hydroxy-3-
oxo-cyclopent-1 ,2-enyl methyl cis-chrysanthemate (Ueda et al . , 1974).
Irradiation of the (+)-trans-isomer produced 11 photoproducts. The
major component was trans-chrysanthemic acid. Other compounds observed
included benzaldehyde (VIII); 2-benzyloxy-5-oxo-2,5-dihydro-3-furyl methyl
trans-chrysanthemate (IV); compound III, compound V, benzyl alcohol,
benzoic acid, phenylacetic acid and two epoxyresmethrin isomers (see
following figure) (Ueda et al . , 1974).
241
C C-C-C-0-CH,-C - Cv
" C^ \
° \ / \
o
o-
CH„-C00H
VI
CnAC\ /
r/"c\ K
C C-C-C-0-CH,-C=C
II
0 HO-C fc=0
0
cv c c
oc c
V C-C-C-0-CH,-C=C,
III
0 HO-C' C»0
o
/C=C\A
C C-C-C-0-CH2-C=C
IV
o
CH20H
VII
0-°»
VIII
/
C00H
IX
C C-C-C-0-CH,-OC
1 0=V\"cH2"O
" OH
242
TETRAMETHRIN (Phthal thrin, Neo-Pynamin, NIA 9260, FMC 9260, SP 1103)
The microsomal fraction of rat liver homogenates was incubated with
tetramethrin (I). The major metabolites were chrysanthemumic acid (V)
and tetradydrophthalimide (X). Addition of NADPH2 decreased formation
of compound (X), increased tetramethrin oxidation and produced primarily
the propenol derivative II and the hydroxychrysanthemumic acid VI. Only
a small amount of the hydrolysis product N-hydroxymethyl phthal imide
(IX) was observed. This product went non-enzymatically to compound X.
Minor amounts of compounds III, IV, VII and VIII were also observed
(Suzuki and Miyamoto, 1973).
Studies conducted with homogenates of three strains of houseflies
showed that the major microsomal metabolites were compounds V and X.
Addition of NADPH2 did not affect formation of compound X. Small
amounts of compounds III, IV, VII and VIII were observed. Similar
results were obtained when tetramethrin was applied to flies by injec-
tion (Miyamoto and Suzuki, 1973; Suzuki and Miyamoto, 1974).
Acetone powder preparations of milkweed bugs, cockroaches (Blattella
germanica L.), houseflies, cabbage loopers (Trichoplusia ni Hubner)
and yellow mealworms (Tenebrio molitor L.) hydrolyzed both (+)-trans-
and (+)-cis-isomers of tetramethrin. Of these two isomers, the (+)-
trans-isomer was cleaved more rapidly (Jao and Casida, 1974).
243
H3C >CH3
I
II
III
IV
R=
-CH3
-CH2OH
-CHO
-COOH
/R
Hs^ ch3
0^ /\/CH=C
X-CH-CH X
HOT
H3
V
VI
VII
VIII
■CH3
•CH2OH
-CHO
-COOH
t
->- VI
I
■*- II
■>- VII
t
III
IX
VIII
1
->- IV
244
R-7465 [2-(a-naphthoxy)-l^,N^-diethy1 propionamide]
Labeled R-7465 was applied to roots of tomato plants. Translocation
of the material throughout the leaves occurred within 8 h. Extraction
of the plants and analyses revealed the presence in the organic fraction
of three metabolites identified as: 2-(a-naphthoxy)-N-ethyl propionamide;
2- ( 5-hydroxy-l -naphthoxy ) -N-ethyl propi onami de ; 2- ( 5-hydroxy-l -naphthoxy ) -
N,N-diethyl propionamide; and 1 ,4-naphthoquinone. The aqueous fraction
contained a conjugate of 4-hydroxy R-7465 identified as a hexose con-
jugate. Two other compounds, which gave positive glycoside tests, were
identified as different hexose conjugates of 4-hydroxy R-7465 and a
hexose conjugate of the monodesethyl 4-hydroxy R-7465. The 5-hydroxy
R-7465 and its desethyl analog were also present in small amounts after
enzymatic hydrolysis of the conjugates. However, the sources of these
two compounds after hydrolysis were unresolved (Murphy et al . , 1973).
245
?Conj.
C 0 Et
i u I
Q-C-C-N-Et
?Conj.
C 0 H
i ii •
O-C-C-N-Et
4- HO- Con j.
(hexose-2)
C 0 H
« ' » >
O-C-C-N-Et
OH
4-HO-N-desethy?
Naphthoquinone
246
RQBENZ (Robenidine hydrochloride) [1 ,3-Bis(p_-chlorobenzylideneamino)
guanidine hydrochloride]
Carbonyl-1I+C-labeled robenz was administered as a single dose to rats.
A small amount was converted to C02. The major urinary metabolite
(88%) was identified as p_-chlorohippuric acid. A minor metabolite,
about 2% of urinary radioactivity, was identified as p_-chlorobenzoic
acid. About 12 other unidentified materials were also present. More
than 60% of the radioactivity in feces was unreacted robenz. Liver,
kidney and muscle contained p_-chlorohippuric acid, £-chlorobenzoic
acid and robenz (Zulalian and Gatterdam, 1973).
Chickens were administered robenidine (I) ll*C-labeled in the a-carbon
of p_-chlorobenzylidene or in the aminoguanidine carbon. Within 24 h,
82% of the label had been excreted, mostly as unchanged robenidine.
After solvent extraction, column chromatography and mass spectral
analyses, the metabolites were identified as p_-chlorobenzoic acid (II),
3-amino-4-(p-chlorobenzylideneamino)-5-(p_-chlorophenyl )-(4H)-l ,2,4-
triazole (X), and compounds III to IX (Zulalian et al . , 1975).
247
cl"{3"CH=N"NHi"NH"N=CH'(~^cl — ►• C1,CV^
II II
NHHC1 *-* ' *-f\)
Robenz (I)
IUhQ
(X)
oO< — * Q<-—<X
(id /
\ /
Ornithine & Lysine Conjugates Ornithine
Conjugates
H2N-CH2-CH2-CH2-CH-C^ H2N-CH,-CH2-CH2-CH,-CH-(/
NH2 >>H 2222 ^ ^
Ornithine lvsinP
N2 N5 N2 N,
VI
""• "OC ""Ok"
V
248
ROTENONE
Rotenone is stable in the solid state but degradation is accelerated
by the presence of organic solvents. Air and light are required (Cahn
et al . , 1945). The rate of decomposition varies with solvents, temper-
ature and access of air. Decomposition produced the yellow crystalline
dehydrorotenone and rotenonone and a complex mixture of other oxidation
products of rotenone (Jones and Haller, 1931).
249
S-1358 [S-n_-Butyl S'-(p-tert-butyl benzyl )-N-3-pyridyldithiocarbon-
i mi date]
Male Sprague-Dawley rats were intubated with an aqueous suspension of
labeled S-1358 in 10% Tween 80. Excretion of radioact-vity was almost
complete within 4 days. Depending on the dose level, 36 to 43% was
excreted in urine and 54 to 57% in feces. After separation of meta-
bolites by TLC, identification procedures included the use of NMR,
IR, MS and derivatization:
I. S-n-butyl S/-(p_-2-methyl isopropanol ) benzyl P[-3-pyridyldithio-
carbonimidate
II. 3-aminopyridine
III. 2-(3'-pyridylimino)-4-carboxythiazolidine
IV. 4-(2-methyl isopropanol )benzyl methylsulfide
V. 4-(2-methyl isopropanol jbenzyl methyl sulfone.
VI. 4-[2-(2-methylpropanoic acid)]benzyl methylsulfide
VII. 4-[2-(2-methylpropanoic acid)]benzyl methylsulfone
VIII. bi s (p-tert-butyl benzyl disulfide)
IX. S- (p-tert-butyl benzyl )N-3-pyridyldithiocarbamate
Urine contained metabolites I, IV, V, VI and VII. The latter four
were also present probably as glucuronide conjugates. Feces also
contained metabolites I, II, IV, V, VI and VII. Analysis of bile
indicated the presence of compounds IV, V, VI and VII both free and
as glucuronides, metabolite I free and conjugated, metabolites VIII
and IX. In each case, there was also some unidentified material
(Ohkawa et al . , 1975).
250
CH^ CH,
™>{yyy> ^v^^Ot-
VIII ^ IX
/
^-CH2-CH2-CH2-CH3
11 S-1358 3
X I
/S-CH2-CH2-CH2-CH3
| V-CH-COOH "*— ] \ /=\ I
GLUC.
Ill i
CH.
CH3
CH,
=nSH
ch>-s-c^O"["cH2°h — *■ ch'_s"ch'Oi"
COOH
CH.
IV VI.
/ \ / \
GLUC. [Sulfoxide] [Sulfoxide] GLUC.
9 _ ?H3 P CH,
CH3 0 CH,
'2-Oi"cH2°H — *■ cH4cHfO"i"
CH3-S-CH2-<\ /K-CH20H ►" CH,-S-CH^V >C-C0OH
v X / vii
GLUC. GLUC.
251
SALITHION [2-Methoxy-(4H)-l ,3,2-benzodioxaphosphorin-2-sulfide]
After oral administration of 32P-salithion to mice, analyses indicated
that this material was rapidly degraded and excreted. In houseflies,
salithion persisted for a comparatively long time. Analysis of the
chloroform-soluble fraction of houseflies indicated the presence only
of the oxo analog (Ohkawa et al . , 1970).
252
SAN-6706 [4-Chloro-5-dimethylamino-2-(a,a,a-trifluoro-m-tolyl)-3(2H)-
pyridazinone]
SAN-9789 (Norflurazone) [4-Chloro-5-methylamino-2-(a,a,a-trifluoro-
m-tolyl-3(2H)-pyridazinone]
Both compounds were readily absorbed from nutrient solution by cotton
(Gossypium hirsutum L. "Coker 203"), corn (Zea mays L. "WF9") and
soybean (Glycine max (L.) Merr. "Lee") plants. In corn and soybean
plants, these compounds were translocated more rapidly and in greater
amount than in cotton. SAN-6706 was not degraded to any great extent
in cotton. In corn and soybean, significant amounts of the mono- and
des-methyl derivatives were seen after 24 h. Metabolism of SAN-9789
also was more rapid in corn and soybean than in cotton (Strang and
Rogers, 1974).
253
SUMITHION (Fenitrothion, Accothion) [0,0-Dimethyl 0-(3-methyl-4-
nitrophenyl )phosphorothioate]
Labeled sumithion was applied to apple tree. After 21 days, nearly
86% of the residue on the apple surface was sumithion. In the tissues
degradation was more rapid, and approximately 45% of the radioactive
carbon was in the form of degradation products. In addition to sumioxon,
the S-methyl isomer of sumithion, p_-nitrocresol and its 3-glucoside,
and desmethyl sumithion were also found. The latter product was detected
only in fruit harvested on the 21st day (Hosokawa and Miyamoto, 1974).
Irradiation of sumithion in various solvents produced considerable
photodecomposition rate variations.
Solvent/Surface
Product
Bean
leaves
Water
Acetone
1*
2*
+ sunlight
Carboxysumithion
+
+
+
+
+
Methyl parathion
+
Sumioxon
+
+
+
+
+
Carboxysumioxon
+
+
+
3-methyl -4-ni trophenol
+
+
+
+
+
3-carboxy-4-ni trophenol
+
+
+
+
Sumithion S- isomer
+
C02
+
Unknowns
+
+
+
+
+
(Ohkawa et al . , 1974b)
1* Silica gel chroma topi ates + UV
2* Silica gel chromatoplates + sunlight
Solvent
Half-life (min)
Air
Nitrogen
Water
50% Aq. CH30H
Acetone
CH3OH
Benzene
<5
<5
20
60
50
100
100
>240
>360
>360
(Ohkawa et al .
, 19741
Sumithion can isomerize to the S_-methyl analog. The latter is a more
potent cholinesterase inhibitor. The I50 varied from 2.34 x 10"5
(human blood serum) to 1.47 x 10"6 for fly head for sumithion and 9.04 x
10"8 to 5.26 x 10"9, respectively, for S-methyl sumithion. The hydrolysis
rate was also determined at pH 10.99 and 25C: KHyd(min_1) for sumithion
= 3.54 x 10_l+ and for S-methyl sumithion = 2.96 x 10"1 (Kovacicova et al . ,
1973).
254
[Methoxy-ll+C]sumithion was used to assay glutathione-dependent demethyl-
ation. Results of these studies indicated the presence of a glutathione-
dependent enzymatic breakdown of sumithion in both Heliothis zea and
Heliothis virescens but was lower in the latter (Plapp, 1973).
Sumithion has been used over a period of years for spruce budworm
control. Some studies have shown that, although 70-85% of the initial
dose deposited on trees was lost within two weeks after spraying, about
10% persists for at least 10 months. In view of these findings, a
survey was made to check residue accumulations in areas of N.B., Canada,
which had been treated for up to 5 consecutive years. No measurable
amounts of sumithion or known breakdown products were found in any
tested soils. Balsam fir foliage contained measurable year-end residues
but no major breakdown products. Total residues appeared to have
accumulated in foliage in relation to dosage and number of applications.
Maximum residue observed was 1 ppm sumithion in Spring 1973 in fresh
balsam fir foliage (Yule, 1973 and 1974; Yule and Duffy, 1972).
255
TERBUFOS (Counter) [0,0-Diethyl S-(tert-butylthiomethyl )phosphoro-
dithioate]
In soil, terbufos exhibited a half-life of 4 to 5 days. The sulfoxide
formed by oxidation reached a maximum at about 14 days. The sulfone
appeared one week after the start of incubation of soil with terbufos.
Some other compounds observed in less than 1% amounts were the
thiolophosphate, thiolophosphate sulfoxide and the thiolophosphate
sulfone (Laveglia and Dahm, 1975).
256
TFM [4-Nitro-3-trifluoromethyl phenol]
When rainbow trout were exposed in vivo to 11+C-labeled TFM, only the
glucuronide conjugate was detected and was excreted primarily in bile.
The highest glucuronide levels were found in liver (Lech, 1972 and
1973: Lech and Costrini, 1972). Coho salmon exposed to TFM excreted
about 35 times more conjugated than free TFM in a 24-h study period
(Hunn and Allen, 1975a).
When rainbow trout were exposed to 5 mg/1 solution of TFM, the concen-
tration of free TFM in gallbladder bile rose to 4.12 yg/ml after 2 h
and the TFM glucuronide rose to 196 yg/ml . Plasma concentration of
TFM was 2.73 yg/ml and of TFM glucuronide, 0.87 yg/1 (Hunn and Allen,
1974). Within 24 h after transfer to fresh water, TFM disappearance
from the fish plasma was complete. Concentration of free TFM in the
bile remains stable during 12 h of withdrawal but the conjugated TFM
concentrations rise. Then, between 12 and 24 h of withdrawal, the
levels of both declined (Hunn and Allen, 1975b).
Chironomid larvae (Chironomus tentans Fabricius) were exposed to TFM.
TFM accumulation from water was dependent on concentration and water
hardness. The half-life varied from 3.6 to 15.3 h. Analyses of homo-
genates of exposed larvae indicated the presence of TFM glucuronide
and sulfate as well as another conjugate which was hydrolyzed by
0.25M HC1 and 0.25M NaOH but not by g-glucuronidase or by sulfatase.
RTFM was also observed (Kawatski and Bittner, 1975). In other in
vitro studies, all fish tissue homogenates (except trout brain) produced
metabolites. Except bluegill liver, all homogenates produced TFM
glucuronide (Kawatski and McDonald, 1974).
When rainbow trout were pre-exposed to sal icyl amide, TFM toxicity was
increased; blood levels of TFM increased and TFM glucuronide decreased.
The half-life of i.p. administered TFM was increased from 1.59 to
4.13 h (Lech, 1974). Administration of novobiocin produced similar
effects (Lech et al . , 1973). Administration of salicylamide to the
sea lamprey did not increase TFM toxicity. ' In vitro studies indicated
lower glucuronyl transferase than in rainbow trout and in vivo studies
showed a higher free to conjugated TFM ratio in sea lamprey than in
trout (Lech and Statham, 1975).
Studies were conducted with li+C-TFM in a model stream community.
Uptake and accumulation by several plant and animal components was
basically an adsorption phenomenon consisting of a rapid initial
uptake and then a reduced linear uptake phase. Elimination of TFM
accumulations was rapid: in riffle dwelling species, an average
half-life of 17.8 h; in pool-dwelling species, 140 h (Maki , 1974).
257
Scud (Gammarus pseudolimnaeus) concentrated TFM by a factor of about
58 in 7 days. After being transferred to TFM-free water, they elim-
inated half of the accumulated TFM in 3.5 days and 98% after 14 days
(Sanders and Walsh, 1975).
When TFM was
was released.
incubated with isolates from river muds, some fluoride
The organisms seemed to be Pseudomonas sp. Although
cultures degraded TFM somewhat, isolates were unable to do so (Kempe,
1973).
TFM was exposed to sunlight and to UV lamp. TFM half-life in aqueous
solution exposed to sunlgith was about 100 h; on silica gel plates,
71 h. A number of degradation products were observed. One chroma-
tographed the same as RTFM. None were identified (Dawson, 1973).
OH
OH
Microorganism
-»-
no
TFM
Rat, Trout liver
& kidney prep.
CF,
NH?
RTFM
Trout liver
&
kidney prep,
OH
Rat
Trout
Rat
Trout liver
& kidney prep.
Glucuronide
Glucuronide
258
THIABENDAZOLE (TBZ) [2-(4*-thiazolyl )benzimidazole]
14C- and 35S-labeled thiabendazole was orally administered to sheep.
Within 96 h, sheep excreted 75% of the dose via urine and 14% in feces.
Chromatography indicated that nearly all of the radioactivity was in
the form of metabolites. Residues were distributed throughout most
body tissues initially. 35S was detectable in only a few tissues at
less than 0.2 ppm by the 16th day and 0.06 ppm or less after 30 days.
The metabolites were identified as the 5-hydroxy analog and the sulfate
and glucuronide esters (Tocco et al . , 1964).
In pepper plants, thiabendazole (TBZ) accumulated only in the leaves.
Disappearance of TBZ from the leaves exceeded that of methyl -2-
benzimidazolecarbamate (MBC) by three to fourfold. 2-Aminobenzimidazole,
a degradation product of MBC, was also present at levels up to 2% of
the parent compound (Ben-Aziz and Aharonson, 1974).
^C-Thiabendazole was sprayed on sugar beet leaves. The plants were
grown for 34 days under incandescent and fluorescent illumination.
Analyses accounted for 97-98% of the radioactivity as unchanged
thiabendazole. When treated beet leaves were exposed to sunlight
for the equivalent of 14 8-hr days, only 78% of the radioactivity
was present as unchanged thiabendazole. The remainder appeared to
be photoproducts. In addition to benzimidazole-2-carboxamide,
benzimidazole and polar and polymer products were formed. When photo-
lysis was conducted on glass plates, benzimidazole-2-carboxamide and
benzimidazole were observed (Jacob et al . , 1975).
Thiabendazole was not metabolized by potatoes or cotton (Tisdale and
Lord, 1973).
259
THIOLCARBAMATES
BENTHIOCARB [S- (4-Chl orobenzyl ) -N ,N-di ethyl thiol carbamate]
BUTYLATE [S-Ethyl-N,N-(di-2-methyl propyl ) thiol carbamate]
CYCLOATE [S-Ethyl-N-ethyl-N-cyclohexyl thiol carbamate]
DIALLATE [S- ( 2 , 3-Di chl oroal lyl ) -N ,N-di i sopropyl thiol carbamate]
EPTC [^-Ethyl-N,N-dipropylthiolcarbamate]
MOLINATE [S-Ethyl-N,N-hexamethylenethiol carbamate]
PEBULATE [S-Propyl -N-butyl -N-ethyl thiol carbamate]
TRIALLATE [S- ( 2 ,3 ,3-Tri chl oroal lyl -N ,N-di i sopropyl thiol carbamate]
VERMOLATE [S-Propyl-N,N-di propyl thiol carbamate]
Thiocarbamates are detected in the liver of mice 20 min after i.p.
treatment with EPTC, molinate, pebulate, and vernolate at 1 m mole/ kg
but not after administration of benthiocarb, butyl ate, or cycloate
(Casida et al . , 1974).
260
EPTC
(Eptam)
1,2,3,4
Pebulate
(Tillam)
1,2,3
Benthiocarb
(Saturn)
1
Butyl ate
(Sutan)
1,5
Cycloate
(Ro-Neet)
1
Molinate
(Ordram)
1,2
Vernolate
(Vernam)
1,2
♦Formed with
DEGRADATION PRODUCTS*
Sulfoxide Sulfone C02 EtS02-CH3 N-depropyl
2 2 2 1
1. Mouse liver microsome - NADPH system
2. Living mice
3. Photolysis
4. Corn
5. Soil
After oxidation to the sulfoxide, cleavage by the GSH-S-transferase
system occurred with EPTC and pebulate. Mercaptans were released.
(Casida et al . , 1974 and 1975)
261
BENTHIOCARB (Saturn) [4-Chlorobenzyl N,N-diethylthiol carbamate]
The fate of lltC- labeled benthiocarb was studied with white mice in
vivo and in vitro. After oral administration, benthiocarb was
rapidly translocated into organs. There was rapid urinary excretion
of labeled material; slight excretion in feces; and only a little
expired. The major metabolites identified were: 4-chlorohippuric
acid, 4-chlorobenzoic acid, glucuronide of 4-chlorobenzoic acid, and
4-chlorobenzyl alcohol. In liver homogenates, the microsomal fraction
exhibited highest activity and NADP accelerated the degradation. In
vitro metabolites were identified as: N-desethyl benthiocarb, bis(4-
chlorobenzyl )mono- and di-sul fides, and 4-chlorobenzoic acid
(Ishikawa et al . , 1973).
11+C-Benzyl methylene labeled benthiocarb was taken up through the
roots and translocated into whole plants by rice, barnyard grass,
wild amaranth, smartweed, and lambsquarters plants. It was trans-
located from a leaf into other leaves also. When applied to seeds,
it was rapidly absorbed and accumulated mostly in the embryo. The
plants degraded benthiocarb rapidly. No metabolites were identified
(Nakamura et al . , 1974).
262
0
II
Cl\ />-CH2-S-C-N-(C2H5)2
C1-<C /VcH2-S-C-^-C2H5
CI
< ci^Qh
CH2-S-C-NH
CH2),S
CH2)2S2
: Vv A -cho
Cl-^ yO-CH20-Glu.
O
ci-A A-cooh
Cl/ \-COO-Glu.
1U-<
Cl
0 H
//-C-li-CH -COOH
// 2
263
PEBULATE (Till am) [S-Propyl butyl ethyl thiocarbamate]
When tobacco seedlings (Nicotiana tobacum L. Kentucky 14) were incubated
in nutrient solution with pebulate-ll*C, in the roots the concentration
of pebulate reached a maximum 1 day after treatment and decreased after
5 days of treatment. Very little pebulate accumulated in the shoots.
The data indicated very rapid metabolism of pebulate after it was
within the plant and incorporation into plant constituents. No meta-
bolites were identified (Long et al., 1974b).
264
TIBA [2,3,5-Triiodobenzoic acid]
11+C-Carboxy-labeled TIBA was applied to soybeans at the beginning of
the flowering stage. Residue analyses indicated the presence of
conjugates in addition to 2,5-diiodobenzoic acid (2,5-DIBA) and 3,5-
diiodobenzoic acid (3,5-DIBA). Seeda also contained conjugates of
TIBA and 3,5-DIBA (Spitznagle, 1970).
I I
-C00H
TIBA
I I
COOH
<Q>"cooh
i
2,5-TIBA
COOH
MIBA
COOH
2-OH-MIBA
COOH
3,5-DIBA
COOH
2-0H-3,5-DIBA
265
TIN COMPOUNDS
FENTIN ACETATE [Tri phenyl tin acetate]
When fentin was added to soil, the amount that could be extracted
with methanol decreased with time. Some fentin acetate was adsorbed
to the soil. When [ll+C]triphenyltin acetate was incubated with soil,
50% of the label evolved as lt+C02 in 140 days. In sterile soil, only
0.47% evolved in 60 days. Several Aspergillus sp. were able to degrade
fentin in liquid culture with release of il*C02. A Gram-negative
bacteria was also able to metabolize fentin (Barnes et al . , 1973).
Photochemical degradation of fentin at X>250 produced diphenyltin,
monophenyltin, and inorganic tin (Chapman and Price, 1972; Barnes
et al., 1973).
In distilled water, fentin underwent rapid hydrolysis with formation
of triphenyltin hydroxide (Barnes et al . , 1973).
When rats were exposed p.o. to labeled tin, it was found that 50% of
absorbed tin was excreted within 48 h (Hiles, 1974).
266
TIRPATE (Ent 27696) [2,4-Dimethyl-l ,3-ditholane-2-carboxaldehyde
6- (methyl carbamoyl )oxime]
The half-life of tirpate, when administered to young tobacco plants
(Nicotiana tobacum) in hydroponic culture, was about 8-9 h. ^C-
Tirpate was readily taken up and translocated throughout the shoot
but was not rapidly retranslocated to new young leaves. The initial
metabolite was the sulfoxide. The sulfoxide nitrile was also found.
Identification was by GC-MS. The conjugated materials were not
identified. Some were released by sulfatase or glucosidase. One
material released by sulfatase exhibited an Rf similar to that of
the sulfoxide (Hill and Krieger, 1975).
267
TOXAPHENE (Camphene chlorinated to 67-69% chlorine by weight and an
average C10H8C110 composition)
Technical toxaphene is a complex mixture consisting of at least 175
C10 polychloro compounds (Casida et al . , 1974b; Khalifa et al . , 1974).
Male rats were orally administered 36Cl-toxaphene. Within 9 days
after dosing, the rats excreted over 50% of the administered dose.
About 30% of this was in the urine and 70% in the feces. Although
excretion in feces plateaued early, excretion in urine continued
upward. Ionic chloride was excreted in large amount (Crowder and
Dindal , 1974). Other studies confirm the rapid elimination of chloride
with a half-time of 2 to 3 days. When 14C- toxaphene was used, only
low 11+C-levels were observed in tissues several days after administration.
Similar observations were made after administration of toxicant B from
toxaphene. Urinary and fecal metabolites included CO2, dechlorinated
materials and acidic compounds (Ohsawa et al . , '1 975) . Most of the
36C1 -toxaphene was metabolized before excretion. Less than 1% of the
36C1 in the urine and less than 3% in feces appeared as unmetabolized
toxaphene. Subfractions of toxaphene did not differ greatly (Casida
et al . , 1974a). The only urinary metabolite identified when *6C1-
toxaphene was administered to rats was chloride ion. Tissue residues
were very low when 1UC- toxaphene was used (Casida et al . , 1974c).
The closely related polychlorinated norbornenes were also studied.
Hexachloronorbornene (II) was added to a culture of Clostridum
butyricum. Analyses of the medium showed the presence of compounds
III, IV and V. The pentachloronorbornene VI gave rise to compounds
III and IV. Tetrachloronorbornene (III) gave rise to compound IV
(Schuphan and Ballschmitter, 1972).
Toxaphene was applied to alfalfa, range grass and winter wheat.
Analyses gave no evidence of toxaphene metabolism (Carl in et al . ,
1976).
Toxaphene reacted rapidly with hematin in aqueous media to produce
dechlorinated toxaphene derivatives. About half of the carbon-
chlorine bonds were broken. Toxicant fractions A and B underwent
dechlorination, dehydrochlorination and a combination of both
(Holmstead et al . , 1975).
268
H2 rU
A-S
C^Cl
2,2,5-endo-6-exo-8,9,10
heptachl oronorbornane
(Toxicant B)
I
II
IV
269
TRIAZINES
Ametryne
Atrazine
Bromosimazine
Cyanazine
Cyprazine
Fluorosimazine
Iodoatrazine
Iodopropazine
Iodosimazine
Metribuzin
Prometone
Prometryne
Propazine
Simazine
Simetryne
WL 9385
270
Photodecomposition of symmetrical triazines was found to be dependent
on the nature of the substituent and the solvent. The rate constant
^decreased in the order: I>Br>Cl>F; ethyl > propyl; and methanol >
n-butanol . Decomposition exhibited zero-order rate constants. Materials
tested included:
Ametryne
Atrazine
Bromosimazine
Fluorosimazine
Iodoatrazine
Iodopropazine
Iodosimazine
Prometryne
Propazine
Simazine
Simetryne
(Ruzo et al., 1973)
271
AMETRYNE [2-Ethyl ami no-4-i sopropyl ami no-6-methyl thi o-s_- triazi ne]
In nutrient solution-sugarcane system, ametryne degraded rapidly (90%
in 30 days) to more polar materials. Dealkylated ametryne was the
major product at 20 days. 2-Methylthio-4,6-diamino-s_-triazine and
ammeline formed in substantial amounts by 30 days. When ring-ll+C-
ametryne was applied to sugarcane, some ^C02 was formed. Ametryne
was not metabolized to hydroxyametryne in sugarcane. In addition to
C02> another volatile metabolite was observed but not identified.
In soil, ametryne was degraded through N^-dealkylation and 2-hydroxy-
lation (Goswami, 1972; Goswami and Green, 1974).
272
ATRAZINE [2-Chloro-4-ethylamino-6-isopropylamino-s-triazine]
Canada thistle (Crisium arvense L. ) plants were treated with labeled
atrazine. Analyses indicated that over 90% of the material was present
in the shoot where the atrazine was applied. TLC showed that most
(64%) of the chloroform extracted material was unaltered atrazine;
6%, 2-amino-4-chloro-6-isopropylamino-s-triazine; 5%, 2-amino-4-chloro-
6-ethylamino-s^-triazine; and 25% unidentified. The water-soluble
fraction contained 42% of the lkC in the form of 2-ethyl aminos-hydroxy-
s'isopropyl ami no-s-triazine; 2-amino-4-hydroxy-6-isopropylamino-s^-
triazine; and 2-amino-4-ethylamino-6-hydroxy-s-triazine. About 58%
was unidentified (Burt, 1974).
The degradation of atrazine in submerged soil was measured. When
ring- C-atrazine was used, some lt+C02 evolved. A metabolite, hydroxy-
atrazine, was degraded more rapidly than atrazine by microorganisms.
Products of microbial degradation of atrazine and hydroxyatrazine,
an atrazine metabolite, included the product 2-amino-4-chloro-6-
isopropylamino-s_-triazine. These studies indicated that two pathways
may be simultaneously operative: (1) biological, with dealkylation;
and (2) chemical, with hydrolysis of the halide followed by microbial
degradation (Goswami and Green, 1971).
Atrazine was applied to shoots of fall panicum, Texas panicum (P_.
texanum Buckl . ) , witchgrass (P. capillare L. ) , giant foxtail (Setaria
faberii Herrm.), yellow foxtail (S. glauca L. Beauv.), green foxtail
(S. viridis L. Beauv.), giant green foxtail (S_. viridis var. major
Gaud Posp. ) , robust white foxtail (S^. viridis var. robusta-alba
Schreiber) and robust purple foxtail (S^. viridis var. robusta-purpurea
Schreiber). Analyses of plant extracts indicated the presence of
hydroxyatrazine, monodealkylated hydroxyatrazine, and amino acid or
peptide conjugates (Thompson, 1972).
Further studies were conducted to elucidate the metabolism of atrazine
in sorghum (Sorghum vulgare Pers., N.D. 104). The major pathway was
shown to involve the glutathion conjugate. ' Subsequent reactions
removed the glycine moiety and then glutamic acid in that order.
From the S-cysteine derivative, rearrangement produced the N-analog
t[-(4-ethylamino-6-isopropyl-s_-triazinyl-2)cysteine (VIII) . Addition
of alanine produced the N-lanthionine derivative (IX). Two other
compounds were observed in sorghum for the first time: 2-amino-4-
hydroxy-6-isopropylamino-s-triazine (III) and 2,4-diamino-6-hydroxy-
£-triazine (ammeline) (IVj. The two mono-N-dealkylated products and
ammeline (IV) were observed and one more new metabolite identified
as NUIV-bis(4-ethylamino-6-isopropylamino-s-triazinyl )cystine (X)
(Lamoureux et al . , 1973; Shimabukuro et al . , 1973b).
273
The degradation of atrazine by rat liver preparations was investigated.
Cochromatography with standards was used for identification. These
studies indicated that dealkylation was the predominant reaction and
preceded conjugation with glutathione. Removal of the isopropyl group
apparently occurred more easily than removal of the ethyl group.
However, addition of MADPH to 10800xg supernatant and the microsomal
fraction brought about removal of the second alkyl group to produce
2-chloro-4,6-diamino-s_-triazine (XIV). When GSH as well as NADPH
was added to the mixture, GSH-conjugates were formed with atrazine
and the two mono-N-dealkylated derivatives but not with the diamino
analog. However, when the desethyl or diamino derivatives were used
as substrates, some GSH-conjugate of the diamino derivative was formed
(Dauterman and Muecke, 1974).
In soil, atrazine hydrolysis proceeded with a second-order kinetics
under non-sterile conditions and first-order kinetics under sterile
conditions. Laboratory studies indicated that about half to two-
thirds of applied atrazine was hydrolyzed non-biological ly by soil
samples (Agnihotri, 1971). After application to soil, atrazine
degradation produced both mono-N-dealkyl derivatives and the hydroxy-
atrazine (II) (Sirons et al . , 1973). The major metabolite, hydroxy-
atrazine, probably occurred through non-biological processes. Degra-
dation was greater at pH 5.5 than at pH 7.5 (Best and Weber, 1974).
In the presence of nitrite and acid, atrazine reacts to form an N[-
nitrosamine (NNA). Maximum NNA formation occurs at pH 1 . Thermal
decomposition on GLC produces atrazine (Wolfe et al . , 1975).
274
ti 0 COOH
CH,-CH-N-C-CH,-CH,-CH-NH,
i-Pr
J ' fcOOH
'2 vn2
S-G
N^ N
S-G
H2N^N ])■(
XIII
K ? N H
S-CH2-fH-C00H
X HJJ-CH-CH2SH
,.pr^H/^t i-Pr>^N^tt
.N H
VIII
IV
G-S = Glutathione
275
CYANAZINE [2-Chl oro-4- ( 1 -cyano-1 -methyl ethyl ami no ) -6-ethyl ami no-s_-
triazine]
When applied to soil, cyanazine degraded primarily to des-isopropyl
atrazine. The anticipated amide, the initial hydrolysis product of
the nitrile, was also seen (Sirons et al . , 1973).
Using a system developed by R. Metcalf, 1HC-ring-labeled cyanazine
was introduced into an aquatic model ecosystem. After 35 days, analyses
of the components were conducted. In addition to unchanged cyanazine
(I), N-deethyl cyanazine (II), cyanazine amide (III), f[-deethyl cyanazine
amide (IV), and three unknowns were found in the water. Radioactivity
did not increase in the food chain of algae to mosquitoes to fish (a
decrease from 1.3 to 0.05 ppm was observed), indicating that this
compound does not concentrate through the food chain (Yu et al . , 1975a).
Compound
Organism Found
Algae [Oedogonium cardiacum (Huss.)] Ue
Crab (Uca Minax]~ II, U^ Uc, Ue
Daphnia (Daphnia magna Strauss.) Ue
El odea (Elodea canadensis) Uc, Ue
Mosquito (Culex pi pi ens quinquefasciatus Say) Ue
Fish (Gambusia affinis Baird and Girard) Ue
Snail (not identified)
Ua» Ub, Uc = Three unidentified metabolites
Ue ' = Unextractable 14C
276
CYPRAZINE [2-Chloro-4-cyclopropylamino-6-isopropylamino-s-triazine]
ll+C-Ring-labeled cyprazine (I) was administered by stomach tube to
rats which were sacrificed after 3 days. Feces and urine were collected
daily and pooled. About 98% of the radioactivity was excreted within
72 h. Very little (<0.1%) appeared as ll*C02 and carcass and hide
contained 7.5% of the lkC. Paper, thin-layer and gas chromatography,
derivatization and mass spectral analyses were used to separate and
identify the metabolites. Compounds II to IV were identified and
VI to IX were characterized (Larsen and Bakke, 1975).
i-C3H7NH-
-NH2
-NH2
i-C3H7NH-
i-C3H7NH-
CH3
I
H0-CH2-CH-NH-
-NH2
CH3
HOOC-CH-NH-
CH3
CI- lo-CH-NH-
I.
Cl-
II.
H0-
III.
Cl-
IV.
H0-
V.
Cl-
VI.
Cl-
VII.
Cl-
VIII.
Cl-
H2C— -CH—
-NH
-NH2
-NH2
-NH2
-NH2
-NH2
CH2 CH-
NH-
CH? — CH-
•NH-
CH, — CH-NH- HO-CHo-a
277
METRIBUZIN (BAY-94337, SEMCOR) [4-Amino-6-tert-butyl-3-methylthio-
as-triazin-5(4H)-one]
Metribuzin was added to nutrient solutions in which sugarcane cuttings
of cultivar H50-7209 had been established. After one week, very little
parent material was present in the nutrient solution or plant tissue.
The deaminated product II, the hydrolysis product III, and the diketo
product IV were detected in small amounts. Most of the metribuzin
metabolites present in sugarcane were not identified (Hilton et al . ,
1974).
Preliminary greenhouse studies with metribuzin indicated that soybean
cultivars exhibited different responses to exposure through nutrient
solutions. The major portion of the metabolites was water-soluble.
The "Semmes" and "Coker" cultivars produced primarily 6-tert-butyl-
a£-triazin-3,5-(2H,4H)-dione (IV). The major metabolite from "Bragg"
roots and stems was an N-glucoside conjugate (Smith and Wilkinson,
1974).
The rates of degradation of metribuzin and two analogs were studied.
All three herbicides exhibited pseudo first-order kinetics.
(CH3)
3^3"
(CH3)
3J3'
II
-CH,
(CH3)3-C
N-NH,
(CH3)3-C
278
k x lO"2
tl/2
AEa
R
°C
day"1
(days)
(kcal/mole)
t-butyl
5
20
1.84
1.52
377
46
12.7
35
4.40
16
i -propyl
5
20
2.07
1.50
335
46
13.3
35
4.56
15
cyclohexyl
5
20
2.53
1.75
274
40
10.5
35
4.21
17
(Hyzak and Zimdahl , 1974)
A number of asymmetric triazin-5(4H)-ones were irradiated in carbon
tetrachloride, methanol, benzene and water. Photolysis yielded
essentially identical results in each case. The major product was
identified as the 5-hydroxy triazine. Chromatography and mass spectra
indicated minor products resulting from oxidation and desulfurization.
Compounds tested were the 6-t-butyl , 6-isopropyl and 6-cyclohexyl
analogs. Photolysis produced the following derivatives of these three
compounds:
4-amino-3,5-diketo-
3-hydroxy-5-keto-
5-hydroxy-3-keto-
4-amino-5-keto-
4-azo-5-keto- and
5-hydroxy-as-l ,2,4-triazine.
(Pape and Zabik, 1972)
-NH:
S-CH,
279
PROMETONE [2 ,4-Bi s ( i sopropyl ami no) -6-methoxy-s-triazi ne]
Rats were administered ^C-ring-prometone. Urine was collected and
analyzed and eight metabolites were identified or characterized by mass
spectrometry or trimethylsilyl derivatives. The major metabolites
identified were ammeline (31.5%) and 2,4-diamino-6-methoxy-s_-triazine
(10-14%). Other metabolites included: 2-amino-4-(l-carboxyethylamino)-
6-methoxy-s-triazine; 2-amino-4-(l-carboxyethyl ami no) -6- hydroxy -s-triazine;
2-amino-4-methoxy-6-(2-propan-l-ol)amino-s_-triazine; 2-amino-4-hydroxy-
6-(2-propan-l-ol )amino-s-triazine; and 2-amino-4-hydroxy-6-i sopropyl amino-
s-triazine (Bakke and Price, 1973).
280
PROPAZINE [2,4-Bis(ethylamino)-6-chloro-s_-triazine]
Propazine was applied to six species and varieties of Setaria and
three species of Panicum. In all cases, the hydroxypropazine was
formed (Thompson, 1972).
281
SIMAZINE [2-Chloro-4,6-bis (ethyl amino )-s_-triazine]
Six species and varieties of Setaria and three Panicum species were
exposed to 1I+C-simazine. After absorption, simazine was metabolized
to water-soluble compounds. Hydroxy derivatives were detected but
peptide conjugates apparently were the only major metabolites formed
by each species or variety. Hydroxysimazine was detected by chroma-
tographic analysis (Thompson, 1972).
Simazine was added to a nutrient solution in the presence of citrus
tree roots. Hydroxysimazine was not observed. Monodealkylation was
followed by di-dealkylation of the simazine (Jordan and Jolliffe,
1973).
Simazine was applied three times at the rate of 2.8 kg/ha and five
times at the rate of 5.6 kg/ha. After 12 and IS months, respectively,
the total simazine residue was less than 10% of the annual dose (Clay
and Stott, 1973).
Black walnut (Juglans nigra L. ) and yellowpoplar (Liriodendron
tulipifera L. ) 1-year-old seedlings were placed in nutrient solutions
to which simazine had been added. Analyses after 3 days exposure
showed the presence of simazine and monodealkylated simazine in leaves,
stems and roots. The concentration of the monodealkylated simazine
was greater in the yellowpoplar than in black walnut. Other degradation
products found included 2-chloro-4,6-diamino-s_-triazine, found in
higher concentrations in yellowpoplar than black walnut, and hydroxy-
simazine which was found in yellowpoplar but not in black walnut.
Two other compounds found in both plants were not identified (Wichman
and Byrnes, 1975).
282
WL 9385 [2-Azi do-4- t-butyl ami no-6-ethyl ami no-s_-triazi ne]
In the presence of moisture, in all soils tested, WL 9385 decomposed
with formation of the corresponding 2-amino derivative. The rate
constant is about 1.5 to 2.0 mg/g soil/day with some dependence on
soil pH indicated. The reaction is not of a biological nature. In
the solid state, this herbicide changes from white to yellow-brown
when exposed to daylight or ultraviolet light. A half-life of about
240 h was observed. Decomposition followed first order kinetics
(Barnsley and Gabbott, 1966).
283
TRIDEMORPH (Calixin) [2,6-Dimethyl N-tridecylmorpholine]
After the use of tridemorph on cereals, residues in grain were not
detectable (less than 0.05 ppm) after 48 days. The half-life is
about 5 or 6 days. Tridemorph is almost completely adsorbed from
aqueous solution by soil at pH 6.7 and 7.5. Within 30 days, 80% of
tridemorph added to Limburgerhof soil was degraded. The degradation
was initiated by formation of tridemorph-N-oxide. Carbon dioxide and
2,6-dimethylmorpholine formed subsequently. Tridemorph half-life in
loamy sand soil was about 8 weeks (Anon., BASF 1974).
284
TRIFLURALIM [2,6-Dinitro-N,N-dipropyl-a,a,a-trifluoro-p_-toluidine]
Trifluralin readily decomposed when aqueous solutions were exposed
to sunlight. Under acidic conditions, the main product was 2-amino-
6-nitro-a,a,a-trifluoro-p_-to1uidine (XIII). Under alkaline pH, 2-
ethyl-7-nitro-5-trifluoromethylbenzimidazole (XI) was the main compound
(80%) of the photolytic products. Two other compounds, which were
present under all conditions were identified as 2,3-dihydroxy-2-ethyl-
7-nitro-l-propyl-5-trifluoromethylbenzimidazole (II) and 2-ethyl-7-
nitro-5-trifluoromethylbenzimidazole-3-oxide (VII). These latter two
degraded readily by heat or irradiation. Further irradiation of
compounds II and VII helped elucidate the photolytic degradation of
trifluralin. About 25 compounds were detected; 14 were identified
(Crosby and Leitis, 1973; Leitis and Crosby, 1974). Photolysis of
trifluralin vapor produced II, III, VI, VII, XI, XII, XV and XVI
(Soderquist et al . , 1975).
285
HN t-C-CH
(VIII) 3
HN_ _c-0H 02tKJ\^)
(XV) CH I ||
2 5 HN C-C H
F 2 5
3 (VII)
HN C-CH=CH
286
TRIFORIME (Cela W524) [N,N'-Bis(l-formamido-2,2,2-trichloroethyl )
piperazine]
A soil drench application of triforine was applied to barley plants
in pots. The biological half-life was 9 to 10 days when applied at
the rate of 5 mg/plant but rose to 25 to 26 days with 50 mg. In the
shoots four metabolites were observed. One was identified as piperazine
and another was tentatively identified as N-monoglyoxyl -piperazine
(Bruchhausen and Stiasni, 1973; Fuchs et al . , 1972).
287
URACILS
BROMACIL [5-Bromo-3-sec-butyl -6-methyl uraci 1 ]
Aqueous solutions of bromacil were irradiated 6 days in the laboratory
and for 4 summer months outdoors. In sunlight, a low yield of 5-bromo-
6-methyl uracil was obtained. Laboratory photolysis yielded this
compound also. Other studies indicated the formation of four volatile
substances after irradiation of a 10 ppm aqueous bromacil solution for
6 days. The major product (37%) was 6-methyl uraci 1 . The mass spectrum
of a second compound was identical to that of 5-bromo-6-methyl uraci 1 .
The mass spectra of the two other products were consistent with the
addition of a water molecule to 6-methyl uracil to form 5-hydroxy-6-
methyl-5,6-dihydrouracil and photooxidation of the latter to form
2-hydroxyimidazole (Moilanen and Crosby, 1974).
Of 55 fungal and 73 bacterial cultures isolated from soil, only four
fungi were capable of degrading bromacil. One culture was identified
as Penicillium paraherquei Abe. (Torgeson and Mee, 1967).
Bromacil was incubated in various soils to determine its persistence.
The half -life in flooded soil was 155 days; in flooded soil plus bean
straw, 198 days (Wolf and Martin, 1974).
UREAS
Buturon
Chlorbromuron
Dimilin
Fluometuron
Linuron
Methbenzthiazuron
Monolinuron
Monuron
289
BUTURON [N-(4-Chlorophenyl )-N ' -methyl -N ' -(1 -methyl prop-2-ynyl )urea]
After application of buturon to leaves, no p_-chloroaniline was observed.
Other metabolites less polar than buturon were not demonstrated and
the unextractable material was not characterized (Haque et al . , 1974).
Ultraviolet irradiation of buturon in methanol, methanol /water and
benzene produced dechlorobuturon and ^-phenyl -N' -methyl urea. Highly
polymerized material was also present (Kotzias et al . , 1973).
When buturon was incubated with Rhizopus japonicus, the methyl propynyl
group was lost to form the 1 - (4-chl orophenyl ) -3-methyl urea (Wallnofer
et al., 1973a).
290
CHLORBROMURON [3-(3-Chloro-4-bromophenyl )-l-methoxy-l -methyl urea]
After application of chlorbromuron to corn and pigweed, the desmethyl
and phenyl urea metabolites were present in greater amount than the
desmethoxy and unidentified metabolites (Palm, 1971).
291
DIMILIN (Diflubenzuron, TH 60-40, OMS 1804, PH-6040)
[l-(4-Chlorophenyl )-3-(2,6-difluorobenzoyl )urea]
Dimilin was incubated for 1 h with sheep microsomes. Slightly more
than 99% of the parent compound was unchanged. Metabolites identified
included compounds II, III, V, VI, VII and IX. When the salt marsh
caterpillar, Estigmene acrea, was fed 11+C-labeled dimilin, 99+% of the
parent material was recovered unchanged in both feces and body homo-
genates. Incubation of dimilin with the soil microorganism (Pseudomonas
putida) produced no evidence of degradation. When incubated with soil,
dimilin degradation was very low. Traces of products cochromatographed
with 4-chlorophenylurea (V) and 4-chloroaniline (VI) (Metcalf et al . ,
1975a).
A model ecosystem was constructed and contained water, alga (Oedogonium
cardiacum) , snail (Physa sp.), mosquito larva (Culex pipiens quinque-
fasciatus) , fish (Gambusia affinis), plankton (Daphnia magna), sorghum
(Sorghum "vulgare) and the salt marsh caterpillar (Estigmene acrea).
Fourth instar caterpillars fed on dimilin treated sorghum leaves and
dispersed the material into the aquatic portion of the system. In
addition to those metabolites identified, there were nine unidentified
compounds. No azobenzenes were observed (Metcalf et al . , 1975a).
SYSTEM
Found in Ecosystem
Compou
nd
Sheep
Found
Microsomes
I
+
II
+
III
+
IV
V
+
VI
+
VII
+
VIII
IX
+
Soil Water Alga Snail Mosquito Fish
+ + + + +
+ +
+ + +
+ + + + +
+ + + +
+
+
(Metcalf et al . , 1975a)
Dimilin was irradiated in methanol for 9 h at 254 nm. Some colored
material was produced. TLC analysis showed the presence of 2-difluoro-
benzamide (II), methyl phenyl carbamate (XI), and methyl 4-chlorophenyl-
carbamate (X). In aqueous dioxane, a dark brown solution formed after
4-h irradiation. In addition to compound II, 4-chloroaniline (VI) and
aniline (XII) were found. Cochromatography, IR and mass spectrometry
were used in the identification of these compounds (Metcalf et al . ,
1975a). In other studies, irradiation in methanol produced compounds II,
X, XI and XIII (Ruzo et al . , 1974c).
292
F
VII
i
IX
'^Q^1
VIII
OCN
o°
XIII
293
FLUOMETURON [1 ,1 -Dimethyl -3- (m-trifluoromethyl phenyl )urea]
The metabolism of fluometuron in corn (Zea mays var. Dixie 18) and wheat
(Triticum aestivum var. Wakeland) was studied. In both species, metabolism
involved two-step demethylation and then hydrolysis to the aniline.
Ring hydroxylation was indicated. Further metabolism of the aniline
derivative into numerous metabolites occurred with an indication of
formation of the hydroxyaniline derivative (Neptune, 1970).
Sour orange (Citrus auranthium L.) or sweet lime (C. limetioides Tanaka)
were exposed to 14C-fluometuron. After 4 days, analyses showed the
presence of desmethyl fluometuron, 3-trifluoromethyl phenyl urea, and 3-
trifluoromethylaniline (Menashe and Goren, 1973).
After incubation of fluometuron with Rhizopus japonicus, desmethyl-
fluometuron was observed (Wallnofer et al . , 1973c).
294
LINURON [3-(3,4-Dichlorophenyl)-l-methoxy-1-methylurea]
When linuron was applied to corn or pigweed, the desmethyl and phenyl urea
metabolites were present in larger amounts than the desmethoxy and
unidentified metabolites (Palm, 1971).
Data derived from studies of adsorption of linuron on humic acid,
saturated with Fe3+, Al3+, Cu2+, Zn2+, Ni2+, Ca2+, H+ was found to
be consistent with a physical type of adsorption. Infrared spectro-
scopy showed no coordination of linuron to the cations on humic acid
(Khan and Mazurkewich, 1974).
295
METHBENZTHIAZURON (MBT, Tribunil) [W2-Benzothiazolyl )-l ,3-dimethylurea]
MBT was applied to hydroponic cultures of Triticum vulgare and allium
cepa. Analyses indicated that MBT was metabolized to the 1-hydroxymethyl
analog initially and subsequent loss of the hydroxymethyl group (Pont et
al . , 1974). In other studies with sensitive and resistant plants, MBT
passed rapidly from roots towards leaves where active metabolism seemed
to occur. Metabolites identified include the 3 -hydroxymethyl analog and
its glucoside and the 3-demethylated analog. The 1-OH-methyl analog was
suggested as another metabolite. One other metabolite was characterized
and the structure most compatible with the information was that of a
l,2-bis(MBT) ethane (Collet and Pont, 1974).
296
MONOLINURON (Aresin) [3- (4-chl orophenyl )-l-methoxy-l -methyl urea]
Monolinuron was sprayed on ground waste. After 3 weeks of composting,
the material was extracted and analyzed. Most of the residue was unreacted
monolinuron. About 0.4% was demethyl monolinuron (Muller and Korte,
1975).
Incubation of monolinuron with Rhizopus japonicus produced desmethyl
monolinuron (Wallnofer et al., 1973c).
297
MONURON [3- (4-Chlorophenyl) -1,1 -dimethyl urea]
Young leaves were cut from 2-week-old plants of bean (Phaseolus vulgaris
L. var. Black Valentine) and corn (Zea mays L. var. Batam Cross) and
exposed to carbonyl-11+C-labeled monuron in water. After monuron uptake
by the leaves, analyses showed the presence in both plants of: l-(4-
chlorophenyl )-3-methylurea; 4-chlorophenylurea; an unidentified conjugate:
and 1 ,1 -dimethyl -3-(2-hydroxy-4-chlorophenyl ) urea. Although the conjugates
were not identified, these studies indicated the presence of a monuron-
polypeptide larger than 5000 and three glucose conjugates. The latter
were identified as mono-B-D-glucose conjugates of 2-hydroxy-4-chloro-
phenylurea; l-(2-hydroxy-4-chlorophenyl )-3-methylurea; and 1 ,1-dimethyl-
3-(2-hydroxy-4-chlorophenyl ) urea (Lee and Fang, 1973; Lee et al . , 1973).
Incubation of monuron with Rhizopus japonicus produced l-(4-chlorophenyl )-
3-methylurea (Wallnofer et al . , 1973c).
298
polypeptide complexes
H 0 CH,
CI
OH
CH„
H 0 CH,
A-?-lJ-CH3
ci-v y— n-c-n-ch3
°<5-fi
CH,
, - ^OGl
CI
C-N-CH,
H«H 3
*■ CI
H 0
//
N-C-NH„
T^O-GT
C.-TV-
N-C-NH,
^1=' H 0
299
WARFARIN [3- (a-Acetonyl benzyl )-4-hydroxycoumarin]
In vivo studies with Wistar-derived warfarin susceptible strain (TAS)
rats indicated that warfarin metabolism was the limiting step with
regard to toxicity. Using in vitro studies, 6-, 7-, 8-, and 4'-hydroxy-
warfarins were separated by means of thin-layer and paper chromatography
and identified by mass spectrometry and UV spectra (Townsend et al . ,
1975).
300
ZECTRAN (Mexacarbate) [4-Dimethylamino-3,5-Xylyl N-methyl carbamate]
Bacteria, mold and fungi were screened for their ability to degrade
zectran. All organisms tested were able to metabolize this pesticide.
A bacteria (HF-3) and a fungus (Trichoderma viride) were further
investigated. The major T. viride metabolite was 4-dimethylamino-3,5-
xylenol (DMAX). Methylamino zectran (MAZ) and methyl formami do zectran
(MFZ) were formed by HF-3. Other degradation products identified by
TLC were amino zectran (AZ) and formamido zectran (FZ). Addition of
cofactors and carbon sources altered the metabolic patterns. Decar-
bamylation predominated in the presence of ATP, NADP+ and NADPH;
demethylation, in the presence of NAD+ and FAD. Thus, T. viride could
be induced to degrade zectran via -demethylation of the N-dimethyl
group whereas metabolism of zectran normally proceeds principally via
decarbamylation in this organism (Benezet and Matsumura, 1974).
Irradiation of zectran in cyclohexane or ethanol by a high-pressure
xenon-mercury lamp produced a number of compounds. Three major products
were produced: MAZ, DMAX and 2,6-dimethyl-4-hydroxy-N-methyl benzamide
(HMB) (Silk and Unger, 1973).
A scheme was proposed by Meikle (1973) to explain the gradual flow of
zectran metabolites to water-soluble compounds and other plant substances,
301
\ -g
o +->
3
oj -a
-* o
•r- i.
■— Q.
CT1
/
o
302
BIBLIOGRAPHY
Aaseth, J.
1975. The effect of N-acetyl homocysteine and its thiolactone
on the distribution and excretion of mercury in methyl mercuric
chloride injected mice. Acta Pharmacol. Toxicol., 36(3) : 1 93-202 .
Abe, Y., N. Itaya, Y. Fujita, and N. Muramoto.
1974. Studies on Pyrethroidal Compounds. Part IV. Thermal
Behavior of Furamethrin. Botyu-Kagaku, 39(1):1-10.
Abernathy, CO., and J.E. Casida.
1973. Pyrethroid insecticides: Esterase cleavage in relation
to selective toxicity. Science, 179:1235-1236.
Abernathy, CO., K. Ueda, J.L. Engle, L.C Gaughan, and J.E. Casida.
1973. Substrate-specificity and toxicological significance
of pyrethroid-hydrolyzing esterases of mouse liver microsomes.
Pest. Biochem. Physiol., 3(3):300-311.
Adams, C.H.M., and K. Mackenzie.
1969. Dehalogenation of Isodrin and Aldrin with alkoxide bases.
J. Chem. Soc, (C):480-486.
Addison, J.B., P.J. Silk, and I. Unger.
1974. The photochemical reactions of carbamates. II.
The solution photochemistry of Matacil (4-dimethyl-amino-m-
tolyl-f\[-methyl carbamate) and Landrin (3,4,5-trimethylphenyl-
N-methyl carbamate). Bull. Environ. Contam. Toxicol., 11:250-255.
Agarwal , H.C, and B. Gupta.
1974. Distribution and metabolism of DDT in the catfish
Heteropneustes fossil is in relation to the signs of poisoning.
Toxicol. Appl . Pharmacol., 29:204-209.
Agnihotri , N.P.
1971. Relative biological and non-biological inactivation
of Atrazine in soil. Diss. Abstr., 31B (Pt. 1):7042.
Agosin, M., N. Scaramelli, L. Gil, and M.E. Letelier.
1969. Some properties of the microsomal system metabolizing
DDT in Triatoma infestans. Comp. Biochem. Physiol., 29:785-793.
Aharonson, N., and A. Ben-Aziz.
1973. Determination of residues of Benomyl , its hydrolysis
produce, and Thiabendazole in various crops. J. Assoc. Off.
Anal. Chem., 56(6) :1330-1334.
Aharonson, N., and A. Ben-Aziz.
1974. Persistence of residues of Velsicol VCS-506 and two of
its metabolites in tomatoes and grapes. J. Agric. Food Chem.,
22(4):704-706.
Aharonson, N., and U. Kaf kaf i .
1975. Adsorption of Benzimidazole fungicides on Mont-
morillonite and Kaolinite Clay surfaces. J. Agric. Food Chem.,
23(3):434-437.
Ahlborg, U.G., J.E. Lindgren, and M. Mercier.
1974. Metabolism of Pentachlorophenol . Arch. Toxicol.,
32:271-281.
303
Ahmad, S., and A.J. Forgash.
1975. Metabolism of 11+C-Diazinon by gypsy moth larvae. J. Econ.
Entomol., 68(5) : 571 -576.
Ahmed, M. , and D.D. Focht.
1973a. Oxidation of polychlorinated biphenyls by Achromobacter
pCB. Bull. Environ. Contain. Toxicol., 10(2) :70-72.
Ahmed, M. , and D.D. Focht.
1973b. Degradation of polychlorinated biphenyls by two species
of Achromobacter. Can. J. Microbiol., 19:47-52.
Akagi, H., and E. Takabatake.
1973. Photochemical formation of methyl mercuric compounds from
mercuric acetate. Chemosphere, 3:131-133.
Akagi, H., and E. Takabatake.
1974. Photochemical methylation of inorganic mercury in the
presence of solid sulfur. Chem. Lett. : 761 -764.
Akira, K. , and J.S. Hart.
1974. Uptake of inorganic mercury by bed sediments. J. Environ.
Qual., 3(3):273-278.
Akitake, H., and K. Kobayashi .
1975. Studies on the metabolism of chlorophenols in fish--III.
Isolation and identification of a conjugated PCP excreted by
goldfish. Bull. Jpn. Soc. Sci . Fish., 41 (3) :321-327.
Alberts, J.J., J.E. Schindler, and R.W. Miller.
1974. Elemental mercury evolution mediated by humic acid.
Science, 184:895-897.
Alley, E.G., D.A. Dollar, B.R. Layton, and J. P. Minyard, Jr.
1973. Photochemistry of Mi rex. J. Agric. Food Chem., 21(1):
138-139.
Alley, E.G., B.R. Layton, J. P. Minyard, Jr.
1974a. Identification of the photoproducts of the insecticides
Mirex and Kepone. J. Agric. Food Chem., 22(3) :442-445.
Alley, E.G., B.R. Layton, J. P. Minyard, Jr.
1974b. Photoreduction of Mirex in aliphatic amines. J. Agric.
Food Chem., 22(4) :727-729.
Al-Rubae, A.Y., and CO. Knowles.
1972. Metabolism of chloropropylate and bromopropylate acaricides
by twospotted spider mites and houseflies. J. Econ. Entomol.,
65(6):1600-1603.
Al-Shahristani , H., and K.M. Shihab.
1974. Variation of biological half-life of methylmercury in man.
Arch. Environ. Health, 28:342-344.
Altom, J.D., and J.F. Stritzke.
1973. Degradation of Dicamba, Picloram and four phenoxy herbicides
in soils. Weed Sci., 21 (6) :556-560.
Aly, O.M., and M.A. El-Dib.
1971. Studies on the persistence of some carbamate insecticides
in the aquatic environment-I. Hydrolysis of Sevin, Baygon,
Pyrolan, and Dimetilan in waters. Water Res., 5:1191-1205.
304
Anderson, J.P.E.
1971. Factors influencing insecticide degradation by a soil
fungus, Mucor alternans. Diss. Abstr., 32B. (6) :3414-3415.
Ando, M., T. Nakamura, and M. Makagawa.
1974. Metabolism of Hymexazol , 3-Hydroxy-5-methylisoxazole, in
the rats. Agric. Biol. Chem. , 38(12) :2451-2456.
Ando, M., M. Nakagawa, T. Nakamura, and K. Tomita.
1975. Metabolism of Isoxathion, 0,0-Di ethyl 0-(5-Phenyl-3-
isoxazolyl )phosphorothioate in the rats. Agric. Biol. Chem.,
39(4):803-809.
Andrade, P.S.L., Jr., and W.B. Wheeler.
1974a. Mirex transformation products in the environment.
Abstracts 168th ACS Meeting, Atlantic City, N.J., September 9-13,
PEST 44.
Andrade, P.S.L., Jr., and W.B. Wheeler.
1974b. Biodegradation of Mirex by sewage sludge organisms.
Bull. Environ. Contam. Toxicol., 11 (5) :415-416.
Andrade. P., Jr., W.B. Wheeler, and D.A. Carlson.
1975. Identification of a Mirex metabolite. Bull. Environ.
Contam. Toxicol., 14(4) :473-479.
Andrawes, N.R., and H.W. Dorough.
1970. Metabolism of temik in boll weevils and houseflies. Tex.
Agric. Exp. Stn. Prog. Rep., PR-2833, 1-8.
Andrawes, N.R., R.R. Romine, and W.P. Bagley.
1973. Metabolism and residues of temik aldicarb pesticide in
cotton foliage and seed under field conditions. J. Agric. Food
Chem., 21(3):379-386.
Anon.
1973. Basagran, a new herbicide. Publication of BASF
Aktiengesellschaft, Agricultural Research Station, D 6703
Limburgerhof , GPE/IF, 44 pages.
Anon.
1974. Luprosil. Publication of BASF GPE/IF, Limburgerhof,
47 pages.
Apple, E.J.
1969. The metabolism and detoxification of DDT in mammals.
Diss. Abstr., 29B(10) :3606.
ApSimon, J.W., J. A. Buccini, A.S.Y. Chau.
1974. The acid-catalyzed Wagner-Meerwein rearrangement of
Dieldrin. Tetrahedron. Lett. No. 6:539-542.
Archer, B.L., B.G. Audley, and N.P. Mann.
1973. Decomposition of 2-Chloroethylphosphonic acid in stems
and leaves of Hevea brasiliensis. Phytochemistry, 12:1535-1538.
Archer, T.E.
1973. Endosulfan residues on alfalfa hay exposed to drying by
sunlight, ultraviolet light and air. Pestic. Sci., 4:59-68.
Archer, T.E.
1974a. The effect of ultraviolet radiation filtered through pyrex
glass upon residues of Dicofol (kelthane; 1 ,1 '-bis-(p_-chloro-
phenyl ) 2,2,2-trichloroethanol ) on Apple Pomace. Bull. Environ.
Contam. Toxicol., 12(2) :202-203.
305
Archer, T.E.
1974b. Dissipation of Parathion and related compounds from
field sprayed spinach. J. Agric. Food Chem., 22(6) :974-977.
Arurkar, S.K.
1971. Metabolic and stability studies of Formetanate Acaricide.
Diss. Abstr., 32B(3):1633.
Asai, R.I., F.A. Gunther, and W.E. Westlake.
1974. Influence of some soil characteristics on the dissipation
rate of Landrin insecticide. Bull. Environ. Contam. Toxicol.,
ll(4):352-358.
Atchison, G.J., and H.E. Johnson.
1975. The degradation of DDT in brook trout eggs and fry.
Trans. Am. Fish. Soc, 104(4) :782-784.
Atlas, R.M., and R. Bartha.
1972. Biodegradation of petroleum in seawater at low
temperatures. Can. J. Microbiol., 18(12) :1851-1855.
Audley, B.G., and B.L. Archer.
1973. Decomposition of 2-chloroethylphosphonic acid in aqueous
solution: formation of 2-hydroxyethylphosphonic acid. Chem.
Ind., 634-635.
Avrahami , M.
1975. Hexachlorobenzene. IV. Accumulation and elimination
of HCB in pigs after oral dosing. N.Z. J. Exp. Agric, 3:285-287.
Avrahami, M., and R.T. Steele.
1972a. Hexachlorobenzene. I. Accumulation and elimination
of HCB in sheep after oral dosing. N.Z. J. Agric. Res., 15(3):
476-481 .
Avrahami, M., and R.T. Steele.
1972b. Hexachlorobenzene. II. Residues in laying pullets fed
HCB in their diet and the effects on egg production, egg hatch-
ability, and on chickens. N.Z. J. Agric. Res., 15(3) :482-488.
Ayeke, C.A.
1969. The metabolism of (l-2-Clt+Chloroethyl )trimethyl ammonium
chloride and its nitrogen interaction effects on forage quality
in coastal bermuda-grass (Cynodon dactylon (L) Pers.). Diss.
Abstr., 29B(8):2689.
Azouz, W.M., D.V. Parke, and R.T. Williams.
1954. The metabolism of Dichlorobenzenes. Biochem. J.,
57:XII.
Babiker, A.G.T., and H.J. Duncan.
1975. Mobility and breakdown of Asulam in the soil and the
possible impact on the environment. Biol. Conserv., 8(2):
97-104.
Bagley, G.E., and E. Cromartie.
1973. Elimination pattern of Aroclor 1254 components in the
bobwhite. J. Chromatogr., 75:219-226.
Baker, R.D., and H.G. Applegate.
1970. Effect of temperature and ultraviolet radiation on the
persistence of methyl parathion and DDT in soils. Agron. J.,
62:509-512.
306
Bakke, J.E., and C.E. Prince.
1973. Rat urinary metabolites from 2-Methoxy-4,6-bis(iso-
proplyamino)-s-triazine (Prometone). J. Agric. Food Chem.,
21(4):640-644.
Balba, M.H., and J.G. Sana.
1974a. Metabolism of Lindane-14 by wheat plants grown from
treated seed. Environ. Lett., 7(3) : 181 -1 94.
Balba, M.H., and J.G. Saha.
1974b. Degradation of Matacil by the ascorbic acid oxidation
system. Bull. Environ. Contam. Toxicol., 1 1 (2) : 193-200.
Baldwin, M.K.
1971. The metabolism of the chlorinated insecticides Aldrin,
Dieldrin, Endrin, and Isodrin.. Thesis for degree of Doctor of
Philosophy, University of Surrey, Guildford.
Baldwin, M.K.
1973. Structural studies and photochemical rearrangement of an
animal metabolite of HEOD, the active component of Dieldrin.
Pestic. Sci., 4:227-237.
Baldwin, M.K., A. Porter, W.P. Hayes, and D.T. Burns.
1974. Synthesis and structural studies of 9-Anti -Hydroxy HEOD.
Pestic. Sci., 5:121-134.
Ballester, M., J. Riera, and C. Badia.
1974. A rearrangement in the synthesis of Perchloro-1 ,1-
Diphenylethylene from DDE, and related results. Tetrahedron
Lett., 12:1199-1202.
Bandal , S.K., H.B. Clark, and S.C. Anderson.
1974. Leaching and metabolism of 1 ,1 ,l-Trifluoro-N_-[2-methyl-
4- ( phenyl sul fonyl ) phenyl] methanesulfonamide (Destun Herbicide)
in a sandy loam soil. Abstracts, 167th ACS Meeting PEST 61.
Barkes, L., and R.W. Fleming.
1974. Production of dimethyl selenide gas from inorganic
selenium by eleven soil fungi. Bull. Environ. Contam. Toxicol.,
12(3) :308-311 .
Barnes, D., A.T. Bull, and R.C. Poller.
1973. Studies on the persistence of the organotin fungicide
fentin acetate (triphenyltin acetate) in the soil and on surfaces
exposed to light. Pestic. Sci., 4:305-317.
Barnett, J.R., H.W. Dorough.
1974. Metabolism of Chlordane in rats. J. Agric. Food Chem.,
22(4) :612-619.
Barnsley, G.E., and P. A. Gabbott.
1966. A new herbicide 2-Azido-4-ethylamino-6-t-butylamino-
1 ,3,5-triazine. Proc. Eighth Brit. Weed Control Conf., 2:372-376.
Bartl , P., and F. Korte.
1975a. BEITRAGE ZUR 0K0L0GISCHEN CHEMIE XCVIII. Photo-
chemisches Verhalten des Herbizids Sencor (4-Amino-6-tert.-
butyl-3-(methylthio)-l ,2,4,triazin-5-(4H)-on) in Losung.
Chemosphere, 4(3) :169-172.
307
Bartl , P., and F. Korte.
1975b. BEITRAGE ZUR OKOLOGISCHEN CHEMIE IC. Photochemisches
und thermisches Verhalten des Herbizids Sencor (4-Amino-6-
tert.-butyl-3-(methylthio)-l ,2,4-triazin-5-(4H)-on) als Festkorper
und auf Oberflachen. Chemosphere, 4(3) : 1 73-1 76.
Baude, F.J., J. A. Gardiner, and J.C.Y. Han.
1973. Characterization of residues on plants following foliar
spray application of Benomyl . J. Agric. Food Chem., 21(6):
1084-1090.
Baude, F.J., H.L. Pease, R.F. Holt.
1974. Fate of Benomyl on field soil and turf. J. Agric. Food
Chem., 22(3):413-418.
Baughman, R.G., and R.A. Jacobson.
1975. Crystal and molecular structure of organophosphorus
insecticides. I. Ronnel . J. Agric. Food Chem., 23(4) :811.
Baur, J.R., and R.W. Bovey.
1974. Ultraviolet and volatility loss of herbicides. Arch.
Environ. Contam. Toxicol. 2(3):275-288.
Baxter, R.A., P.E. Gilbert, R.A. Lidgett, J.H. Mainprize, and
H.A. Vodden.
1975. The degradation of polychlorinated biphenyls by micro-
organisms. Sci . Total Environ., 4:53-61.
Beckert, W.R., A. A. Moghissi, F.H.F. Au., E.W. Bretthauer, and
J.C. McFarlane.
1974. Formation of methylmercury in a terrestrial environment.
Nature, 249(5458) :674-675.
Bedford, J.W.
1971. Uptake, metabolism, and elimination of DDT and Dieldrin
by freshwater mussles. Diss. Abstr., 23B(1):416.
Begum, S., S. Gab, H. Parlar, and F. Korte.
1973. BEITRAGE ZUE OKOLOGISCHEN CHEMIE LXIV. Reaktions-
verhalten Von Kelevan in Losung, Als Festkorper Und in Der
Gasphase Bei Uv-Bestrahlung. Chemosphere, 6:235-238.
Begum, S., J. P. Lay, W. Klein, und F. Korte.
1975. BEITRAGE ZUE OKOLOGISCHEN CHEMIE CIII. Ausscheidung
Speicherung und Verteilung von Chloroalkylen-9 lkC Futterung
an Ratten. Chemosphere 4(4) : 241 -246.
Beland, F.A., S.O. Farwell, and R.D. Geer.
1974. Anaerobic degradation of 1 ,1 ,1 ,2-Tetrachloro-2,2-bis
(p_-chlorophenyl )ethane (DTE). J. Agric. Food Chem., 22(6):
1148-1149.
Ben-Aziz, A., and N. Aharonson.
1974. Dynamics of uptake, translocation, and disappearance of
thiabendazole and methyl -2-benzimidazolecarbamate in pepper and
tomato plants. Pest. Biochem. Physiol., 4:120-126.
Ben-Bassat, D., and A.M. Mayer.
1975. Volatilization of mercury by algae. Physiol. Plant.,
33:128-132.
Benezet, H.J., and F. Matsumura.
1973. Isomerization of y-BHC to a-BHC in the environment.
Nature , 243 ( 5407 ) : 480-481 .
308
Benezet, H.J., and F. Matsumura.
1974. Factors influencing the metabolism of mexacarbate by
microorganisms. J. Agric. Food Chem., 22(3) :427-430.
Benke, G.M., K.L. Cheever, F.E. Mirer, and S.D. Murphy.
1974. Comparative toxicity, anticholinesterase action and
metabolism of methyl parathion and parathion in sunfish and
mice. Toxicol. Appl . Pharmacol., 28:97-109.
Benke, G.M., and S.D. Murphy.
1974. Effect of TOTP pretreatment on paraoxon and methyl
paraoxon detoxification in rats. Res. Commun. Chem. Pathol.
Pharmacol., 8(4) :665-672.
Benke, G.M., and S.D. Murphy.
1975. The influence of age on the toxicity and metabolism
of methyl parathion and parathion in male and female rats.
Toxicol. Appl. Pharmacol., 31:254-269.
Berck, B.
1974. Fumigant residues of carbon tetrachloride, ethylene
dichloride, and ethylene dibromide in wheat, flour, bran,
middlings, and bread. J. Agric. Food Chem., 22(6) :977-984.
Berlin, M., J. Gage, and S. Holm.
1975. Distribution and metabolism of 2,4,5,2' ,5'-penta-
chlorobiphenyl . Arch. Environ. Health, 30:141-147.
Best, J. A., and J.B. Weber.
1974. Disappearance of s-triazines as affected by soil pH
using a balance-sheet approach. Weed Sci., 22(4) :364-373.
Beynon, K.I.
1971. The fate and effects of frescon molluscicide in aquatic
systems. Schriftenreihe Verein fur Wasser. - Boden.,
und Lufthygiene, 34:95-107.
Benynon, K.I., K.E. Elgar, B.L. Mathews, and A.N. Wright.
1973. The analysis of crops to determine neutral conjugates
of an N-hydroxymethyl derivative of monocrotophos insecticide.
Analyst, 98:194-201.
Beynon, K.I., D.H. Hutson, and A.N. Wright.
1973. The metabolism and degradation of vinyl phosphate
insecticides. Residue Rev., 47:55-142.
Beynon, K.I., T.R. Roberts, G. Stoydin, and A.N. Wright.
1974a. The fate of the herbicide Benzolyprop-ethyl in crops
grown in treated soils. Pestic. Sci., 5:443-450.
Beynon, K.I., T.R. Roberts, and A.N. Wright.
1974b. The degradation of the herbicide Benzoyl prop-ethyl
following its application to wheat. Pestic. Sci., 5:429-442.
Beynon, K.I., T.R. Roberts, and A.N. Wright.
1974c. Degradation of the herbicide Benzoyl prop-ethyl in soil.
Pestic. Sci., 5:451-463.
Beynon, K.I., T.R. Roberts, and A.N. Wright.
1974d. The degradation of the herbicide Benzoyl prop-ethyl on
the foliage of cereal seedlings. Pest. Biochem. Physiol.,
4:98-107.
309
Bhan, V.M., E.W. Stoller, and F.W. Slife.
1970. Toxicity, absorption, translocation, and metabolism of
2,4-D in yellow nutsedge. Weed Sci . , 18(6) :733-737.
Bhulya, Z.H.
1969. Factors affecting persistence of DDT in arrendondo fine
sand. Diss. Abstr., 30B(1 ) :22-23.
Billen, G.
1973. Etude De L'Ecometabolisme Du Mercure Dans Un Milieu
D'eau Douce. Hydrobiol . Bull., 7:60-68.
Billen, G., C. Join's, and R. Wollast.
1974. A bacterial methylmercury-mineralizing activity in river
sediments. Water Res., 8:219-225.
Binkley, R.W., and T.R. Oakes.
1974a. Photochemical reactions of Alkyl 2,4-Dichlorophenoxy-
acetates. Chemosphere, 3(1 ) :3-4.
Binkley, R.W., and T.R. Oakes.
1974b. Photochemical reactions of methyl phenoxyacetates.
J. Org. Chem., 39(1 ) :83-86.
Binkley, R.W., T.R. Oakes, and E. Siebert.
1974. Photochemical reactions of 2,4-Dichlorophenoxy acetic
acid derivatives. Abstracts, 167th ACS Meeting, PEST 69.
Biros, F.J., and H.F. Enos.
1973. Oxychlordane residues in humas adipose tissue. Bull.
Environ. Contam. Toxicol., 10(5) :257-260.
Bishara, R.H., G.S. Born, and J.E. Christian.
1972. Radiotracer distribution and excretion study of chloro-
phenothane in rats. J. Pharm. Sci., 61 (12) : 1 91 2-1916.
Bisogni, J.J., Jr., and A.W. Lawrence.
1975. Kinetics of microbially mediated methylation of mercury
in aerobic and anaerobic aquatic environments. J. Water Pollut.
Control Fed., 47(1 ) :35-50.
Black, A.L., Y.C. Chiu, T.R. Fukuto, and T.A. Miller.
1973. Metabolism of 2,2-Dimethyl-2,3-Dihydrobenzofuranyl-7
NHTiethyl-N-(2-Toluenesulfenyl )carbamate in the housefly and
white mouse. Pest. Biochem. Physiol., 3(4) :435-446.
Bladel, R. Van, and A. Moreale.
1974. Adsorption of Fenuron and Monuron (substituted ureas)
by two montmorillonite clays. Soil Sci. Soc. Am. Proc, 38(2):
244-249.
Blake, J., and D.D. Kaufman.
1975. Characterization of Acylanilide-Hydrolyzing Enzyme (s)
from Fussarium oxysporum Schlecht. Pest. Biochem. Physiol.,
5:304-313.
Block, W.D., and H.H. Cornish.
1959. Metabolism of bi phenyl and 4-chlorobi phenyl in the
rabbit. J. Biol. Chem., 234(12) :3301-3302.
Bock, K.W., and D. Winne.
1975. Glucuronidation of 1-naphthol in the rat intestinal loop.
Biochem. Pharmacol., 24:859-862.
310
Bollag, J-M., E.J. Czaplicki, and R.D. Minard.
1975. Bacterial metabolism of 1-Naphthol. J. Agric. Food Chem..
23(l):85-90.
Bond, C.A., D.W. Woodhan, E.H. Ahrens, and J.G. Medley.
1975. The cumulation and disappearance of Mirex residues. II.
In milk and tissues of cows fed two concentrations of the
insecticide in their diet. Bull. Environ. Contam. Toxicol.,
14(1):25-31.
Bontoyan, W.R., and J.B. Looker.
1973. Degradation of commercial ethylene bisdithiocarbamate
formulations to ethylenethiourea under elevated temperature
and humidity. J. Agric. Food Chem., 21 (3) : 338-341 .
Borchard, R.E., L.G. Hansen, W.H. Huber, R.L. Metcalf, M.E. Welborn.
1974. Pharmacokinetics of Aroclor 1254 components after
intravenous administration to swine and sheep. Arch. Environ.
Contam. Toxicol., 2(2) : 1 79-192.
Bordeleau, L.M.
1972. Biochemical transformations of herbicide-derived anilines
in soil. Diss. Abstr., 32B(9) :5341-5342.
Borg, L., K. Erne, E. Hanko, and H. Wanntorp.
1970. Experimental secondary methyl mercury poisoning in the
goshawk (Accipiter G. gentilis L.). Environ. Pollut. 1:91-104.
Bosik, J.J.
1971. Metabolism of C-2307 (dimethyl phosphate, ester with
3-Hydrox,y-N-Methoxy-N-Methyl-cis-Crotonamide) in rats. Diss.
Abstr., 32B(6):3415.
Bowman, M.C.
1972. Determination and persistence of Bay 68138 and two of
its metabolites in turf grass. Int. J. Environ. Anal. Chem.,
1:307-316.
Boyer, A.C.
1975. Sorption of tetrachlorvinphos insecticide (Gardona)
to the hemolymph of Periplaneta americana. Pest. Biochem.
Physiol., 5:135-141.
Brattsten, L.B.
1972. Role of mixed function oxidases of insects in their
response to xenobiotics. Diss. Abstr., 32B(8):4645.
Braun, H.E., F.L. McEwen, R. Frank, and G. Ritcey.
1975. Residues of leptophos and its metabolites following
application to various crop plants. J. Agric. Food Chem.,
23(l):90-95.
Briggs, D.E., R.H. Waring, and A.M. Hackett.
1974. The metabolism of carboxin in growing barley. Pestic.
Sci., 5:599-607.
Bristol, D., L. Cook, M. Koterba, and D.C. Nelson.
1974. Determination of trace residues of 2,4-D and 2,4-
Dichlorophenol in potato tubers. Abstracts 168th ACS Meeting,
Atlantic City, N.J., September 9-13, PEST 44.
311
Brown, B.S., J. Mills, and J.M. Hulse.
1974. Chemical and biological degradation of waste plastics.
Nature, 250(5462) :161-163.
Brown, J.R., and H. Hughes, and S. Viriyanondha.
1969. Storage, Distribution and Metabolism of 1,1 -Bis (4-
chlorophenyl )-2,2,2-trichloroethanol . Toxicol. Appl . Pharmacol.,
15(l):30-37.
Brown, N.J., and A.W.A. Brown.
1970. Biological fate of DDT in a sub-arctic environment. J.
Wildl. Manage., 34(4) :929-940.
Bruce, R.B., W.R. Maynard, G.D. Cloyd, and D.L. Gilbert.
1974. Fenfluramine residues in chickens and eggs. J. Agric.
Food Chem., 22(6) : 1108-11 11 .
Bruchhausen, V.V., and M. Stiasni.
1973. Transport of the systemic fungicide Cela W 524 (Triforine)
in barley plants. II. Uptake and Metabolism. Pestic, Sci . ,
4:767-773.
Brunker, R.L., and T.L. Bott.
1974. Reduction of mercury to the elemental state by a yeast.
Am. Soc. Microbiol., 27(5) :870-873.
Buchenauer, H., L.V. Edgington, and F. Grossmann.
1973. Photochemical transformation of thiophanate-methyl and
thiophanate to alkyl benzimidazol-2-yl carbamates. Pestic.
Sci., 4:343-348.
Buckland, J.L., R.F. Collins, M.A. Henderson, and E.M. Pullin.
1973a. Radiochemical distribution and decline studies with
bromoxynil octanoate in wheat. Pestic. Sci., 4:689-700.
Buckland, J.L., R.F. Collins, and E.M. Pullin.
1973b. Metabolism of bromoxynil octanoate in growing wheat.
Pestic. Sci., 4:149-162.
Bull, D.L.
1974. Fate of methomyl on cotton. Environ. Entomol . , 3(4):
723-724.
Bullard, R.W., G. Holguin, and J.E. Peterson.
1975. Determination of chlorophacinone and diphenadione
residues in biological materials. J. Agric. Food Chem.,
23(1 ) :72-74.
Bullivant, M.J., and G. Pattenden.
1973. Photolysis of bio-allethrin. Tetradhedron Lett. ,
38:3679-3680.
Bunyan, P.J., and J.M.J. Page.
1973. Pesticide-induced changes in hepatic microsomal enzyme
systems. Some effects of 1 ,1-di (p_-chlorophenyl )-2,2-dichloro-
ethylene (DDE) and 1 ,1-di (p_-chlorophenyl )-2-chlorothylene (DDMU)
in the rat and Japanese Quail. Chem. -Biol. Interact., 6:249-257.
Burse, V.W., R.D. Kimbrough, E.C. Villanueva, R.W. Jennings,
R.E. Linder, and G.W. Sovocool .
1974. Polychlorinated biphenyls: Storage, distribution,
excretion, and recovery; liver morphology after prolonged
dietary ingestion. Arch. Environ. Health, 29:301-307.
312
Burt, G.W.
1974. Translocation and metabolism of Atrazine in Canada
Thistle. Weed Sci., 22(2): 11 6-11 9.
Burt, P.E., M. Elliott, A.W. Farnham, N.F. Janes, P.H. Needham,
and D.A. Pulman.
1974. The Pyrethrins and related compounds. XIX. Geometrical
and optical isomers of 2,2-Dimethyl-3-(2,2-dichlorovinyl )-
cyclopropane carboxylic acid and insecticidal esters with
5-benzyl-3-furyl methyl and 3-phenoxybenzyl alcohols. Pestic.
Sci., 5:791-799.
Burt, P.E., and R.E. Goodchild.
1974. Knockdown by pyrethroids: Its role in the intoxication
process. Pestic. Sci., 5:625-633.
Buser, H.-R., and H.-P. Bosshardt.
1975. Studies on the possible formation of polychloroazobenzenes
in Quintozene treated soil. Pestic. Sci., 6:35-41.
Bush, B., C.F. Tumasonis, and F.D. Baker.
1974. Toxicity and persistence of PCB homologs and isomers
in the avian system. Arch. Environ. Contam. Toxicol., 2(3):
195-212.
Buswell, J. A., and R.B. Cain.
1973. Microbial degradation of piperonylic acid by Pseudomonas
fluorescens. FEBS Lett., 29(3) :297-300.
Butts, E.R. , and C.L. Foy.
1974. Comparative uptake and metabolism of methazole in prickly
sida and cotton. Pest. Biochem. Physiol., 4(1 ):44-55.
Cahn, R.S., R.F. Phipers, and E. Broadaty.
1945. The stability of Derris in insecticidal dusts. The
solvent—powder effect. J. Soc. Chem. Ind., 64(1 ) :33-40.
Cameron, B.D., L.F. Chasseaud, and D.R. Hawkins.
1975. Metabolic fate of Clopidol after repeated oral adminis-
tration to rabbits. J. Agric. Food Chem., 23(2) :269-274.
Capdevila, J., E.D. Villar, and P. Poblete.
1973. The effect of DDT treatment on the levels of DDT-
Dehydrochlorinase in Musca domestica. Comp. Biochem. Physiol.,
44b:441-450.
Capel , I.D., P. Millburn, and R.T. Williams.
1974. The conjugation of 1- and 2-Naphthols and other phenols
in the cat and pig. Xenobiotica, 4(10) :601-615.
Carl in, F.J., J.J. Ford, and L.R. Kangas.
1976. The nature of toxaphene residues on crops. Abstracts,
168th ACS Meeting, PEST 22.
313
Carlson, G.P.
1974. Epoxidation of Aldrin to Dieldrin by lobsters. Bull.
Environ. Contam. Toxicol., 11(6): 577-582 .
Carlson, G.P.
1973. Comparison of the metabolism of Parathion by lobsters
and rats. Bull. Environ. Contam. Toxicol., 9(5) :296-300.
Case, F.H., and R.U. Schock, Jr.
1943. The nitration of certain halobiphenyls. II. Di- and
Tetra-nitro derivatives of 2,2'-dichlorobiphenyl . J. Am. Chem.
Soc, 65:2086-2088.
Casida, J.E., R.A. Gray, and H. Tilles.
1974a. Thiocarbamate sulfoxides: Potent, selective, and
biodegradable herbicides. Science, 184:573-574.
Casida, J.E., R.L. Holmstead, S. Khalifa, J.R. Knox, T. Ohsawa,
K.J. Palmer, and R.Y. Wong.
1974b. Toxaphene insecticide: A complex biodegradable mixture.
Science, 183:520-521.
Casida, J.E., S. Khalifa, J.R. Knox, and T. Ohsawa.
1974c. Studies of toxaphene: Component toxicities and metabolic
fate in mammals. Abstracts, 168th ACS Meeting PEST 21.
Casida, J.E., E.C. Kimmel , H. Okkawa, and R. Ohkawa.
1975. Sulfoxidation of thiocarbamate herbicides and metabolism
of thiocarbamate sulfoxides in living mice and liver enzyme
systems. Pest. Biochem. Physiol., 5:1-11.
Casper, H.H., J.C. Pekas, and W.E. Dinusson.
1973. Gastric Absorption of a pesticide (1-naphthyl N-methyl-
carbamate) in the fasted rat. Pest. Biochem. Physiol., 2(4):
391-396.
Catelani, D., and A. Colombi.
1974. Metabolism of biphenyl. Biochem. J., 143:431-434.
Catelani, D., A. Colombi, C. Sorlini, and V. Treccani .
1973. Metabolism of biphenyl. Biochem. J., 134:1063-1066.
Catelani, D., G. Mosselmans, J. Nienhaus, C. Sorlini, and V. Treccani.
1970. Microbial degradation of aromatic hydrocarbons used as
reactor coolants. Experientia, 26(8) :922-923.
Catelani, D., C. Sorline, and V. Treccani.
1971. The metabolism of biphenyl by Pseudomonas putida.
Experientia, 27:1173-1174.
Chadwick, R.W., L.T. Chuang, and K. Williams.
1975. Dehydrogenation: A previously unreported pathway of
lindane metabolism in mammals. Pest. Biochem. Physiol.,
5:575-586.
Chadwick, R.W. and J.J. Freal .
1972. Comparative acceleration of Lindane metabolism to
chlorophenols by pretreatment of rats with Lindane or with
DDT and Lindane. Food Cosmet. Toxicol., 10:789-795.
Chakrabarti, J.K., and O.M. Friedman.
1973. Studies on the hydrolysis of cyclophosphamide. II.
Isolation and characterization of intermediate hydrolytic
products. J. Heterocycl . Chem., 10:55-58.
314
Chambers, J.E., and J.D. Yarbrough.
1973. Organophosphate degradation by insecticide-resistant
and susceptible populations of Mosquitofish (Gambusia affinis).
Pest. Biochem. Physiol., 3(3) : 31 2-316.
Chambon, P., M. Riotte, M. Daudon, R. Chambon-Mongenot, and
J. Briquier.
1971. Study of the metabolism of dibutyl and diethyl phthalates
in the rat. C.R. Acad. Sci. Paris, 273 Series D:2165-2168.
Chan, T.M., J.W. Gillett, and L.C. Terriere.
1967. Interaction between microsomal electron transport
systems of trout and male rat in cyclodiene epoxidation.
Comp. Biochem. Physiol., 20:731-742.
Chang, R.L., S. Symchowicz, and Chin-Chung Lin.
1973. Oxidative demethylation of 11+C-griseofulvin by liver
microsomes of rats and mice. Biochem. Pharmacol., 22:1389-1392.
Chang, S.C., C.W. Woods, and A.B. Borkovec.
1970. Metabolism of C-labeled N2, N2, N\ N^-tetramethylmel amine
in male house flies. J. Econ. Entomol . , 63X5) : 1 51 0-1 51 3.
Chapman, A.H., and J.W. Price.
1972. Degradation of triphenyltin acetate by ultra-violet light.
Int. Pest Control, 14(1):11-12.
Chasseaud, L.F., D.R. Hawkins, B.D. Camerson, B.J. Fry, and
V.H. Saggers.
1972. The metabolic fate of bentazon in the rat. Xenobiotica,
2(3):269-276.
Chen, P.R.S.
1972. Studies on the amidase which hydrolyzes dimethoate.
Diss. Abstr., 32B(8) :4645-4646.
Chen, R.W., H.E. Ganther, and W.G. Hoekstra.
1973. Studies on the binding of methylmercury by thionein.
Biochem. Biophys. Res. Commun., 51 (2) :383-390.
Cheng, H.M., and J.E. Casida.
1973. Metabolites and photoproducts of 3-(2-Butyl )phenyl
N-methyl carbamate and !N-benzenesulfenyl-N-methyl carbamate.
J. Agric. Food Chem., 21 (6) :1037-1047.
Chiba, M., and F. Doornbos.
1974. Instability of benomyl in various conditions. Bull.
Environ. Contam. Toxicol., 11 (3) :273-274.
Chin, B., J.M. Eldridge, and L.J. Sullivan.
1974. Metabolism of carbaryl by selected human tissues using
an organ-maintenance technique. Clin. Toxicol., 7(1 ) : 37-56.
Chin, W., N. Kucharczyk, and A.E. Smith.
1973. Nature of carboxin (Vitavax)-derived bound residues in
barley plants. J. Agric. Food Chem., 21 (3) :506-507.
Chisholm, D.
1974. Persistence of fensulfothion in soil and uptake by
rutabagas and carrots. Can. J. Plant Sci., 54:667-671.
315
Chopra, S.L., and C.L. Arora.
1974. Infrared spectra of the complexes of malaoxon with some
anhydrous metal chlorides. Pestic. Sci., 5:271-274.
Chow, A.Y.K., and S.D. Murphy.
1974. Production of a methemoglobin-forming metabolite of
3,4-dichloraniline by liver in vitro. Bull. Environ. Contam.
Toxicol., 13(1):9-13.
Clark. A.G., S. Murphy, and J.N. Smith.
1969. The metabolism of hexachlorocyclohexanes and penta-
chlorocyclohexenes in flies and grass grups. Biochem. J.,
113:89-96.
Clark, D.E., J.S. Palmer, R.D. Radeleff, H.R. Crookshank, and
F.M. Farr.
1974. Residues of chlorophenoxy acid herbicides and their
phenolic metabolites in tissues of sheep and cattle. J. Agric.
Food Chem., 23(3) :573-578.
Clay, D.V., and K.G. Stott.
1973. The persistence and penetration of large doses of
Simazine in uncropped soil. Weed Res., 13(1 ) :42-50.
Clegg, D.E.
1974. Residues of Clenpirin [2-(3,4-dichlorophenylimino)-10
r^-butyl pyrrolidine] in the fatty tissues of steers and in butter
fat. Pestic. Sci., 5:769-779.
Clegg, D.E., and P.R. Martin.
1973. Residues of the carbamate acaricide, 3-methyl-5-isopropyl-
phenyl-N-(n-butanoyl )-N-methyl carbamate (promacyl) and two
metabolites in the tissues and milk of cattle. Pestic. Sci.,
4:447-457.
Cliath, M.M., and W.F. Spencer.
1972. Dissipation of pesticides from soil by volatilization
of degradation products. Environ. Sci. Toxicol., 6(10):910-914.
Coats, G.E., and C.L. Foy.
1974. Effect of petroleum oils on the uptake of Atrazine-11+C
by corn. Weed Sci., 22(3) :220-225.
Coats, J.R., R.L. Metcalf, and I. P. Kapoor.
1974. Metabolism of the methoxychlor isostere, dianisylneopentane,
in mouse, insects, and a model ecosystem. Pest. Biochem. Physiol.,
4:201-211.
Cocks, J. A.
1974. The metabolism of 1-naphthyl methyl carbamate by Periplaneta
americana. Pestic. Sci., 5:505-510.
Cole, E.R., G. Crank, and A-Salam Sheikh.
1973. Photochemistry of heterocyclic compounds I. Photo-
dehydrodimerization of Benzimidazole. Tetrahedron Lett.
No. 32:2987-2988.
Collet, G.F., and V. Pont.
1974. Distribution et Metabolisme du Methabenzthiazuron chez
des Especes Vegetal es. Weed Res., 14:151-165.
316
Collins, J. A.
1969. Chlorinated hydrocarbon pesticides: Degradation and
effect on the growth of bacteria. Diss. Abstr. 30B(4) :1426-1427.
Collins, R.F.
1973. Perfusion studies with Bromoxynil Octanoate in soil.
Pestic. Sci., 4:181-192.
Cooke, A.S.
1970. The effect of p_,p_'-DDT on tadpoles of the common frog
(Rana temporaria). Environ. Pollut., 1(1): 57-71 .
Cox, D.P., and M. Alexander.
1973. Production of trimethylarsine gas from various arsenic
compounds by three sewage fungi. Bull. Environ. Contam.
Toxicol., 9(2):84-88.
Craine, E.M., M.J. Parnell, and L.R. Stone.
1974. A method for analysis of swine tissue for the primary
metabolite of dimetridazole at the 2-ppb level. J. Agric.
Food Chem., 22(5) : 377-881 .
Creaven, P.J., and D.V. Parke.
1966. The stimulation of hydroxylation by carcinogenic and
non-carcinogenic compounds. Biochem. Pharmacol., 15:7-16.
Crosby, D.G., and E. Leitis.
1973. The photodecomposition of trifluralin in water. Bull.
Environ. Contam. Toxicol., 10(4) : 237-241 .
Crosby, D.G., and K.W. Moilanen.
1973. Photodecomposition of chlorinated biphenyls and dibenzo-
furans. Bull. Environ. Contam. Toxicol., 10(4) :372-377.
Crosby, D.G., and K.W. Moilanen.
1974. Vapor-phase photodecomposition of aldrin and dieldrin.
Arch. Environ. Contam. and Toxicol., 2(l):62-74.
Crosby, D.G., and A.S. Wong.
1973a. Photodecomposition of p_-chlorophenoxyacetic acid.
J. Agric. Food Chem., 21 (6) : 1049-1052 .
Crosby, D.G., and A.S. Wong.
1973b. Photodecomposition of 2,4,5-trichlorophenoxyacetic
acid (2,4,5-T) in water. J. Agric. Food Chem., 21 (6) :1052-1054.
Cross, R.J.
1973. Organomercurials in the environment. Chem. Ind.,
719-721.
Crowder, L.A., E.F. Dindal.
1974. Fate of 36Cl-Toxaphene in rats. Bull. Environ. Contam.
Toxicol., 12(3):320-327.
Cruickshank, P. A., and H.C. Jarrow.
1973. Ethyl enethiourea degradation. J. Agric. Food Chem.,
21:333-335.
Currie, R.A.
1974. Determination of leptophos, leptophos oxon and a
possible phenolic photoconversion metabolite in rapeseed grain.
J. Assoc. Off. Anal. Chem., 57:1056-1060.
317
Daly, R.W. , Jr.
1972. Degradation of 2,4-DBEE in an aquatic environment.
Diss. Abstr., 32B(7):3806.
Daniel , J.W.
1972. The biotransformation of organomercury compounds. Biochem.
J., 130(2] 1:64-65.
Daniel, J.W. and H. Bratt.
1974. The adsorption, metabolism and tissue distribution of
Di(2-ethylhexyl )phthalate in rats. Toxicology, 2:51-65.
Dannals, L.E., R.J. Puhl , and N. Kucharczyk.
1974. Dissipation and degradation of Alar in soils under
greenhouse conditions. Arch. Environ. Contam. Toxicol.,
2(3) .-213-221.
Darrow, D.C., and R.F. Addison.
1973. The metabolic clearance of 1J*C-p_,p_' -DDT from plasma and
its distribution in the thorny skate, Raja radiata. Environ.
Physiol. Biochem., 3:196-203.
Dauterman, U.C., and W. Muecke.
1973. In vitro metabolism of Atrazine by rat liver. Pest.
Biochem. Physiol., 4:212-219.
Davidek, J., J. Seifert.
1973. The stability of phaltan and captan in wort. Z. Lebensm.-
Unters.-Forsch., 153:301-304.
Davis, A.C., J.B. Bourke, and R.J. Kuhr.
1974. Disappearance of Monitor residues from cole crops.
J. Econ. Entomol., 67(6) :766-768.
Dawson, V.K.
1973. Photodecomposition of the piscicides TFM(3-trifluoro-
methyl-4-nitrophenol) and antimycin. Master's Thesis presented
to U. of Wisconsin, La Crosse, 62 pages.
DeBaun, J.R., J.B. Miaul lis, J. Knarr, A. Mihailkovski , J.J. Menn.
1974a. Metabolism of the trichloromethylthio (TMT) moiety of
Captan in the rat: Inactivation of the putative fungal toxophore,
Abstracts, 167th ACS Meeting, April 1-5, PEST 45.
DeBaun, J.R., J.B. Miaul lis, J. Knarr, A. Mihailovski, and J.J. Menn.
1974b. The fate of N-Trichloro (li+C) methyl thio-4-cyclohexene-
1 ,2-dicarboximide (["^C] Captan) in the rat. Xenobiotica,
4(2):101-119.
de Frenne, E., J. Eberspacher, and F. Lingens.
1973. The bacterial degradation of 5-Amino-4-chloro-2-phenyl-
3(2H)-pyridazinone. Eur. J. Biochem., 33(2) :357-363.
de Frenne, E., J. Eberspacher, F. Lingens, and W. Schafer.
1974. Bacterial hydroxylation of pyrazon compounds. Z.
Naturforsch., 296:283-285.
Dejonckheere, W., and R.H. Kips.
1974. Photodecomposition of methidathion. J. Agric. Food
Chem., 22(6):959-968.
Dejonckheere, W., W. Steurbaut, R. Dynoodt, and R.H. Kips.
1974. Uptake and translocation of dimefox and schradan in
hops. Pestic. Sci . , 5(5) :549-559.
318
Dejonckheere, W. , W. Steurbaut, and R.H. Kips.
1975. Residues of quintozene, hexachlorobenzene, dichloran, and
pentachloroaniline in soil and lettuce. Bull. Environ. Contam.
and Toxicol., 13(6) :720-729.
Dekhuijzen, H.M., and C.R. Vonk.
1974. The distribution and degradation of chlormequat in wheat
plants. Pest. Biochem. Physiol., 4:346-355.
DeLacy, T.P., and C.H.L. Kennard.
1972a. Insecticides. Part I. Crystal structires of 1,1-Bis-
(fJ-chlorophenyl ) -2, 2-dimethyl propane. J. Chem. Soc, Perkin
Transactions II., 2121-2147.
DeLacy, T.P., and C.H.L. Kennard.
1972b. Insecticides. Part II. Crystal structures of 1,1-Bis-
(p_-chlorophenyl )-2,2,2-trichloroethene(p_,p_'-DDT) and l-(o-
chlorophenyl )-l -(p_-chlorophenyl )-2,2,2-trichloroethane (o,p_'-DDT) .
J. Chem. Soc, Perkin Transactions II., 2148-2153.
Demint, R.J., J.C. Pringle, Jr., A. Hattrup, V.F. Burns and P. A. Frank.
1975. Residues in crops irrigated with water containing trichloro-
acetic acid. J. Agric. Food Chem., 23(l):31-84.
Desaiah, D. , L.K. Cutkomp, and R.B. Koch.
1974. A comparison of DDT and its biodegradable analogues tested
on ATPase enzymes in cockroach. Pest. Biochem. Physiol., 4:232-238.
Devonshire, A.L., and P.H. Needham.
1974. The fate of some organophosphorus compounds applied topically
to peach-potato aphids (Myzus persicae (Sulz.)) resistant and
susceptible to insecticides. Pestic. Sci . , 5:161-169.
deVos, R.H., M.C. ten Noever deBrauw, and P.D.A. Olthof.
1974. Residues of pentachloronitrobenzene and related compounds in
greenhouse soils. Bull. Environ. Contam. Toxicol., 11 (6) : 567-571 .
Dexter, A.G.
1970. Fate of 2,4-Dichlorophenoxyacetic acid in several plant
species. Diss. Abstr., 30(7) :2988-2989.
DiCuollo, C.J., J. A. Miller, W.L. Mendelson, and J.F. Pagano.
1974. Metabolic and tissue residue studies on Parabendazole in
sheep. J. Agric. Food Chem., 22:948-953.
Dieter, S., and A. Jumar.
1969. Model luntersuchungen uber den Abbau des herbiziden
Wirkstoffes Proximpham. Arch. Pflanzenschutz, 5(6) :445-453.
Dimond, J.B., R.B. Owene, Jr., and A.S. Getchell.
1975. DDT residues in forest biota: Further Data. Bull. Environ.
Contam. Toxicol., 13(1 ) :117-122.
Dinamarca, M.L., A. Ramirez, E.D. Villar, and J. Capdevila.
1974. DDT-dehydrochlorinase. III. Enzymic oxidation of gluta-
thione. Int. J. Biochem., 5:1-9.
Doll-wet, H.H.A., and J. Kumamoto.
1970. Ethylene production of ethyl propyl phosphonate, Niagara
10637. Plant Physiol., 46:786-789.
Donaldson, T.W., D.E. Bayer, and O.A. Leonard.
1973. Absorption of 2,4-Dichlorophenoxyacetic acid and 3-(p_-
chlorophenyl )-l ,1-dimethylurea (Monuron) by barley roots. Plant
Physiol., 52:638-645.
319
Dorough, H.W.
1974. Metabolism of methazole in wheat and onions. Bull.
Environ. Contam. Toxicol., 12(4) :493-500.
Dorough, H.W., and R.W. Hemken.
1973. Chlordane residues in milk and fat of cows fed HCS 3260
(High Purity Chlordane) in the diet. Bull. Environ. Contam.
Toxicol., 10(4):208-216.
Dorough, H.W., J. P. McManus, S.S. Kumar, R.A. Cardona.
1974. Chemical and metabolic characteristics of 1-Naphthyl-e
D-Glucoside. J. Agric. Food Chem., 22(4) :642-645.
Dorough, H.W., D.M. Whitacre, and R.A. Cardona.
1973. Metabolism of the herbicide Methazole in cotton and
beans, and fate of certain of its polar metabolites in rats.
J. Agric. Food Chem., 21 (5) :797-803.
Douch. P.G.C.
1973. The metabolism of benomyl fungicide in mammals.
Xenobiotica, 3(6) :367-380.
Dressman, R.C.
1972. The conversion of phenylmercuric salts to diphenyl-
mercury and phenylmercuric chloride upon gas chromatographic
injection. J. Chromatogr. Sci . , 10:468-472.
Duff, W.G., and R.E. Menzer.
1973. Persistence, mobility and degradation of 11+C-dimethoate
in soils. Environ. Entomol . , 2(3) : 309-318.
Duhm, B., W. Maul, H. Medenwald, K. Patzschke, and L.-A. Wegner.
1961. Radioaktive Untersuchungen mit einem neuen Molluscicid.
Z. Naturforsch., 16b:509-515.
Dumas, T., and E.J. Bond.
1975. Bromide residues in apples fumigated with ethylene
dibromide. J. Agric, Food Chem., 23(1 ) :95-98.
Dunn, G.L., G. Gallagher, Jr., L.D. Davis, J. R.E. Hoover, and
R.J. Stedman.
1973. Metabolites of methyl 5(6)-butyl-2-benzimidazolecarbamate
(Parbendazole) . Structure and synthesis. J. Med. Chem.,
16(9):996-1002.
Eastin, E.F.
1971a. Fate of fluorodifen in resistant peanut seedlings.
Weed Sci., 19(3) :261-265.
Eastin, E.F.
1971b. Movement and fate of fluorodifen-l-11+C in cucumber
seedlings. Weed Res., 11:63-68.
Eastin, E.F.
1971c. Movement and fate of p_-Nitrophenyl-a,a,a-trifluoro-
2-nitro-p_-tolyl ether in peanut seedlings. Weed Sci. Soc.
Am. Abstr., 44.
Eben, A., and G. Kimmerle.
1972. Unpublished data (Bayer AG). Referred to in Ueyama and
Takase, Agr. Biol. Chem., 39(9) : 1 71 9-1 727( 1 975) .
320
Edwards, T., B.C. McBride.
1975. Biosynthesis and degradation of methylmercury in human
feces. Nature, 253:462-464.
Eidel'nant, N.M., and V.E. Mostovaya.
1972. Studies of the metabolism of 2,4-D in plants. Agrokhimiya,
11:121-124.
Eisenbrand, G., 0. Lingerer, and R. Preussman.
1974. Rapid formation of carcinogenic N-Nitrosamines by inter-
action of nitrite with fungicides derived from Dithiocarbamic
Acid in vitro under simulated gastric conditions and in vivo in
the rat stomach. Food Cosmet. Toxicol., 12:229-232.
Eliasson, L.
1973. Translocation and persistence of 2,4-D in Populus
tremula L. Weed Res., 13:140-147.
El-Refai, A., and M.M. Mowafy.
1973. Propanil hydrolysis: Inhibition in rice plants by
Diazinon and Carbaryl translocated from the soil. J. Assoc.
Off. Anal. Chem., 56(5) : 11 78-1 182.
El-Zorgani, G.A., and M.E.H. Omer.
1974. Metabolism of Endosulfan isomers by Aspergillus niger.
Bull. Environ. Contam. Toxicol., 12(2) :182-185.
Englehardt, F., P.R. Wallnofer, and R. Plapp.
1973. Purification and properties of an Aryl Acylamidase of
Bacillus sphaericus, catalyzing the hydrolysis of various
Phenylamide herbicides and fungicides. Appl . Microbiol.,
26(5):709-718.
Engst, R., R.M. Macholz, and M. Kujawa.
1974. Metabolismus des Lindan. Abbau von Lindan durch
Schimmelpilzkulturen. Unkonjugierte Metabolite. Nahrung,
18(8) :737-745.
Engst, R., R.M. Macholz, and M. Kujawa.
1975. Identifizierung von Metaboliten under der Abbauweg
des Hexachlorbenzols in einer Schimmelpilzkultur. Die Nahrung,
19(7) :603-606.
Ercegovich, CD., N.L. Hartwig, S. Witkonton, and P. Carroll.
1972. Persistence of 5,6-Dichloro-2-trifluoromethylbenzimidazole,
a major degradation product of Fenazaflor, in Hagerstown silt
loam soil. Environ. Entomol . , 1 (6) : 730-733.
Ernst, W.
1969. 10. Metabolism of substituted Dinitrophenols and ureas
in mammals and methods for the isolation and identification of
metabolites. J. S. Afr. Chem. Inst., XXII, S79-S88.
Ernst, W.
1972. Degradation of [llfC]DDT on silica gel G chromatograms
under laboratory conditions. J. Chromatogr., 67:179-181.
Ernst, W.
1975. Aufnahme, Ausscheidung und Umwandlung Von Lindan-11+C
Durch Mytilus edulis. Chemosphere, 4(6) :375-380.
321
Ernst, W., and H. Goerke.
1974. Anreicherung, Verteilung, Umwandlung and Ausscheidung von
DDT-lt+C bei Solea solea (Pisces: Soleidae). Mar. Biol. (Berl),
24:287-304.
Exner, J.H., G.A. Burk, and D. Kyriacou.
1973. Rates and products of decomposition of 2,2-Dibromo-3-
nitrilopropionamide. J. Agric. Food Chem. , 21 (5) :838-842.
Fahmy, M.A.H., and T.R. Fukuto.
1972. Oxidative rearrangement of ^-(Dimethoxyphosphinothioyl )
Carbamate esters. Tetrahedron Lett., 41:4245-4248.
Fahmy, M.A.H., A. Khasawinah, and T.R. Fukuto.
1972. Alkaline hydrolysis of Phosphoramidothioate esters. J. Org.
Chem., 37:617-625.
Fang, S.C.
1973. Uptake and biotransformation of Phenyl mercuric Acetate by
aquatic organisms. Arch. Environ. Contam. Toxicol., l(l):18-26.
Fang, S.C.
1974. Uptake, distribution, and fate of 203Hg-ethyl mercuric chloride
in the guppy and the coontail. Environ. Res., 8(1 ):112-118.
Fang, S.C, E. Fall in, M.L. Montgomery, and V.H. Freed.
1973. The metabolism and distribution of 2,4,5-Trichlorophenoxy-
acetic acid in female rats. Toxicol. App. Pharmacol., 24:555-563.
Fang, S.C, E. Fall in, M.L. Montgomery, and V.H. Freed.
1974. Metabolic studies of C-labeled Propham and Chlorpropham
in the female rat. Pest. Biochem. Physiol., 4:1-11.
Fell , V.J., CH. Lamoureau, E. Styrvoky, R.G. Zaylskie, E.J. Tacker,
and G.M. Holman.
1973. Metabolism of o,p_'-DDT in rats. J. Agr. Food Chem., 21(6):
1072-1078.
Feil, V.J., CH. Lamoureux, and R.G. Zaylskie.
1974. Metabolism of o,p_'-DDT in chickens. Abstracts, 167th
ACS Meeting, PEST 79, April 1-5.
Feil, V.J., CH. Lamoureux, and R.G. Zaylskie.
1975. Metabolism of o_,p_'-DDT in chickens. J. Agric. Food Chem.,
23(3):382-388.
Feiner, E., B. Krauthacker, V. Simeon, and M. Skrinjaric-Spol jar.
1975. Mechanism of inhibition in vitro of mammalian acetyl-
cholinesterase and cholinesterase in solutions of 0_,0_-di methyl
2,2,2-trichloro-l-hydroxyethyl phosphonate (Trichlorphon) .
Biochem. Pharmacol., 24:717-722.
Feit, P.W., and N. Rastrup-Andersen.
1973. 4-Methanesulfonyloxybutanol : Hydrolysis of Busulfan.
J. Pharm. Sci., 62(6) :1 007-1 008.
Feung, C, R.H. Hamilton, and R.0. Mumma.
1973. Metabolism of 2,4-Dichlorophenoxyacetic Acid. V. Identi-
fication of metabolites in soybean callus tissue cultures. J.
Agric. Food Chem., 21 (4) :637-640.
Feung, C, R.H. Hamilton, and R.0. Mumma.
1975. Metabolism of 2,4-Dichlorophenoxyacetic Acid. VII. Compar-
ison of metabolites from five species of plant callus tissue
cultures. J. Agric. Food Chem., 23(3) :373-376.
322
Finlayson, D.G., and D.L. Suett.
1975. Persistence and bioactivity of Chlorofenviphos in
carrots and soil in greenhouse experiments. J. Econ. Entomol . ,
68(2):140-142.
Fisher, J.D.
1974. Metabolism of the herbicide Pronamide in soil. J. Agric.
Food Chem., 22(4) :606-608.
Fiveland, T.J., L.C. Erickson, and C.I. Seely.
1972. Translocation of 11+C-assimilates and 3-Amino-l ,2,4-
Triazole and its metabolites in Agropyron repens. Weed Res.,
12:155-163.
Flashinski, S.J., and E.P. Lichtenstein.
1974a. Metabolism of Dyfonate by soil fungi. Can. J. Microbiol,
20(3): 399-411.
Flashinski, S.J., and E.P. Lichtenstein.
1974b. Degradation of Dyfonate in soil inoculated with Rhizopus
arrhizus. Can. J. Microbiol., 20(6) :871-875.
Flashinski, S.J., and E.P. Lichtenstein.
1975. Environmental factors affecting the degradation of
Dyfonate by soil fungi. Can. J. Microbiol., 21(l):17-25.
Fleeker, J.R.
1973. Removal of the acetate-moiety of 2,4-Dichlorophenoxy-
acetic Acid in Ribes sativum. Phytochemistry, 12:757-762.
Fleeker, J.R., H.M. Lacy, I.R. Schultz, and E.C. Houkom.
1974. Persistence and metabolism of Thiophanate-methyl in soil.
J. Agric. Food Chem., 22(4) :592-595.
Forgash, A.J., and S. Ahmad.
1974. Hydroxylation and demethylation by gut microsomes of
gypsy moth larvae. Int. J. Biochem., 5:11-15.
Fournier, J.-C.
1975a. Degradation microbienne de la 2,4-Dichlorobenzamide
dans des modeles de laboratoire. II. Influence de 1 'addition
de substrats carbones simples sur la biodegradation de la
2,4-Dichlorobenzamide. Chemosphere, 4(1 ) :35-40.
Fournier. J.-C.
1975b. Degradation Microbienne De L' Isoproturon Dans Des
Modeles De Laboratoire. Chemosphere, 4(4) : 207-214.
Francis, A.J., R.J. Spanggord, and G.I. Ouchi .
1975. Degradation of Lindane by Escherichia coli . Appl .
Microbiol., 29(4):567-568.
Frank, A.
1971. Studies on the metabolism of 2-(2-Furyl )benzimidazole
in certain mammals. Acta Pharmacol, et toxicol., 29(2):1-124.
Frankenberg, L., and B. Sorbo.
1975. Effect of cyanide antidotes on the metabolic conversion
of cyanide to thiocyanate. Arch. Toxicol., 33:81-89.
Freal , J.J., and R.W. Chadwick.
1973. Metabolism of hexachlorocyclohexane to chlorophenols and
effect of isomer pretreatment on Lindane metabolism in rat. -
J. Agric. Food Chem., 21 (3) :424-427.
323
Frear, D.S., and H.R. Swanson.
1973. Metabolism of substituted diphenylether herbicides in
plants. I. Enzymatic cleavage of fluorodifen in peas (Pi sum
sativum L.). Pest. Biochem. Physiol., 3:473-482.
Frear, D.S., and H.R. Swanson.
1975. Metabolism of cisanilide (cis-2,5-Dimethyl-l -Pyrrol i-
dinecarboxanilide) by excised leaves and cell suspension
cultures of carrot and cotton. Pest. Biochem. Physiol., 5:73-80.
Freeman, L.R., P. Angel ini, G.J. Silverman, and C. Merritt, Jr.
1975. Production of hydrogen cyanide by Pseudomonas fluorescens.
Appl. Microbiol., 29(4) : 560-561 .
Freitag, K.-D., and R. Bock.
1974. Degradation of triphenyltin chloride on sugar beet plants
and in rats. Pestic. Sci., 5:731-739.
French, A.
1969. Reductive dechlorination of p_,p_' -DDT by Escherichia
coli and Pseudomonas aeruginosa. Diss. Abstr. , 30B(1 ):240-241 .
Fries, G.F.
1972. Degradation of chlorinated hydrocarbons under anaerobic
conditions. Adv. Chem. Ser., 111:256-270.
Fries, G.F., and G.S. Marrow.
1974. Retention and elimination of 2,3,7,8-tetrachlorodibenzo-
p_-dioxin fed continuously to rats. Abstracts, 167th ACS Meeting,
PEST 72.
Fries, G.F., and G.S. Marrow.
1975. Retention and excretion of 2,3,7,3-Tetrachlorodibenzo-
p_-dioxin by rats. J. Agric. Food Chem., 23(2) :265-269.
Fries, G.F., G.S. Marrow, Jr., and C.H. Gordon.
1973. Long-term studies of residue retention and excretion by
cows fed a polychlorinated biphenyl (Aroclor 1254). J. Agric.
Food Chem., 21 (1 ) :117-121 .
Fryer, J.D., J.R. Hance, and J.W. Ludwig.
1975. Long-term persistence of paraquat in a sandy loam soil.
Weed Res., 15:189-194.
Fuchs, A., M. Viets-Verweij, and F.W. de Vries.
1972. Metabolic conversion in plants of the systemic fungicide
Triforine Q[,N/-bis-(l-formamido-2,2,2-trichloroethyl )-piperazine;
CELA U 524]. Phytopathol . Z., 75:111-123.
Fujita, M., A. Ishii, and Y. Sakagami.
1969. Photo-decomposition of Endrin. J. Hyg. Chem., 15(1):9-12.
Fukoto, T.R.
1972. Metabolism of carbamate insecticides. Drug Metab. Rev.,
1(1):117-151.
Furukawa, K. , and K. Tonomura.
1972. Induction of metallic mercury-releasing enzyme in mercury-
resistant Psejjd^monas_. Agric. Biol. Chem., 36(13) :2441-2448.
Gab, S., W. Klein, and F. Korte.
1973. Photo reaktionen Des Aldrin/Dieldrin-Metaboliten
Dihydrochlorden-1 ,3-Dicarbonsaure. Chemosphere, 2(3) : 107-1 10.
324
Gab, S., S. Nitz, H. Parlar, and F. Korte.
1975a. Beitrage Zur Okologischen Chemie CV. Photomineralisation
of certain aromatic Xenobiotica. Chemosphere, 4(4) :251 -256.
Gab, S., H. Parlar, and F. Korte.
1974. Beitrage Zur Okologischen Chemie - LXI. Photoreaction
Des Al dri n/Di el dri n-Metabol i ten Di hydochl ordendi carbonsaure .
Tetrahedron, 30:1145-1151.
Gab, S., V. Saravanja, and F. Korte.
1975b. Beitrage zue Okologischen Chemi LXXIII. Irradiation
studies of Aldrin and Chlordene adsorbed on a silica gel
surface. Bull. Environ. Contam. Toxicol., 13(3) :301-306.
Gagne, J., and J. Brodeur.
1972. Metabolic studies on the mechanisms of increased
susceptibility of weanling rats to Parathion. Can. J. Physiol.
Pharmacol., 50(9) :902-915.
Garcia, J.D., M.G. Yang, J.H.C. Wang, and P.S. Belo.
1974. Carbon-mercury bond cleavage in blood of rats fed methyl
mercuric chloride. Proc. Soc. Exp. Biol. Med., 146:66-70.
Gardiner, J. A., J.J. Kirkland, H.L. Klopping, and H. Sherman.
1974. Fate of Benomyl in animals. J. Agric. Food Chem., 22(3):
419-427.
Gardner, A.M., J.T. Chen, J.A.C. Roach, and E.P. Ragelis.
1973. Polychlorinated bi phenyls: Hydroxylated urinary metabolites
of 2,5,2' ,5'-tetrachlorobiphenyl identified in rabbits. Biochem.
Biophys, Res. Commun., 55(4) :1377-1384.
Garrett, R.J.B., N.E. Garrett.
1974. Mercury incorporation by mature and immature red blood
cells. Life Sci., 15:733-740.
Garretto, M., and M.A.Q. Khan.
1975. Hydroxylation and epoxidation of chlordene by the mixed-
function oxidase of the tropical and cold fresh water fish.
Gen. Pharmacol., 6:91-96.
Gehring, P.J., C.G. Kramer, B.A. Schwetz, J.Q. Rose, and V.K. Rowe.
1973. The fate of 2,4,5-Trichlorophenoxyacetic Acid (2,4,5-T)
following oral administration to man. Toxicol. Appl . Pharmacol.,
26:352-361.
Geier, G., and I.W. Ernt.
1967. Kinetik und Mechanismus von Methyl quecksibler-
Komplexbildungen. Chimia, 27(12) :635-637.
Getzin, L.W.
1973. Persistence and degradation of carbofuran in soil.
Environ. Entomol . , 2(3) :461-467.
Gibson, J.R.
1971. Comparative biochemistry of Parathion metabolism in three
species of fishes. Diss. Abstr. , 32B(4):2365.
Gilbert, M.D., S.P. Monselise, L.J. Edgerton, G.A. Maylin, L.J. Hicks,
and D.J. Lisk.
1975. Metabolism studies with Ethephon in cherry leaves.
J. Agric. Food Chem., 23(2) :290-292.
325
Gilbert, M.D., A. Pendergrass, F.M. Isenberg, and D.J. Lisk.
1974. Fate of neodecanoic acid in onion and soil. J. Agric.
Food Chem., 22(4) : 589-592.
Gilman, A. P., and A. Vardanis.
1974. Carbofuran. Comparative toxicity and metabolism in the
worms Lumbricus terrestris L. and Eisenis foetida S. J. Agric.
Food Chem., 22(4) :625-628.
Gledhill, W.E.
1975. Biodegradation of 3,4,4'-Trichlorocarbanil ide, TCC, in
sewage and activated sludge. Water Res., 9:649-654.
Golab, T., and W.A. Althaus.
1975. Transformation of Isopropalin in soil and plants. Weed
Sci., 23(3):165-171.
Golab, T., C.E. Bishop, A.L. Donoho, J. A. Manthey, and L.L. Zornes.
1975. Behavior of lhC Oryzalin in soil and plants. Pest.
Biochem. Physiol., 5:196-204.
Goren, R., and M.J. Burkovac.
1973. Mechanism of Naphthaleneacetic Acid conjugation.
Plant Physiol., 51:907-913.
Goswami , K.P.
1972. Fate of Ametryne in soil, nutrient solution-sugarcane
and soil-sugarcane systems. Diss. Abstr. 33B(6) :2436-2437.
Goswami, K.P., and R.E. Green.
1971. Microbial degradation of the herbicide Atrazine and its
2-Hydroxy analog in submerged soils. Enviorn. Sci. Technol . ,
5(5):426-429.
Goswami, K.P., and R.E. Green.
1974. Ametryne metabolite in transpired/guttated water from
sugarcane shoot. J. Agric. Food Chem., 22(2) :340-342.
Goto, M., M. Hattori, and K. Sugiura.
1975. Metabolism of Pentachloro- and Hexachloro-bi phenyls in
the rat. Chemosphere, 4(3) :177-180.
Graetz, D.A.
1970. I. Parathion degradation in lake sediments. II.
Adsorption of insecticides by organo-clay complexes. Diss.
Abstr., 31B(6):3464-3465.
Graham, R.E., K.R. Burson, C.F. Hammer, L.B. Hansen, and C.T. Kenner.
1973. Photochemical decomposition of heptachlor expoide. J.
Agric. Food Chem., 21 (5) :824-834.
Grant, D.J.W., and J.V. Wilson.
1973. Degradation and hydrolysis of amides by Corynebacterium
pseudodiphteriticum NCIB 10803. Microbios., 8:15-22.
Grant, D.L., W.E.J. Phillips, and D.C. Villeneuve.
1971. Metabolism of a polychlorinated biphenyl (Aroclor 1254)
mixture in the rat. Bull. Environ. Contam. Toxicol., 6(2) :102-112.
326
Greaves, J.
1972. How super rats survive. New Sci . , 56(816) :1 56-168.
Greb, W., W. Klein, F. Coulston, L. Golberg, and F. Korte.
1973. Excretion rates of pure Di- and Trichlorobiphenyl-11+C
in the rhesus monkey. Chemosphere, 2(4) : 143-146.
Greb, W., W. Klein, F. Coulston, L. Golberg, and F. Korte.
1975a. Beitrage zur Okologischen Chemie. LXXXIII. In vitro
Metabolism of Polychlorinated bi phenyl s-11+C. Bull. Environ.
Contam. Toxicol., 13(4) :424-432.
Greb, W. , W. Klein, F. Coulston, L. Golberg, and F. Korte.
1975b. Beitrage zur Okologischen Chemie. LXXXIV. Metabolism
of lower polychlorinated biphenyls-1LfC in the rhesus monkey.
Bull. Environ. Contam. Toxicol., 13(4) :471-476.
Grover, R.
1974. Adsorption and desorption of trifluralin, triallate and
dial late by various adsorbents. Weed Sci., 22(4) :405-408.
Grunwell, J.R., and R.H. Erickson.
1973. Photolysis of Parathion (0, O-Di ethyl -0- (4-ni trophenyl )
thiophosphate). New Products. J. Agric. Food Chem., 21(5):
929-931 .
Guirguis, G.N., and W.A. Brindley.
1975. Carbaryl penetration into and metabolism by alfalfa leaf-
cutting bees, Megachile pacifica. J. Agric. Food Chem., 23(2):
274-279.
Hall, R.J.
1974. The metabolism of ammonium fluoride and sodium mono-
fluoracetate by experimental Acacia georginae. Environ. Pollut.,
6:267-280.
Hall men, U.
1975. Translocation and complex formation of root-applied 2,4-D
and Picloram in susceptible and tolerant species. Physiol. Plant.,
34:266-272.
Hallmen, U.
1974. Translocation and complex formation of Picloram and 2,4-D
in rape and sunflower. Physiol. Plant., 32:78-83.
Hallmen, U., and L. Eliasson.
1972. Translocation and complex formation of picloram and 2,4-D
in wheat seedlings. Physiol. Plant., 27:143-149.
Hamelink, J.L.
1970. The dynamics of DDT in the lentic environment. Diss.
Abstr., 30B(12):(part 1), 5312-5313.
Hammerschlag, R.S., and H.D. Sisler.
1973. Benomyl and methyl -2-benzimidazolecarbamate (MBC):
Biochemical, cytological and chemical aspects of toxicity to
Ustilago maydis and Saccharomyces cerevesiae. Pest. Biochem.
Physiol., 3(1 ) :42-54.
327
Casida.
phenyl epoxygeranyl ether juvenoid
Biochem. Physiol., 4:393-406.
Hammock, B.D., S.S. Gill, and J.E.
1974. Insect metabolism of a
and related compounds. Pest.
Handi, Y.A., and M.S. Tewfik.
1969. Decomposition of the herbicide trifluralin by a
pseudomonad. Acta Microbiol. Pol., Ser. B., 1 (18) :83-84.
Hansen, L.G., I. P. Kapoor, and R.L. Metcalf.
1972. Biochemistry of selective toxicity and biodegradability:
Comparative O-Dealkylation by aquatic organisms. Comp. Gen.
Pharmacol., 3:339-344.
Hansen, L. G., R.L. Metcalf, and I. P. Kapoor.
1974. Biochemistry of selective toxicity and biodegradability.
II. Comparative in vivo and microsomal O-Dealkylation by mice
and flies. Comp. Gen. Pharmacol., 5:157-163.
Haque, A., I. Weisgerber and W. Klein.
1974. Beitrage Zue Okologischen Chemie. LXVIII. Metabolismus
von Buturon-luC in Weizenblattern. Chemosphere, 3(1):9-12.
Haque, R., and D. Hansen.
1974. Colored chlorinated hydrocarbon-clay complexes: An
electron spin resonance study. Abstracts, 167th ACS Meeting,
PEST 63, April 1-5.
Haque, R., and D. Hansen.
1975. New colored chlorinated hydrocarbon-clay complexes.
Bull. Environ. Contam. Toxicol., 13(4) :497-500.
Haque, R., and D. Schmedding.
1975. A method of measuring the water solubility of hydropholic
chemicals solubility of five polychlorinated biphenyls. Bull.
Environ. Contam. Toxicol., 14(1 ) : 13-18.
Hardcastle, J.E., and N. Mavichakana.
1974. Uptake of Mercuric chloride and methyl mercury chloride
from liquid media by Aspergillus niger and Penicillium notatum.
Bull. Environ. Contam. Toxicol., 11(5) :456-460.
Harke, H.P., A. Mauch, and B. Frahm.
1975. Dunnschicht-chromatographische Bestimmung von
und Nicotinmetaboliten im Urin
Harvey, J., Jr., A.G. Jelinek, and H.
1973. Metabolism of methomyl in
21(5):769-775.
Jr. , and H.L.
Decomposition
21(5):784-786
Jr. , and R.W.
Z. Anal
Sherman,
the rat.
Chem., 274
Nicotin
:300.
J. Agric. Food
Pease.
of methomyl
in soil . J. Agric. Food
Chem.
Harvey, J.
1973.
Chem.
Harvey, J.
1973.
J. Agric.
Hassall , K.A.
1975. Species and sex differences in the reductive dechlori-
nation of DDT by supplemented liver preparations. Pest.
Biochem. Physiol., 5:126-134.
Reiser.
Metabolism of methomyl in tobacco, corn and cabbage.
Food Chem., 21 (5) :775-783.
328
Hassall, K.A., and D. Manning.
1972. Anaerobic metabolism of DDT analogs by pigeon liver
preparations. Pest. Biochem. Physiol., 2(3) :331 -336.
Hattula, M.L., and 0. Karlog
1973. Absorption and elimination of polychlorinated bi phenyls
(PCB) in goldfish. Acta Pharmacol, et toxicol . 32:237-245.
Hawkins, D.R., W.H. Down, L.F. Chasseaud, and J.D. Lewis.
1974. The metabolic fate of tridemorph in rats. Pestic. Sci.,
5:535-542.
Hawkins, D.R., and V.H. Saggers.
1974. The fate of dinobuton and dinoseb on growing apples. Pestic.
Sci., 5:497-504.
Hawton, D., and E.H. Stobbe.
1971a. The fate of nitrofen in rape, redroot pigweed and green
foxtail. Weed Sci., 19(5) :555-558.
Hawton, D., and E.H. Stobbe.
1971b. The fate of nitrofen in echo rape, redroot pigweed and
green foxtail. Wed Sci. Soc. Am. Abstr., 44.
Hedlund, R.T., and C.R. Youngson.
1972. The rates of photodecomposition of picloram in aqueous
systems. Adv. Chem. Ser., 111:159-172.
Hee, S.S.Q., and R.G. Sutherland.
1974. The pyrolysis of some amine salts of 2,4-dichlorophenoxy-
acetic acid. J. Agr. Food Chem., 22:86-90.
Heenan, M.P., and J.N. Smith.
1974. Water-soluble metabolites of p_-Nitrophenol and 1-Naphthyl N-
Methyl carbamate in flies and grass grubs. Biochem. J., 144:303-310.
Helling, C.S., G. Dennison, and D.D. Kaufman.
1974. Fungicide movement in soil. Phytopathology, 64(8) : 1091 -11 00.
Helweg, A.
1975a. Degradation of 14C-labeled maleic hydrazide in soil as
influenced by sterilization, concentration and pretreatment.
Weed Res., 15:53-58.
Helweg, A.
1975b. Degradation of lltC-maleic hydrazide in soil as influenced
by adsorption of activated carbon. Weed Res., 15:129-133.
Herlihy, M. , and W. Quirke.
1975. The persistence of 2-chloro-6-(trichloromethyl )-pyridine
in soil. Comm. in Soil Sci. and Plant Anal., 6(5) : 51 3-520.
Herring, J.L., E.J. Hannan, and D.D. Bills.
1972. UV-irradiation of Aroclor 1254. Bull. Environ. Contam.
Toxicol., 8(3) :153-157.
Heuer, B., B. Yaron, and Y. Birk.
1974. Guthion half-life in aqueous solutions on glass surfaces.
Bull. Environ. Contam. Toxicol., 11 (6) :532-537.
Hicks, B.W.
1970. Fate of 2, 3-Dihydro-2,2-dimethyl-7-benzofuranyl-N^-methyl car-
bamate (furadan) and 2-methyl-2-(methylthio)propionaldehyde-0-(methyl-
carbamoyl )oxime (temik) in laying hens. Diss. Abstr., 31 (5) :2741-2742.
329
Hicks, 6.F., Jr., and T.R. Corner.
1973. Location and consequences of 1 ,1 ,l-Trichloro-2,2-bis
(p_-chloropheny1 )ethane uptake by Bacillus megaterium. Appl .
Microbiol., 25(3) :381-387.
Hiles, R.A.
1974. Adsorption, distribution and excretion of inorganic
tin in rats. Toxicol. Appl. Pharmacol., 27:366-379.
Hill, J.E., and R.I. Krieger.
1975. Uptake, translocation, and metabolism of tirpate in
tobacco Nicotiana tabacum. J. Agric. Food Chem., 23(6) :1125-1129.
Hilton, H.W., N.S. Nomura, W.L. Yauger, Jr., S.S. Kameda.
1974. Adsorption, translocation, and meatbolism of metribuzin
(Bay 94337) in sugarcane. J. Agric. Food Chem., 22(4) :578-582.
Hirata, H., and K. Ishizuka.
1975. Identification of the metabolite (M-l ) of 2-tert-Butyl-
4-(2,4-dichloro-5-isopropoxyphenyl )-A2-l ,3,4-oxadiazolin-5-one
(Oxadiazon) in rice plants. J. Agric. Biol„ Chem., 39(7):
1447-1454.
Hirwe, A.S., R.L. Metcalf, P.-Y. Lu, and L.-C. Chio.
1975. Comparative metabolism of 1 ,l-Bis-(£-Chlorophenyl )-
2-Nitropropane (Prolan) in mouse, insects, and in a model
ecosystem. Pest. Biochem. Physiol., 5:65-72.
Hoagland, R.E., and D.S. Frear.
1976. Behavior and fate of ethylenethiourea in plants.
J. Agric. Food Chem., 24(1 ) :1 29-133.
Hoagland, R.E., G. Graf, and E.D. Handel.
1974. Hydrolysis of 3' ,4'-dichloropropionanilide by plant aryl
acylamidases. Weed Res., 14:371-374.
Hock, W.K.
1969. Studies of the biodegradation and more of antifungal
action of chloroneb (1 ,4-dichloro-2,5-dimethoxybenzene).
Diss. Abstr., 29B(8):2705.
Hodgson, R.H.
1971. Alteration of diphenamid metabolism by ozone. Weed
Sci. Soc. Am. Abstr., 44-45.
Hodgson, R.H., K.E. Dusbabek, and B.L. Hoffer.
1974. Diphenamid metabolism in tomato: Time course of an ozone
fumigation effect. Weed Sci., 22(3) :205-210.
Hodgson, R.H., D.S. Frear, H.R. Swanson, and L.A. Regan.
1973. Alteration of diphenamid metabolism in tomato by ozone.
Weed Sci., 21 (6) :542-549.
Holloman, M.E., B.R. Layton, M.V. Kennedy, and C.R. Swanson.
1975. Identification of the major thermal degradation products
of the insecticide mirex. J. Agric. Food Chem., 23(5) :1 011-1012.
Holm, H.W., and H.F. Cox.
1974. Mercury in aquatic systems: Methylation, oxidation-
reduction, and bioaccumulation. EPA 660/3-74-021:1-29.
Holm, H.W. , and M.F. Cox.
1975. Transformation of elemental mercury by bacteria.
Appl. Microbiol., 29(4) :491 -494.
330
Holmstead, R.L., S. Khalifa, and J.E. Casida.
1974. Toxaphene composition analyzed by combined gas chroma-
tography - chemical ionization mass spectrometry. J. Agric.
Food Chem., 22(6) :939-943.
Holmstead, R.L., S. Kahlifa, and J.E. Casida.
1975. Studies of the reaction of toxaphene and mirex with
ferroprotoporphyrin model systems. Abstracts, 170th ACS
Meeting, PEST 131.
Hook, G.E.R., T.C. Orton, J. A. Moore, and G.W. Lucier.
1975. 2,3,7,8-Tetrachlorodibenzo-p_-dioxin-induced changes in
the hydroxylation of biphenyl by rat liver microsomes. Biochem.
Pharmacol., 24:335-340.
Hosier, C.F. , Jr.
1974. Degradation of Zectran in alkaline water. Bull. Environ.
Contam. Toxicol., 12(5) : 599-605.
Hosokawa, S., and J. Miyamoto.
1974. Metabolism of lt+C-labelled sumithion, 0,0-dimethyl
0-(3-methyl-4-nitrophenyl ) phosphorothioate in apples. Botyu-
Kagaku, 39(2):49-53.
Hsu, I.C., J. P. VanMiller, and J.R. Allen.
1975a. Metabolic fate of 3H-2,5,2' ,5'-tetrachlorobiphenyl
in infant nonhuman primates. Bull. Environ. Contam. Toxicol.,
14(2):233-240.
Hsu, I.C., J. P. VanMiller, J.L. Seymour, and J.R. Allen.
1975b. Urinary metabolites of 2,5,2' ,5'-tetrachlorobiphenyl
in the nonhuman primate. Proc. Soc. Explt'l. Biol. Med.,
150:185-188.
Hsu, J.C., and N.D. Camper.
1975. Degradation of Ioxynil to C02 in soil. Pest. Biochem.
Physiol., 5:47-51.
Hsu, T.S., and R. Bartha.
1974. Biodegradation of chloroaniline-humus complexes in soil
and in culture solution. Soil Sci . , 118(3) :213-220.
Huckins, J.N., J.E. Swanson, and D.L. Stalling.
1974. Perchlorination of polychlorinated biphenyls. J. Assoc.
Off. Anal. Chem., 57:416-417.
Hughes, A.F., and C.T. Corke.
1974. Formation of tetrachloroazobenzene in some Canadian
soils treated with propanil and 3,4-dichloroaniline. Can.
J. Microbiol., 21(l):35-39.
Hughes, L.B. , Jr.
1971. A study of the fate of carbaryl insecticide in surface
waters. Diss. Abstr., 32B(6):3108.
Hunn, J.B., and J.L. Allen.
1974. Movement of drugs across the gills of fishes. Ann. Rev.
Pharmac, 14:47-55.
Hunn, J.B., and J.L. Allen.
1975a. Renal excretion in coho salmon (Oncorhynchus kisutch)
after acute exposure to 3-trifluoromethyl-4-nitrophenol . J.
Fish. Res. Board Can., 32(10) :1873-1876.
331
Hunn, J.B., and J.L. Allen.
1975b. Residue dynamics of quinaldine and TFM in rainbow trout.
Gen. Pharmacol., 6:15-18.
Hustert, K. , and F. Korte.
1972. Beitrage zur Okologischen Chemie-XXXVIII . Synthese
Polychlorierter Biphenyle and ihre Reaktionen bei UV-Bestrahlung.
Chemosphere, 1(1): 7-1 0 .
Hutacharern, C, and C.O. Knowles.
1975. Metabolism of chlorpyrifos-ll+C in the eastern subterranean
termite. Bull. Environ. Contam. Toxicol., 13(3) :351 -356.
Hutson, D.H., M.K. Baldwin, and E.C. Hoadley.
1975. Detoxication and bioactivation of endrin in the rat.
Xenobiotica, 5(11 ) :697-714.
Hutson, D.H., and E.C. Hoadley.
1972. The comparative metabolism of [11+C-Vinyl] dichlorvos in
animals and man. Arch. Toxicol., 30:9-18.
Hutzinger, 0., W.D. Jamieson, and S. Safe.
1972a. Photochemical degradation of isomerically pure Di-,
Tetra-, Octa-, and Deca-chlorobiphenyls. Abstracts, 164th ACS
Meeting, WATER 23.
Hutzinger, 0., W.D. Jamieson, S. Safe, L. Paulmann, and R. Amnion.
1974. Identification of metabolic dechlorination of highly
chlorinated bi phenyl in rabbit. Nature, 252:698-699.
Hutzinger, 0., D. Nash, and S. Safe.
1972b. Metabolism of isomerically pure Mono-, Di-, Tetra-, and
Hexachloro-biphenyls by Mammal, bird and fish. Abstracts, 164th
ACS Meeting, WATER 39.
Hutzinger, 0., D.M. Nash, S. Safe, A.S.W. Defreitas, R.J. Norstrom,
D.J. Wildish, and V. Zitko.
1972c. Polychlorinated biphenyls: Metabolic behavior of pure
isomers in pigeons, rats, and brook trout. Science, 178:312-314.
Hutzinger, 0., S. Safe, and V. Zitko.
1972d. Photochemical degradation of chlorobiphenyls (PCBs).
Environ. Health Perspect., 1:15-20.
Hutzinger, 0., S. Safe, and V. Zitko.
1972e. Polychlorinated Biphenyls. Analabs Res. Notes, 12(2):1-11
Hylin, J.W.
1973. Oxidative decomposition of ethyl ene-bis-dithiocarbamates.
Bull. Environ. Contam. Toxicol., 10(4) :227-233.
Hyzak, D.L., and R.L. Zimdahl .
1974. Rate of degradation of metribuzin and two analogs in soil.
Weed Sci., 22(l):75-79.
Ide, A., Y. Niki, F. Sakamoto, I. Watanabe, and H. Watanabe.
1972. Decomposition of pentachlorophenol in paddy soil. Agric.
Biol. Chem., 36(11 ) :1937-1944.
Iguchi, T., K. Sawazaki , and A. Hayashi.
1974. Stability of pyrethroid insecticides in mosquito coil
extract (studies on pyrethroid insecticide part V.). J. Agric.
Chem. Soc. Jap. , 48:1-5.
332
Ingram, G.H., and E.M. Pull in.
1974. Persistence of bromoxynil in three soil types. Pestic.
Sci., 5:287-291.
Intrieri, C, and K. Ryugo.
1974. Uptake, transport and metabolism of (2-chloroethyl )-
trimethyl ammonium chloride in seedlings of almond (Primus
amygdalus, BATSCH.). J. Am. Soc. Hortic. Sci., 99(4) :349-352.
Iqbal, Z.M.
1971. Metabolism of 0-ethyl S^S-dipropyl phosphorodithioate
(MOCAP) in plants, rats, and liver microsomal systems. Diss.
Abstr., 31B(11):6665.
Ishikawa, K. , I. Okuda, and S. Kuwatsuka.
1973. Metabolism of benthiocarb (4-Chlorobenzyl N,N-
diethylthiolcarbamate) in mice. Agric. Biol. Chem., 37(1):
165-173.
Ishizuka, K. H. Hirata, and K. Fukunaga.
1975. Absorption, translocation and metabolism of 2-tert-
Butyl-4-(2,4-dichloro-5-isopropoxyphenyl )-A2-],3,4-oxadiazolin-
5-one (Oxadiazon) in rice plants. Agric. Biol. Chem., 39(7):
1431-1446.
Ishizuka, K. , I. Takase, K. Ei Tan, and S. Mitsui.
1973. Adsorption and translocation of 0-ethyl S^,S-Di phenyl
phosphorodithiolate (Hinosan) in rice plants. Agric. Biol.
Chem., 37(6):1307-1316.
Iverson, F., D.L. Grand, and J. Lacroix.
1975. Diazinon metabolism in the dog. Bull. Environ. Contam.
Toxicol., 13(5):611-618.
Iverson, F., and S.L. Hierlihy.
1974. Biotransformation of methyl mercury in the guinea pig.
Bull. Environ. Contam. Toxicol., 11(1):85-91.
Ivie, G.W.
1973. Nature and toxicity of two oxychlordane photoisomers.
J. Agric. Food Chem., 21 (6) :1 1 13-1115.
Ivie, G.W., D.E. Clark, and D.D. Rushing.
1974a. Metabolic transformation of disugran by rumen fluid
of sheep maintained on dissimilar diets. J. Agric. Food Chem.,
22(4):632-634.
Ivie, G.W., H.W. Dorough, and E.G. Alley.
1974b. Photodecomposition of mirex on silica gel chroma topi ates
exposed to natural and artificial light. J. Agric. Food Chem.,
22(6):933-935.
Ivie, G.W., W. Dorough, H.E. Bryant.
1974c. Fate of Mirex-14 in Japanese quail. Bull. Environ.
Contam. Toxicol., 11 (2):129-135.
Ivie, G.W., H.W. Dorough, and R.A. Cardona.
1973. Photodecomposition of the herbicide methazole. J.
Agric. Food Chem., 21 (3) :386-391 .
333
Ivie, G.W., J.R. Gibson, H.E. Bryant, J.J. Begin, J.R. Barnett,
and H.W. Dorough.
1974d. Accumulation, distribution, and excretion of Mirex-:ttC
in animals exposed for long periods to the insecticide in the
diet. J. Agric. Food Chem., 22(4) :646-653.
Iwata, Y., W.E. Westlake, and F.A. Gunther.
1973. Persistence of Parathion in six California soils under
laboratory conditions. Arch. Environ. Contam. Toxicol.,
l(l):84-96.
Iwata, Y., W.E. Westlake, and F.A. Gunther.
1973. Varying persistence of polychlorinated biphenyls in six
California soils under laboratory conditions. Bull. Environ.
Contam. Toxicol., 9(4):204-211.
Jackson, R.B.
1973. The metabolism of allyl alcohol in Trichoderma viride.
J. Gen. Appl. Microbiol., 19:41-54.
Jacob, T.A., J.R. Carlin, R.W. Walker, F.J. Wolf, and W.J. A. VendenHeuvel
1975. Photolysis of thiabendazole. J. Agric. Food Chem.,
23(4):704-709.
Jacobs, L.W., and D.R. Keeney.
1974. Methylmercury formation in mercury-treated river sediments
during in situ equilibration. J. Environ. Qual . , 3(2) :121-126.
Jamet, P., M.-A. Piedallu.
1975. Etude de l'adsorption et de la desorption de la pyrazone
(amino-5-chloro-4-phenyl-2(2H)pyridazinone-3) par differents
types de sols. Weed Res., 15:113-121.
Jamet, P., M-A. Piedallu, M. Hascoett.
1974. Migration et Degradation de L'Aldicarbe Dans Differents
types de sol. Internat'l. Atomic Energy Agency, SM-175/45:
393-415.
Jan, J., M. Komar, and M. Milohnoja.
1975. Excretion of some pure PCB isomers in milk of cows.
Bull. Environ. Contam. Toxicol., 13(3) :313-315.
Janes, N.F., A.F. Machin, M.P. Quick, H. Rogers, D.E. Mundy, and
A.J. Cross.
1973. Toxic metabolites of diazinon in sheep. J. Agric. Food
Chem., 21(1):121-124.
Jansson, B., S. Jensen, M. Olsson, L. Renberg, G. Sundstrom, and
R. Vaz.
1975. Identification by GC-MS of phenolic metabolites of PCB
and p_,p_'-DDE isolated from baltic guillemot and seal. Ambio,
4(2):93-97.
Jao, L.T., and J.E. Casida.
1974. Insect pyrethroid-hydrolyzing esterases. Pest. Biochem.
Physiol., 4:465-472.
Jeffcoat, B., and W.N. Harries.
1973. Selectivity and mode of action of ethyl (+)-2-(N-benzoyl-
3,4-dichloroanilino)propionate in the control of Avena fatua in
cereals. Pestic, Sci., 4:891-899.
334
Jensen, B.L., and R.E. Counsell .
1973. Acid hydrolysis products DDD and DDT precursors. J.
Org. Chem., 38:835-838.
Jensen, H.L.
1961. Some aspects of biological allyl alcohol dissimilation.
Acta Agric. Scand., 11:54-62.
Jensen, S., and L. Renberg.
1972. Contaminants in pentachlorophenol : Chlorinated dioxins
and predioxins. Ambio, l(2):62-65.
Jensen, S., and G. Sundstrom.
1974. Metabolic hydroxylation of a chlorobiphenyl containing
only isolated unsubstituted positions--2,2' ,4,4' ,5,5'-hexa-
chlorobiphenyl . Nature, 251:219-220.
Jhotty, J.S., and H. Singh.
1972. Stability of benomyl in plants. Phytochemistry, 11:
2207-2208.
Johannsen, F.R., and CO. Knowles.
1974. Toxicity and action of fluenethyl acaricide and related
compounds in the mouse, housefly and twospotted spider mite.
Comp. Gen. Pharmacol., 5:101-110.
Johnson, B.T.
1969. The degradation of DDT by soil-borne bacteria. Diss.
Abstr., 29B(9):3156.
Johnson, B.T., and J.0. Kennedy.
1973. Biomagnification of p_,p_'-DDT and methoxychlor by
bacteria. Appl . Microbiol., 26(1):66-71.
Johnson, B.T., and W. Lulves.
1975. Biodegradation of Di-n-Butyl Phthlate and Di-2-Ethylhexyl
Phthalate in freshwater hydrosoil. J. Fish Res. Bd. Can.,
32(3) :333-339.
Johnson, D.L., and M.E.Q. Pilson.
1975. The oxidation of arsenite in seawater. Environ. Lett.,
8(2):157-171.
Joiner, R.L.
1972. A study of the photoalteration products of parathion.
Diss. Abstr., 32B(7) :4169-4170.
Joiner, R.L., and K.P. Baetcke.
1973. Parathion: Persistence on cotton and identification
of its photoalteration products. J. Agric. Food Chem., 21(3):
391-396.
Joiner, R.L., and K.P. Baetcke.
1974. Identification of the photoalteration products formed
from parathion by ultraviolet light. J. Assoc. Off. Anal.
Chem., 57(2):408-415.
Jondorf, W.R., D.V. Parke, and R.T. Williams.
1958. Studies in detoxication: The metabolism of halogeno-
benzenes. 1,2,3,4-, 1 ,2,3,5-Tetrachlorobenzenes. Biochem.
J., 69:181-189.
335
Jones, A.S.
1976. Metabolism of Aldicarb by five soil fungi. J. Agric.
Food Chem., 24(1 ):115-117.
Jones, A.S., and C.S. Hodges.
1974. Persistence of mirex and its effects on soil micro-
organisms. J. Agric. Food Chem., 22(3) :435-439.
Jones, D.W.
1972. Absorption, translocation, and fate of the herbicide
2-(3,4-dichlorophenyl )-4-methyl-l ,2,4-oxadiazolidine-3,5-dione,
in cotton. Diss. Abstr., 32(10:5564.
Jones, H.A., and H.L. Haller.
1931. The "Yellow Compounds" resulting from the decomposition
of rotenone in solution. J. Am. Chem. Soc, 53:2320-2324.
Jordan, L.S., and V.A. Jolliffe.
1973. Simazine dealkylation in conjunction with citrus roots.
Pestic. Sci., 4:467-472.
Jordan. L.S., A. A. Zurqiyah, A.R. DeMur, and W.A. Clerx.
1975. Metabolism of siduron in Kentucky bluegrass (Poa
pratensis L.). J. Agric. Food Chem., 23(2):286-290.
Kaiser, K.L.E., and P.T.S. Wong.
1974. Bacterial degradation of polychlorinated biphenyls.
I. Identification of some metabolic products from Aroclor
1242. Bull. Environ. Contam. Toxicol., 11 (3) :291-296.
Kamada, T.
1971. Hygienic studies of pesticide residues. I. Accumulation
of BHC. Nippon Eiseigaku Zasshi , 26(4) :358-364.
Kamimura, S., M. Nishikawa, H. Saeki , and Y. Takahi.
1974. Absorption and metabolism of 3-Hydroxy-5-methylisoxazole
in plants and the biological activities of its metabolites.
Phytopathology, 64(10) :1273-1281 .
Kapoor, I. P.
1971. Comparative metabolism of DDT, methoxychlor and methio-
chlor in mammals, insects and in a model ecosystem. Diss.
Abstr., 31B(9):5408-5409.
Kapoor, I. P., R.L. Metcalf, A.S. Hirwe, J.R. Coats, and M.S. Khalsa.
1973. Structure activity correlations of biodegradability of
DDT analogs. J. Agric. Food Chem., 21 (2) :310-315.
Karanth, N.G.K., S.6. Bhat, C.S. Vaidyanathan, and V.N. Vasantharajan.
1974. Conversion of Dexon (p_-dimethylaminobenzenediazo sodium
sulfonate) to l^,N-dimethyl-p_-phenylenediamine by Pseudomonas
fragi Bk9. Appl . Microbiol., 27(1 ) :43-46.
Karanth, N.G.K., and V.N. Vasantharajan.
1973. Persistence and effect of dexon on soil respiration.
Soil Biol. Biochem., 5:679-684.
Karapally, J.C., J.G. Saha, and Y.W. Lee.
1973. Metabolism of Lindane-11+C in the rabbit: Ether-soluble
urinary metabolites. J. Agric. Food Chem., 21 (5) :811-818.
Katz, S.A., and M.H. Samitz.
1973. The binding of mercury to bovine serum albumin. Environ.
Res., 6:144-146.
336
Kaufman, D.D., J.R. Plimmer, and U.I. Klingebiel.
1973. Microbial oxidation of 4-chloroanil ine. J. Agric.
Food Chem., 21 (1 ):127-130.
Kawatski, J. A.
1970. Toxicity and metabolism of two chlorinated hydrocarbon
insecticides (Aldrin and Dieldrin) in the freshwater ostracod
Chlamydotheca arcuata (Sars). Diss. Abstr., 30B(9):4429.
Kawatski, J. A., and M.A. Bittner.
1975. Uptake, elimination, and biotransformation of the
lampricide 3-Trifluoromethyl-4-nitrophenol (TFM) by larvae
of the aquatic midge Chironomus tentans. Toxicology, 4:183-194.
Kawatski, J. A., and M.J. McDonald.
1974. Effect of 3-Trifluoromethyl-4-nitrophenol on in vitro
tissue respiration of four species of fish with preliminary
notes on its in vitro biotransformation. Comp. Gen. Pharmacol..
5:67-76.
Kearney, P.C., J.R. Plimmer, V.P. Williams, U.I. Klingebiel,
A.R. Isensee, T.L. Laanio, G.E. Stolzenberg, and R.G. Zaylskie.
1974. Soil persistence and metabolism of N-sec-butyl -4-tert-
butyl-2,6-dinitroaniline. J. Agric. Food Chem., 22(5) :856-859.
Kearney, P.C., E.A. Woolson, J.R. Plimmer, and A.R. Isensee.
1969. Decontamination of pesticides in soil. Residue Rev.,
29:137-149.
Kempe, L.L.
1973. Microbial degradation of the lamprey larvicide 3-
trifluoromethyl-4-nitrophenol in sediment-water systems.
Technical Report No. 18, Great Lakes Fishery Comm., 16 pages.
Kern, A.D., W.F. Meggitt, and D. Penner.
1975. Uptake, movement, and metabolism of cyanazine in fall
panicum, green foxtail, and corn. Weed Sci., 23(4):277-282.
Ketchersid, M.L., and M. G. Merkle.
1975. Persistence and movement of perfluidone in soil. Weed
Sci., 23(5):344-348.
Khalifa, S. , T.R. Mon, J.L. Engel , and J.E. Casida.
1974. Isolation of 2,2,5-endo, 6-exo, 8,9,10-heptachloro-
bornane and an octachloro toxicant from technical toxaphene.
J. Agric. Food Chem., 22(4) :653-657.
Khan, S.U.
1974. Adsorption of bipyridylium herbicides by humic acid.
J. Environ. Qual . , 3(3) :202-206.
Khan, S.U., and R. Mazurkewich.
1974. Adsorption of linuron on humic acid. Soil Sci., 118(5):
339-343.
Kiigemagi, U., R.J. Burnard, and L.C. Terriere.
1975. Analytical methods for the detection of the pesticide
1 ,1 '-methyl endi-2-naphthol (Squoxin) in fish and water.
J. Agric. Food Chem., 23(4):717.
337
Kilzer, L., S. Detera, I. Weisgerber, and W. Klein.
1974. Beitrage zur okologischen Chemie LXXVII: Verteilung
und metabolismus des Aldrin-Dieldrin-metaboliten trans-4,5-
dihydroxy-4,5-dihydroaldrin-lltC in Salatpflanzen und Boden.
Chemosphere, 3(4):143-148.
Kirklan, K., and J.D. Fryer.
1972. Degradation of several herbicides in a soil previously
treated with MCPA. Weed Res., 12:90-95.
Klaassen, CD.
1974a. Biliary excretion of arsenic in rats, rabbits, and
dogs. Toxicol. Appl . Pharmacol., 29(3) :447-457.
Klaassen, CD.
1974b. Biliary excretion of manganese in rats, rabbits, and
dogs. Toxicol. Appl. Pharmacol., 29(3) :458-468.
Klaassen, CD., and D.W. Shoeman.
1974. Biliary excretion of lead in rats, rabbits, and dogs.
Toxicol. Appl. Pharmacol., 29(3) :434-446.
Klee, G.E.
1972. DDT metabolism and movement in deciduous forest soil
microarthropods. Diss. Abstr., 32B(9):5233.
Klein, W., J. Kohli, I. Weisgerber, and F. Korte.
1973. Fate of Aldrin-lt+C in potatoes and soil under outdoor
conditions. J. Agric. Food Chem. , 21 (2) : 152-1 56.
Klein, W. , S. Zarif, and I. Weisgerber.
1972. Beitrage zur Okologischen Chemie XXXVI. Ruckstands-
verhalten von IsodrinluC und seiner Umwandlungsprodukte in
Weisskohl und Mohren. Chem. Mikrobiol. Technol . Lebensm. ,
1:121-125.
Knowles, CO., and S.A. Aziz.
1974. Metabolic fate of benzoyl chloride (2,4,6-trichloro-
phenyl )hydrazone (Banamite Acaricide) in the twospotted spider
mite. J. Econ. Entomol . , 67(5) : 574-576.
Kobayashi, l(. , and H. Akitake.
1975a. Studies on the Metabolism of chlorophenols in fish--
I. Absorption and excretion of PCP by goldfish. Bull. Jap.
Soc. Sci. Fish., 41(l):87-92.
Kobayashi, K. , and H. Akitake.
1975b. Studies on the metabolism of chlorophenols in fish--II.
Turnover of absorbed PCP in goldfish. Bull. Jap. Soc. Sci.
Fish., 41(l):93-99.
Kobayashi, K., H. Akitake, and T. Tomiyama.
1970. Studies on the metabolism of pentachlorophenate, a
herbicide, in aquatic organisms-Ill. Isolation and identi-
fication of a conjugated PCP yielded by a shell -fish, Tapes
philippinarum. Bull. Jap. Soc. Sci. Fish., 36(1 ) : 1 03-1 08.
Kocma, E.
1973. Levels of diethyldithiocarbamate in blood serum after
intra-peritoneal administration of its sodium salt and tetra-
ethylthiuram disulphide. Acta Pol. Pharmacol., XXX(2) :229-234.
338
Kohl i , J.D., R.N. Khanna, B.N. Gupta, M.M. Dhar, J.S. Tandon, and
K.P. Sircar.
1974. Absorption and excretion of 2,4-Dichlorophenoxyacetic
Acid in man. Xenoxibotic, 4(2) :97-100.
Kohl i , J., I. Weisgerber, and W. Klein.
1972. Beitrage zur Okologischen Chemie XLI(l). Umwandlung
und Ruckstandsverhalten von Dieldrin-14C in Zweibeln nach
Saatgutbehandlung. Chem. Mikrobiol. Technol . Lebensm., 1:
149-150.
Kohl i , J., I. Weisgerber, and W. Klein.
1976. Balance of Conversion of [11+C]Lindane in lettuce in
hydroponic culture. Pestic. Biochem. Physiol., 6:91-97.
Kohl i , J., I. Weisgerber, W. Klein, and F. Korte.
1973a. Beitrage Zur Okologischen Chemie. LIX. Ruckstand-
sverhalten und Umwandlun von Dieldrin-ll+C in Kulturpflanzen,
Boden und Sickerwasser Nach Bodenapplikation. Chemosphere,
2(4):153-156.
Kohli, J., S. Zarif, I. Weisgerber, W. Klein, and F. Korte.
1973b. Fate of Aldrin-^C in sugar beets and soil under
outdoor conditions. J. Agric. Food Chem., 21 (5) :855-857.
Kolberg, J., K. Helgeland, and J. Jonsen.
1973. Binding of 2,4-Dichloro- and 2,4,5-Trichlorophenoxyacetic
Acid to bovine serum albumin. Acta Pharmacol. Toxicol., 33:
470-475.
Koransky, W., G. Munch, G. Noack, J. Portig, S. Sodomann, and
M. Wirsching.
1975. Biodegradation of a-Hexachlorocyclohexane V. Character-
ization of the Major urinary metabolites. Naunyn-Schmiedeberg's
Arch. Pharmacol., 288:65-78.
Koshy, K.T., A.R. Friedman, A.L. VanDerSlik, and D.R. Graber.
1975. Photolysis of Benzoic acid 2-(2,4,6-Trichlorophenyl )
hydrazide. J. Agric. Food Chem., 23(6) : 1084-1 088.
Kossman, K.
1970. Uber Abbaugeschwindigkeit und Verteilung Von Phenmedipham
Im Boden. Weed Res., 10:349-359.
Kotzias, D., W. Klein, and F. Korte.
1973. Reaktion Des Buturons Bei UV-Bestrahlung. Chemosphere,
2:87-90.
Kovacicova, J., V. Batora, and S. Truchlik.
1973. Hydrolysis rate and i_n vitro anticholinesterase
activity of fenitrothion and S-methyl fenitrothion. Pestic.
Sci., 4:759-763.
Kraus, P., G. Noack, and J. Portig.
1973. Biodegradation of alpha-hexachlorocyclohexane. II.
Glutathione-mediated conversion to hydrophilic substance by
particulate fractions of rat liver and by homogenates of various
rat organs. Naunyn-Schmiedeberg's Arch. Pharmacol., 279:
199-202.
339
Krieger, R.I., P.W. Lee, A. Black, and T.R. Fukuto.
1973. Inhibition of microsomal aldrin epoxidation by diquat
and several related bipyridylium compounds. Bull. Environ.
Contam. Toxicol., 9(l):l-3.
Ku, T-Y., and P. A. Dahm.
1973. Effect of liver enzyme induction on paraoxon metabolism
in the rat. Pest. Biochem. Physiol., 3(2):175-188.
Kuhr, R.J.
1973. The metabolic fate of methomyl in the cabbage looper.
Pest. Biochem. Physiol., 3(2):113-119.
Kuhr, R.J., and A.C. Davis.
1975. Toxicity and metabolism of carbaryl in the European
corn borer. Pest. Biochem. Physiol., 5:330-337.
Kumar, Y., G.P. Semeluk, P.J. Silk, and I. Unger.
1974. The photochemistry of carbamates VI: The photodecom-
position of meobal (3,4-XYLYL-N-methyl carbamate) and mesurol
(4-methylthio-3,5-XYLYL-N-methyl carbamate). Chemosphere, 3(1):
23-27.
Kurihara, N., and M. Nakajima.
1974. Studies on BHC isomers and related compounds. VIII.
Urinary metabolites produced from y- and 6-BHC in the mouse:
Chlorophenol conjugates. Pest. Biochem. Physiol., 4(2) :220-231 .
Kurihara, N., M. Uchida, T. Fujita, and M. Nakajima.
1974a. Studies on BHC isomers and related compounds. VI.
Penetration and translocation of BHC isomers in the cockroach
and their correlation with physicochemical properties. Pest.
Biochem. Physiol., 4(1):12-18.
Kurihara, N., S. Wakamura, T. Nakamura, and M. Nakajima.
1974b. Isomerization of 1 ,3,4,5, 6-Pentachlorocyclohexene-l .
Agric. Biol. Chem., 38(9) :1717-1723.
Laanio, T.L., P.C. Kearney, and D.D. Kaufman.
1973. Microbial metabolism of dinitramine. Pest. Biochem.
Physiol., 3:271-277.
Labrecque, G.C., M.C. Bowman, R.S. Patterson, and J. A. Seawright.
1972. Persistence of thiotepa and tepa in pupae and adults
of Culex pi pi ens fatigans Wiedemann. Bull. Org. Mond. Sante
(Bull. W.H.O.), 47:675-676.
La Hue, D.W., L.D. Kirk, and G.C. Mustakas.
1975. Fate of dichlorvos residues during milling and oil
extraction of soybeans. Environ. Entomol . , 4(1 ):1 1-14.
Lamoureux, G.L., and K.L. Davison.
1975. Mercapturic acid formation in the metabolism of Propachlor,
CDAA, and Fluorodifen in the rat. Abstracts 170th ACS Meeting,
Chicago, 111., Aug. 25-29, PEST 1.
Lamoureux, G.L., and L. E. Stafford.
1974. The metabolism of 1 ,1 ,l-Trifluoro-N-[2-methyl-4-
(phenylsulfonylJphenyl-^C^U)] methanesulfonamide (Destun)
in plant seedlings. Abstracts, 167th ACS Meeting, PEST 62.
340
Lamoureux, G.L., L.E. Stafford, R.H. Shimabukuro, and R.G. Zaylskie.
1973. Atrazine metabolism in Sorghum: Catabolism of the
glutathione conjugate of Atrazine. J. Agric. Food Chem. ,
21(6):1020-1030.
Landner, L.
1972. The biological alkylation of mercury. Biochem. J.,
130(2) :67-69.
Lane, R.H., R.M. Grodner, and J.L. Graves.
1976. Irradiation studies of mallard duck eggs material
containing mirex. J. Agric. Food Chem., 24(1 ) : 1 92-1 93 -
Lanzilotta, R.P.
1969. Microbial and enzymatic transformations of 3 ' ,4 ' -
Dichloropropionanilide and related compounds. Diss. Abstr.,
29B(11):4016-4017.
Larsen, G.L., and J.E. Bakke.
1975. Metabolism of 2-Chloro-4-cyclopropylamino-6-isopropyl-
amino-s_-triazine (Cyprazine) in the rat. J. Agric. Food Chem.,
23(3):388-392.
Laveglia, J., and P. A. Dahm.
1975. Oxidation of Terbufos (Counter) in three Iowa soils.
Environ. Entomol . , 4(5) :71 5-718.
Lawley, P.D., S.A. Shah, D.J. Orr.
1974. Methylation of nucleic acids by 2,2-dichlorovinyl
dimethyl phosphate (Dichlorvos, DDVP). Chem. -Biol. Interact.,
8:171-182.
Lay, J. P., I. Weisgerber, and W. Klein.
1975. Conversion of the Aldrin/Dieldrin metabolite dihydro-
chlordene dicarboxylic acid - 14C in rats. Pest. Biochem.
Physiol., 5:226-232.
Lay, M.M., and R.D. Ilnicki.
1974. Peroxidase activity and propanil degradation in soil.
Weed Res., 15:111-113.
Lay, M.M., and R.D. Ilnicki.
1975. Effect of soil storage on propanil degradation. Weed
Res., 15:63-66.
Lay, J. P., W. Klein, and F. Korte.
1974. Beitrage zue okologischen Chemie-. LXXXV: Mikrosynthese
und in vitro Metabolismus von Dihydrochlorden-Dicarbonsaure-ll+C
durch Rattenleberorganellen. Chemosphere, 3(5) :1 93-198.
Lay, J. P., W. Klein, and F. Korte.
1975. Beitrage Zue Okologischen Chemie. C. Ausscheidung,
Speicherung und Metabolisierung Von 2,4,6,2' ,4'-Pentachloro-
biphenyl-11+C Nach Langzeitfutterung an Ratten. Chemosphere,
3:161-168.
Lay, J. P., I. Weisgerber, and W. Klein.
1975. Conversion of the Aldrin/Dieldrin metabolite dihydro-
chlordene Dicarboxylic Acid-ll+C in rats. Pest. Biochem.
Physiol., 5:226-232.
341
Leary, J.B.
1971. Gas chromatographic determination of monitor (0,S-Di methyl
Phosphoramidothioate) residues in crops. J. Assoc. Off. Anal.
Chem., 54(6): 1396-1 398.
Leary, J.B.
1974. Gas-liquid chromatographic determination of acephate
and ortho 9006 residues in crops. J. Assoc. Off. Anal. Chem.,
57:189-192.
Lech, J.J.
1972. Isolation and identification of TFM Glucuronide in
bile of TFM exposed rainbow trout. Fed. Proc, 31 (2) :606 .
Lech, J.J.
1973. Isolation and identification of 3-Trifluoromethyl-4-
nitrophenyl glucuronide from bile of rainbow trout exposed to
3-trifluoromethyl-4-nitrophenol . Toxicol. Appl . Pharmacol.,
24:114-124.
Lech, J.J.
1974. Glucuronide formation in rainbow trout--effect of
salicylamide on the acute toxicity, conjugation and excretion
of 3-trifluoromethyl-4-nitrophenol . Biochem. Pharmacol.,
23:2403-2410.
Lech, J.J., and N.V. Costrini.
1972. In vitro and in vivo metabolism of 3-trifluoromethyl-4-
nitrophenol (TFM) in rainbow trout. Compar. Gen. Pharmacol.,
3(10):160-166.
Lech, J.J., S. Pepple, and M. Anderson.
1973. Effects of Novobiocin on the acute toxicity, metabolism
and bi 11 iary excretion of 3-trifluoromethyl-4-nitrophenol in
rainbow trout. Toxicol. Appl. Pharmacol., 25:542-552.
Lech, J.J., and C.N. Statham.
1975. Role of glucuromide formation in the selective toxicity
of 3-trifluoromethyl-4-nitrophenol (TFM) for the sea lamprey:
Comparative aspects of TFM uptake and conjugation in sea lamprey
and rainbow trout. Toxicol. Appl. Pharmacol., 31:150-158.
Lee, S.S. , and S.C. Fang.
1973. Metabolism of monuron in excised leaves of corn and
bean plants. Weed Res., 13:59-66.
Lee, S.S., D.A. Griffin, and S.C. Fang.
1973. Identification of 3-D-glucosides of ring hydroxylated
ureas in monuron- treated bean leaves. Weed Res., 13:234-235.
Leesch, J.G., and T.R. Fukuto.
1972. The metabolism of abate in mosquito larvae and houseflies.
Pest. Biochem. Physiol., 2(2) :223-235.
Lefevre, P. A., and J.W. Daniel.
1973. Some properties of the organomercury-degrading system
in mammalian liver. FEBS Lett., 35(1 ) :121-123.
Leffingwell, J.T., R.C. Spear, and D. Jenkins.
1975. The persistence of ethion and zolone residues on grape
foilage in the central valley of California. Arch. Environ.
Contam. Toxicol., 3(l):40-54.
342
Leistra, M., and J.H. Smelt.
1974. Concentration-time relationships for methyl isothiocyanate
in soil after injection of metham-sodium. Pestic. Sci . , 5:409-417.
Leitis, E., and D.G. Crosby.
1974. Photodecomposition of trifluralin. J. Agric. Food Chem. ,
22(5):842-848.
Lenz, D.E., L.E. Deguehery, and J.S. Holton.
1973. On the nature of the serum enzyme catalyzing paraoxon
hydrolysis. Biochem. Biophys. Acta, 321:189-196.
Lewis, D.K.
1969. Residue studies using ^C-benazolin, with special
reference to its persistence on foliage under glasshouse
conditions. J. Sci. Food Agric, 20:185-190.
Lewis, D.L., D.F. Paris, and G.L. Baughman.
1975. Transformation of malathion by a fungus, Aspergillus
oryzae, isolated from a freshwater pond. Bull. Environ.
Contam. Toxicol., 13(5) :596-601 .
Lewis, R.J.
1970. Warfarin metabolism in man: Identification of metabolites
in urine. J. Clin. Invest., 49(5) :907-913.
Lichtenstein, E.P., T.W. Fuhremann, and K.R. Schulz.
1971. Persistence and vertical distribution of DDT, Lindane,
and Aldrin residues, 10 and 15 years after a single soil
application. J. Agric. Food Chem., 19(4) -.718-721 .
Lichtenstein, E.P., T.W. Fuhremann, and K.R. Schulz.
1974. Translocation and metabolism of [11+C]phorate as affected
by percolating water in a model soil -pi ant ecosystem. J.
Agric. Food Chem., 22(6) :991-996.
Lichtenstein, E.P., A. A. Hochberg, T.W. Fuhremann, R.N. Zahlten,
and F.W. Stratman.
1973. Metabolism of [14C] Parathion and [14C] Paraoxon with
fractions and subfractions of rat liver cells. J. Agric. Food
Chem., 21:416-424.
Lin, C, R. Chang, C. Casmer, and S. Symchowicz.
1973. Effects of phenobarbital , 3-methylcholanthrene, and
griseofulvin on the 0-demethylation of griseofulvin by liver
micromes of rats and mice. Drug Metab. Dispos., 1 (4) : 61 1-618.
Lin, T.H., H.H. North, and R.E. Menzer.
1975a. Metabolism of carbaryl (1-Naphthyl N-methyl carbamate) in
human embryonic lung cell cultures. J. Agric. Food Chem.,
23(2):253-256.
Lin, T.H., H.H. North, R.E. Menzer.
1975b. The metabolic fate of chlordimeform [N-(4-chloro-o-
tolyl )-N' ,N_' -dimethyl formami dine] in human embryonic lung
cell cultures. J. Agric. Food Chem., 23(2) :257-258.
Lingens, V.F.
1973. Abbau von Herbiziden und Fungiziden durch Mikroorganismen
des Bodens. Chimia, 27:628-635.
343
Locke, R.K., and V.W. Mayer.
1974. Physical evidence for the oxidative demethylation in
vitro of 1-naphthyl N-me thy 1 carbamate by the Udenfriend chemical
hydroxylation system. Biochem. Pharmacol., 23:1979-1984.
Lohs, P., B. Luckas, G. Strege, and H. Wetzel.
1974. Zue Persistenz von Thiuram auf Grunem Salat. Die Nahrung,
18(l):53-57.
Lokke, H.
1974. Residues in carrots treated with linuron. Pestic. Sci.,
5:749-757.
Long, J.W., and M.R. Siegel.
1975. Mechanism of action and fate of the fungicide chloro-
thalonil (2,4,5,6-tetrachloroisophthalonitrile) in biological
systems. Chem.-Biol. Interact., 10:383-394.
Long, J.W., L. Thompson, Jr., and C.E. Rieck.
1974a. Absorption, accumulation, and metabolism of benefin,
diphenamid, and pebulate by tobacco seedliags. Weed Sci.,
22(1 ) :42-47.
Long, J.W., L. Thompson, Jr., and C.E. Rieck.
1974b. Metabolism of 14C-pebulate in seedling tobacco. Weed
Sci., 22(l):91-94.
Lu, P.-Y., R.L. Metcalf, A.S. Hirwe, and J.W. Williams.
1975. Evaluation of Environmental Distribution and Fate of
Hexachlorocyclopentadiene, Chlordene, Heptachlor, and Heptachlor
Epoxide in a Laboratory Model Ecosystem. J. Agric. Food Chem.,
23(5) :967-973.
Machin, A.F.
1973. The isolation and possible significance of some toxic
mammalian metabolites of diazinon. Pestic. Sci., 4:425-430.
Machin, A.F., M.P. Quick, and N.F. Janes.
1971. 0-2-Acetyl-6-methyl-pyrimidin-4-yl 0,0-diethyl phosphoro-
thioate: A new degradation product of diazinon. Chem. Ind. ,
(42):1198-1199.
Maekawa, K., Y. Shuto, E. Taniguchi, and Y. Miyoshi.
1974. Thermal decomposition of Bis-(0,0-diemthyl thionophosphoryl )
disulfide. Botyu-Kagaku, 39:21-27.
Maes, R., R.H. Drost, H. Sauer.
1974. GLC determination of ekalux residues in various crops.
Bull. Environ. Contam. Toxicol., 1 1(2):121-127.
Mahler, J.R., D. Bieniek, and F. Korte.
1973. Beitrage Zur Okologischen Chemie. LIV. Solvolyse von
Heptachlor und Dieldrin Unter Hohen Drucken. Chemosphere, 1:31-33.
Mahoney, M.D., and D. Penner.
1975. Bentazon translocation and metabolism in soybean and navy
bean. Weed Sci. , 23(4) :265-271 .
Maki, A.W.
1974. The effects and fate of lampricide (TFM: 3-trifluoromethyl-
4-nitrophenol ) in model stream communities. PhD Diss, submitted
to Michigan State Univ., Dept. Fisheries and Wildlife, 162 pages.
344
Mallinckrodt, M.G., and H.P. Schmidt.
1970. Toxicity and metabolism of aminotriazole in man. Arch.
Toxikol., 27:13-18.
Mansour, M., H. Parlar, and F. Korte.
1975. Beitrage Zur Okologischen Chemie. CI. Reactions-
verhalten von 3,4-Dichloranilin und 3,4-dichlorophenol in
Losung, als Festkorper und in der Gasphase bei UV-Bestrahlung.
Chemosphere, 4(4) :235-240.
Marshall, R.S.
1972. Aldrin epoxication by non-enzymatic systems and its
inhibition by insecticide synergists. Diss. Abstr., 32(9):5233.
Mason, R.W.
1975. Binding of some phenoxyalkanoic acids to bovine serum
albumin in vitro. Pharmacol., 13:177-186.
Mathur, S.P., and J.G. Saha.
1975. Microbial degradation of lindane-C14 in a flooded
sandy loam soil. Soil Sci., 120(4) :301-307.
Matsuo, H., and J.E. Casida.
1970. Photodegradation of two dinitrophenolic pesticide
chemicals, dinobuton and dinoseb, applied to bean leaves.
Bull. Environ. Contam. Toxicol., 5(l):72-78.
Matthews, H.B., and M.W. Anderson.
1975a. The distribution and excretion of 2,4,5,2' ,5'-Pentachloro-
biphenyl in the rat. Drug Metab. Dispos., 3(3) :211-219.
Matthews, H.B., and M.W. Anderson.
1975b. Effect of chlorination on the distribution and
excretion of polychlorinated biphenyls. Drug Metab.
Dispos., 3(5):371-380.
Matthews, H.B., and J.D. McKinney.
1974. Dieldrin metabolism to cis-dihydroaldrindiol by rat
liver microsomes. Drug Metab. Dispos., 2(4) :333-340.
Maxwell, J., D.S. Kaushik, and C.G. Butler.
1974. Behaviour of an aziridine alkylating agent in acid
solution. Biochem. Pharmacol., 23:168-170.
McBride, B.C., and R.S. Wolfe.
1969. Biosynthesis of alkylated arsenic from CH3-B12 in
cell extracts of methane bacteria. Bacteriol. Proc. (P85). 130.
McClure, G.W.
1974. Degradation of anilide herbicides by propham-adapted
microorganisms. Weed Sci., 22:323-329.
McKinney, J.D., and H.M. Mehendale.
1973. Formation of polar metabolites from aldrin by pea
and bean root preparations. J. Agric. Food Chem. , 21(6):
1079-1084.
Medley, J.G., C.A. Bond, and D.W. Woodham.
1974. The cumulation and disappearance of mirex residues I.
In tissues of roosters fed four concentrations of mirex in
their feed. Bull. Environ. Contam. Toxicol., 11:217-223.
345
Mehendale, H.M.
1973. Aldrin epoxidation by plant root extracts. Phytochemistry,
12:1591-1594.
Mehendale, H.M., M. Fields, and H.B. Matthews.
1975. Metabolism and effects of hexachlorobenzene on hepatic
microsomal enzymes in the rat. J. Agric. Food Chem.,
23(2):261-265.
Meikle, R.W.
1973. Metabolism of 4-dimethylamino-3,5-xylyl methyl carbamate
(Mexacarbate, active ingredient of Zectran insecticide): A
unified picture. Bull. Environ. Contam. Toxicol., 10(l):29-36.
Meikle, R.W., C.R. Youngson, R.T. Hedlund, C.A.I. Goring, and
W.W. Addington.
1974. Decomposition of picloram by soil microorgansims: A
proposed reaction sequence. Weed Sci . , 22(3) :263-268.
Menashe, J., and R. Goren.
1973. Detoxification of fluometuron by citrus tissues. Weed
Res., 13:158-168.
Mendoza, C.E., H.A. McLeod, J.B. Shields, and W.E.J. Phillips.
1974. Determination of methomyl in rape seeds, oils and meals.
Pestic. Sci., 5:231-237.
Metcalf, R.A., and R.L. Metcalf.
1973. Selective toxicity of analogs of methyl parathion.
Pest. Biochem. Physiol., 3(2) :149-159.
Metcalf, R.L., I. P. Kapoor, and A.S. Hirwe.
1972. Development of biodegradable analogues of DDT. Chem.
Technol., 105-109.
Metcalf, R.L., P. Lu, and S. Bowlus.
1975a. Degradation and environmental fate of l-(2,6-difluoro-
benzoyl)-3-(4-chlorophenyl )urea. J. Agric. Food Chem.,
23(3):359-364.
Metcalf, R.L., J.R. Sanborn, P.-Y. Lu, and D. Nye.
1975b. Laboratory model ecosystem studies of the degradation
and fate of radiolabeled tri-, tetra-, and pentachlorobiphenyl
compared with DDE. Arch. Environ. Contam., 3(2) :1 51-1 65.
Mick, D.L.
1969. Metabolism of parathion by two species of Rhizobium.
Diss. Abstr., 30B(6) :2746-2747.
Middaugh, D.P., and C.L. Rose.
1974. Retention of two mercuricals by striped mullet, Mugil
cephalus. Water Res., 8:173-177.
Mihara, K. , and J. Miyamoto.
1974. Metabolism of sal ithion (2-methoxy-4H-l ,3,2-benzo-
dioxaphosphorin-2-sulfide) in rats and plants. Agric. Biol.
Chem., 38(10) :1913-1924.
Miller, J.H., P.E. Keeley, C.H. Carter, and R.J. Thullen.
1975. Soil persistence of trifluralin, benefin, and nitralin.
Weed Sci., 23(3) :211-214.
346
Miller, L.L., G.D. Nordblom, and G.A. Yost.
1974. Photochemistry of N-(a-trichloromethyl -£-methoxybenzyl )-£-
methoxyaniline. J. Agric. Food Chem., 22(5) :853-855.
Milnes, M.H.
1971. Formation of 2,3,7,8-tetrachlorodibenzodioxin by thermal
decomposition of sodium 2,4,5-trichlorophenate. Nature, 232:395-396.
Miyamoto, J., and T. Suzuki.
1973. Metabolism of Tetramethrin in Houseflies jn vivo. Pestic.
Biochem. Physiol. 3:30-41.
Miyamoto, J., and T. Suzuki.
1974. Metabolism of phenothrin or 3-phenoxybenzyl d-trans-chrysan-
themumate in mammals. Pest. Biochem. Physiol., 4:438-450.
Miyazaki, S., H.C. Sikka, and R.S. Lynch.
1975. Metabolism of dichlobenil by microorganisms in the aquatic
environment. J. Agric. Food Chem., 23(3) :365-368.
Moilanen, K.W., and D.G. Crosby.
1974. The photodecomposition of bromacil. Arch. Environ. Contam.
Toxicol., 2(1): 3-8 .
Montgomery, M. , T.C. Yu, and V.H. Freed.
1972. Kinetics of dichlobenil degradation in soil. Weed Res.,
12:31-36.
Morallo, B.D.
1970. The metabolism of mobam (4-benzy(b)thienyl N-methyl carbamate)
in resistant and susceptible houseflies. Diss. Abstr. , 30B(7):
3226-3227.
Morikawa, M. , S. Yokoyama, and J. Fukami .
1975. Comparative metabolism of chlordimeform on rat and rice
stem borer. Botyu-Kagaku, 40(4) :162-184.
Mosier, A.R., and W.D. Guenzi.
1973. Picloram photolytic decomposition. J. Agric. Food Chem.,
21(5):835-837.
Mosier, A.R., W.D. Guenzi, and L.L. Miller.
1969. Photochemical decomposition of DDT by a free-radical
mechanism. Science, 164:1083-1085.
Moza, P., I. Weisgerber, W. Klein, and F. Korte
1973. Beitrage Zur Okologischen Chemie. LXIII. Verteilung
und Metabolismus von 2,2'-Dichlorobiphenyl-lt+C in der hoheren
Sumpfpflanze Veronica beccabunga. Chemosphere, 2:217-222.
Moza, P., I. Weisgerber, W. Klein, and F. Korte.
1974. Metabolism of 2,2' -dichlorobi phenyl -lkC in two plant-water-
soil systems. Bull. Environ. Contam. Toxicol., 12(5) :541-546.
Muller, H., and W. Schuphan.
1975. Zur Anwendung von 2,4-Dichlorphenoxyessigsaure (2,4-D)
Bei Tomaten. Qual. Plant., 24(3/4) :405-413.
Muller, W.P., and F. Korte.
1975. Contributions to ecological chemistry CI I - Microbial
degradation of benzo-[a]-pyrene, monolinuron, and dieldrin in
waste composting. Chemosphere, 4(3) : 1 95-1 98 .
347
Muller, W., G. Nohynek, G. Woods, F. Korte, and F. Coulston.
1975a. Comparative metabolism of dieldrin-ll*C in mouse, rat,
rabbit, rhesus monkey and chimpanzee. Chemosphere, 4(2):89-92.
Muller, W., G. Woods, F. Korte, and F. Coulston.
1975b. Metabolism and organ distribution of dieldrin-^C in
rhesus monkeys after single oral and intravenous administration.
Chemosphere, 4(2):93-98.
Munakata, K., and M. Kuwahara.
1967. Photoche ical degr dation products of pentachlorophenol .
Residue Rev., 25:13-23.
Mundy, B.P., F.H.S. Liu, and G.A. Strobel.
1973. a-Aminobutyronitrile as an intermediate in cyanide fixation
by Rhizoctonia solani. Can. J. Biochem., 51:1440-1442.
Munster, J., R.S. Hermann, W. Koranski, and G.-A. Hoyer.
1975. Uber die Rolle von Pentachlorcyclohexen bie Stoffwechsel und
Wirkung von Hexachlorcyclohexan. I. Synthese von 3-Pentachlor-
cyclohexen und seine Identifizierung als Monodehydrochlorierungs-
produkt von a-Hexachlorcyclohexan. Hoppe-Seyler's Z. Physiol. Chem. ,
356:437-447.
Murphy, J. J., J. Didriksen, and R.A. Gray.
1973. Metabolism of 2-(a-naphthoxy)-N,N-diethyl propionamide in
tomato. Weed Sci. , 21 (1 ) :1 1 -1 5.
Murray, D.S., P.W. Santelmann, and J.M. Davidson.
1975. Comparative adsorption, desorption, and mobility of
dipropetryn and prometryn in soil. J. Agric. Food Chem., 23(3):
578-582. "
Nachtomi, E.
1970. The metabolism of ethylene dibromide in the rat. Biochem.
Pharmacol., 19:2853-2860.
Naito, N.
1958. Production of fungi toxic substance by fungi grown on media
containing either 2,4-D or related phenoxy compounds. Jap. J.
Bot., 16(2):153-162.
Naito, N., and Y. Kojima.
1957. Fungi toxic Substance Production by Gloeosporium ol i varum
which was grown on media containing 2-chlorophenoxyacetic acid or
2-methylphenoxyacetic acid. Tech. Bull. Fac. Agr. Kagawa Univ.,
9:18-25.
Naito, N. , and T. Tani.
1955. On a fungi tstatic substance produced in culture filtrates of
Gloeosporium ol i varum on media containing 2,4-D. Ann. Phytopath.
Soc. Jap. 19:129-132.
Naito, N., and T. Tani.
1956a. An antibiotic isolated from culture filtrates of Gloeo-
sporium oli varum grown on media containing 2,4-D. Jap. J. Bot.,
1 5(2) :1 52-163. "
348
Naito, N. , and T. Tarn".
1956b. A fungi toxic substance produced in cultures of Gloeo-
sporium olivarum on media containing 2,4-D. Ann. Phytopath. Soc.
Japan 21774
Nakagawa, M. , M. Ando, and Y. Obata
1975. Fate of isoxathion [0,0-diethyl 0-(5-phenyl -3-isoxazolyl )-
phosphorothioate] in soils. Agric. BioT. Chem. , 39( 9) : 1 763-1 773 .
Nakagawa, M. , and D.G. Crosby.
1974a. Photodecomposition of nitrofen. J. Agric. Food Chem.,
22(5):849-853.
Nakagawa, M. , and D.G. Crosby.
1974b. Photonucleophilic reactions of nitrofen. J. Agric. Food
Chem., 22(6):930-933.
Nakagawa, M. , T. Nakamura, and K. Tomita.
1974. Photolysis of 3-hydroxyisoxazoles. Agric. Biol. Chem.,
38(11 ):2205-2208.
Nakagawa, M., and H. Tamari.
1974. Photodecomposition of credazine, 3-(2-methylphenoxy )
pyridazine. J. Agric. Chem. Soc. Jap., 48(12) :651 -655.
Nakajima, S., N. Naito, and T. Tani.
1973. Microbial transformation of 2,4-D and its analogues.
Chem. Pharm. Bull., 21 (3) :671 -673.
Nakamura, K., J. Ito, and M. Dazai.
1974a. Mechanism of elimination of mercurials in waste water
by activated sludge. J. Ferment. Technol . , 52(11 ) :837-842.
Nakamura, K., J. Ito, and M. Dazai.
1974b. Mercury volatilization and the capacity of activated
sludge for waste water containing mercurials. J. Ferment.
Technol., 52(1 1 ) :843-847.
Neathery, M.W., W.J. Miller, R.P. Gentry, P.E. Stake, and D.M. Blackmon.
1974. Cadmium-109 and methyl mercury-203 metabolism, tissue
distribution, and secretion into milk of cows. J. Dairy Sci.,
57:1177-1183.
Nelson, J.D., W. Blair, F.E. Brinckman, R.R. Colwell, and W.P. Iverson.
1973. Biodegradation of phenylmercuric acetate by mercury-resistant
bacteria. Appl . Microbiol., 26(3) :321 -326.
Nelson, J.O., and F. Matsumura.
1973. Dieldrin (HEOD) metabolism in cockroaches and houseflies.
Arch. Environ. Contam. Toxicol., 1 (3) :224-244.
Neptune, M.D.
1970. Absorption, translocation, and metabolism of fluometuron
in corn and wheat. Diss. Abstr. , 31B(3):1110.
Neudorf, S., and M.A.Q. Khan.
1975. Pick-up and metabolism of DDT, dieldrin and photodieldrin
by a fresh water alga (Anki strode smus amalloides) and a micro-
crustacean (Daphnia pulex). Bull. Environ. Contam. Toxicol.,
13(4):443-449.
349
Neville, G.A., and T. Drakenberg.
1974. Mercuric mercury and methyl mercury complexes of glutathione.
Acta Chem. Scand., B28(4) :473-477.
Newby, L., and B.G., Tweedy.
1970. Comparison of amino acid exudates from leaves of two bean
varieties. Photopathology, 60:6.
Newland, L.W.
1969. The adsorption and degradation of insecticides by lake
sediments. Diss. Abstr. , 30B(3):938.
Newland, L.W., G. Chesters, and G.B. Lee.
1969. Degradation of y-BHC in simulated lake impoundments as
affected by aeration. J. Water Pollut. Control Fed., 41(5):
(part 2):R174-188.
Newsom, H.C., and W.G. Woods.
1973. Photolysis of the herbicide dinitramine (N3,N3-diethyl-2,
4-dinitro-6-trifluoromethyl-m-phenylenediamine). J. Agric. Food
Chem., 21:598-601.
Newsome, W.H.
1974a. A method for determining ethyl enebis (dithiocarbamate)
residues on food crops as bis(trifluoroacetamido)ethane. J.
Agric. Food Chem., 22(5) :886-889.
Newsome, W.H.
1974b. The excretion of ethylenethiourea by rat and guinea pig.
Bull. Environ. Contam. Toxicol., 1 1(2): 174-176.
Newsome, W.H., and G.W. Laver.
1973. Effect of boiling on the formation of ethylenethiourea in
zi neb-treated foods. Bull. Environ. Contam. Toxicol., 10(3):
151-154.
Newsome, W.H., J.B. Shields, and D.C. Villeneuve.
1975. Residues of maneb, ethylenethiuram monosulfide, ethylene-
thiourea, and ethyl enediamine on beans and tomatoes field treated
with maneb. J. Agric. Food Chem., 23(4) :756-757.
Nilles, G.P., and M.J. Zabik.
1974. Photochemistry of bioactive compounds. Multiphase photo-
degradation of basalin. J. Agric. Food Chem., 22(4) :684-688.
Nilles, G.P., and M.J. Zabik.
1975. Photochemistry of bioactive compounds. Multiphase photo-
degradation and mass spectral analysis of basagran. J. Agric.
Food Chem., 23(3) :410-415.
Nilsson, C.-A., K. Anderson, C. Rappe, and S.-0. Westermark.
1974. Chromatographic evidence for the formation of chlorodioxins
from chloro-2-phenoxyphenol s. J. Chromatogr. , 96:137-147.
Nimmo, D.R., J. Forester, P.T. Heitmuller, and G.H. Cook.
1974. Accumulation of Aroclor 1254 in grass shrimp (Palaemonetes
pugio) in laboratory and field exposures. Bull. Environ. Contam.
ToxTcol., ll(4):303-308.
350
Nishimura, M. , and N. Urakawa.
1972. A transport mechanism of mercury into ovarian follicles
in laying quail. Jap. J. Pharmacol., 22:605-616.
Nishiwaki, T., A. Ninomiya, S. Yamanaka, and K. Anda.
1972. Dechlorination of polychlorinated biphenyl by the UV-
irradiation. Nippon Kagaku Kaishi, 11:2225-2226.
Noack, G., and J. Protig.
1973. Biodegradation of alpha-hexachlorocyclohexane. III.
Decrease in liver non-protein thiol after intragastric application
of the drug. Naunyn-Schmiedeberg's Arch. Pharmacol., 280:183-189.
Noack, G., J. Portig, and M. Wirsching.
1975. Biodegradation of a-hexachlorocyclohexane. IV. The extent
of degradation of single doses in vivo. Naunyn-Schmiedeberg's
Arch. Pharmacol., 288:57-64.
Nolan, J., and H.J. Schnitzerling.
1975. Characterization of acetylcholinesterases of acaricide-
resistant and susceptible strains of the cattle tick Boophilus
microplus (Can). Pest. Biochem. Physiol., 5:178-188.
Norback, D.H. , J.F. Engblom, and J.R. Allen.
1975. Tissue distribution and excretion of octachlorodibenzo-p_-
dioxin in the rat. Toxicol. Appl . Pharmacol., 32:330-338.
Nordblom, G.D., and L.L. Miller.
1974. Photoreduction of 4,4'-dichlorobiphenyl . J. Agric. Food
Chem., 22(1 ):57-58.
Norseth, T.
1972. Biotransformation of methyl mercuric salts in the rat
with chronic administration of methyl mercuric cysteine. Acta
Pharmacol. Toxicol., 31:138-148.
North, H.H.
1972. Pesticide metabolism in mammalian cell cultures. Diss.
Abstr., 33B(5):2135.
North, H.H., and R.E. Menzer.
1973. Metabolism of DDT in human embryonic lung cell cultures.
J. Agric. Food Chem., 21 (3) :509-510.
Nose, K.
1972. Decachlorination of polychlorinated biphenyl and its
application to soil and rice analysis. ■ J. Agric. Chem. Soc. Jap.,
46(12) :679-681.
Oda, J., and W. Muller.
1972. Identification of a mammalian break-down product of
dieldrin. Symp. Chemistry of Pesticides under Metabolic and
Environ. Cond., Bonn, Sept. 1970, in Environ. Qual. Safety,
1:248.
Ohkawa, H., and J.E. Casida.
1971. Glutathione S-transferases liberate hydrogen cyanide from
organic thiocyanates. Biochem. Pharmacol., 20:1708-1711.
351
Ohkawa, H., M. Eto, and Y. Oshima.
1970. Metabolism and toxicity of salithion, 2-methoxy-4H-l,3,2-
benzodioxaphosphorin-2-sulfide. Jap. J. Appl. Entomol. Zool.,
14(4):191-194.
Ohkawa, H., Y. Hisada, N. Fujiwara, and J. Miyamoto.
1974a. Metabolism of N-(3' ,5'-dichlorophenyl )succinimide in
rats and dogs. Agric. Biol. Chem., 38(7) : 1359-1 369.
Ohkawa, H., N. Mi k ami, and J. Miyamoto.
1974b. Photodecomposition of Sumithion [0,0-dimethyl-0-(3-methyl-
4-nitrophenyl )phosphorothioate]. Agric. Biol. Chem., 38(11):
2247-2255.
Ohkawa, H., R. Shibaike, T. Hatanaka, and J. Miyamoto.
1975. Metabolism of the fungicide S-n-butyl S'-p_'-tert- butyl benzyl
N-3-pyridyldithiocarbonimidate (S-1358) in rats. Agric. Biol. Chem.,
39(8):1605-1615.
Ohkawa, H., R. Yoshihara, T. Hohara, and J. Miyamoto.
1974c. Metabolism of m-tolyl N-methyl carbamate (Tsumacide) in
rats, houseflies and bean plants. Agric. Biol. Chem., 38(5):
1035-1044.
Ohsawa, M. , and L. Magos.
1974. The chemical form of the methylmercury complex in the bile
of the rat. Biochem. Pharmacol., 23:1903-1905.
Ohsawa, T. , J.R. Knox, S. Khalifa, and J.E. Casida.
1975. Metabolic dechlorination of toxaphene in rats. J. Agric.
Food Chem., 23(1 ) :98-106.
Oloffs, P.C.
1970. Epoxidation of aldrin by cell-free pea root preparations.
Pestic. Sci., 1:228-232.
Olson, W.P.
1973. Dieldrin transport in the insect: An examination of Gerolt's
hypothesis. Pest. Biochem. Physiol., 3(4) :384-392.
Onsuka, F.I., and M.E. Comba.
1975. Isolation and characterization of the photoalteration
products of cis- and trans-chlordane. J. Assoc. Off. Anal. Chem.,
58(l):6-9.
Oppenoorth, S.V., W. Welling, N.W.H. Houx, and J.W. van den Oudenweyer.
1971. Synergism of insecticidal action in inhibition of microsomal
oxidation with phosphorothionates. Nat. New Biol., 223:187-188.
Otake, N., S. Takeuchi, T. Endo, and H. Yonehara.
1966a. Chemical studies on blasticidin S part II. The structure
of cytosinine and uracinine. Agric. Biol. Chem., 30(2) : 1 26-1 31 .
Otake, N., S. Takeuchi, T. Endo, and H. Yonehara.
1966b. Chemical studies on blasticidin S part III. The structure
of blasticidin S. Agric. Biol. Chem., 30(2) : 132-141 .
Ottoboni, A., and J.I. Ferguson.
1969. Excretion of DDT compounds in rat milk. Toxicol. Appl.
Pharmacol., 15:56-61.
352
Page, A.C., J.E. Loeffler, H.R. Hendrickson, C.K. Huston, and
D.M. DeVries.
1972. Metabolic fate of dichlorvos in swine. Arch. Toxikol.,
30:19-27.
Palm, H.L.
1971. Effects and fate of linuron and chlorbromuron in plants.
Diss. Abstr., 32B(6) :3113-3114.
Palut, D.
1970. Investigation of the metabolism of carbaryl- C on animal
model system. Rocz. Panstw. Zakl. Hig., 21(4) :41 7-426.
Pan, S.-K., N. Imura, and T. Ukita.
1973. Fractionation and characterization of mercury -methyl ati on
factor in tuna liver. Chemosphere, 6:247-252.
Pape, B.E., and M.J. Zabik.
1972. Photochemistry of bioactive compounds. Solution-phase
photochemistry of asymmetric triazin-5(4H)-ones. J. Agric. Food
Chem., 20(l):72-75.
Paris, D.F., D.L. Lewis, and N.L. Wolfe.
1975. Rates of degradation of ma lathi on by bacteria isolated from
aquatic system. Environ. Sci. Technol., 9(2):135-138.
Parke, D.V., and R.T. Williams.
1960. The metabolism of halogenobenzenes: (a) Penta- and hexa-
chlorobenzenes. (b) Further observations on 1 ,3,5-trichlorobenzene.
Biochem. J., 74:5-9.
Parker, C, and G.L. Hodgson.
1966. Some studies on the fate of picloram and dicamba in soils
underlying bracken. Proc. Eighth Br. Weed Con. Conf . , 2:614-615.
Parlar, H., and F. Korte.
1973. Beitrage Zur Okologischen Chemie. LX. Zur Photochemie
der Chlordanderivate. Chemosphere, 4:169-172.
Parr, J.F., and S. Smith.
1974. Degradation of DDT in an Everglades muck as affected by
lime, ferrous iron, and anaerobiosis. Soil Sci., 118(1 ) :45-52.
Parr, J.F., G.H. Willis, and S. Smith.
1970. Soil anaerobiosis: II. Effect of selected environments
and energy sources on the degradation of DDT. Soil Sci., 110(5):
306-312.
Paschal, E.H., C.C. Roan, and D.P. Morgan.
1974. Evidence of excretion of chlorinated hydrocarbon pesticides
by the human liver. Bull. Environ. Contam. Toxicol., 12(5) :547-554.
Paulson, G.D., and A.M. Jacobsen.
1974. Isolation and identification of Propham (isopropyl carbanilate)
metabolites from animal tissues and milk. J. Agric. Food Chem.,
22(4):629-631.
Paulson, G.D., A.M. Jacobsen, and G.G. Still.
1974. Alfalfa metabolites of isopropyl carbanilate (Propham): Their
fate when fed to sheep and rats. Abstracts, 168th ACS Meeting,
PEST 3.
353
Paulson, G.D., A.M. Jacobsen, R.G. Zaylskie, and V.J. Feil.
1973. Isolation and identification of Propham (isopropyl carbanilate)
metabolites from the rat and the goat. J. Agric. Food Chem. ,
21(5):804-811.
Pekas, J.C.
1974. Absorption of pesticidal carbamates from perfused intestinal
loops in conscious swine. Food Cosmet. Toxicol., 12:377-379.
Pekas, J.C, and J.L. Giles.
1974. Effect of dosing technique on absorption of carbaryl. Food
Cosmet. Toxicol., 12(1 ): 1 69.
Peoples, S.A., and J.U. Lakso.
1973. The methylation of inorganic arsenic in the ruminant and
carnivore. Proc. West. Pharmacol. Soc, 16:244.
Perscheid, M., H. Schluter, and K. Ballschmi ter.
1973. Aerober Abbau von Endosulfan durch Bodenmikroorganismen.
Aerobic degradation of endosulfan by mircoorganisms. Z. Naturforch.,
28(11/12) :761-763.
Pfaender, F.K.
1972. Metabolism of DDT by axenic cultures and natural microbial
communities. Diss. Abstr., 12B(part ) : 71 95 .
Pfaender, F.K., and M. Alexander.
1973. Effect of nutrient additions on the apparent cometabolism
of DDT. J. Agric. Food Chem., 21(3) :397-399.
Pfeilsticker, K., and H. Rasmussen.
1974. Umsetzungen von radioaktiv markiertem Athylenoxyd-l,2-14C
mit Weizeninhaltsstoffen. Z. Lebensm. Unters.-Forsch., 156:158-162.
Phillips, J., M. Wells, and C. Chandler.
1974. Metabolism of DDT by the freshwater planarian, Phagocata
yelata. Bull. Environ. Contam. Toxicol., 12(3) :355-358.
Phillips, R.A.
1972. The kinetics of metabolism of mercuric chloride in the rat.
Diss. Abstr., 33B(6):2679.
Ping, C.L., H.H. Cheng, and B.L. McNeal.
1975. Variations in picloram leaching patterns for several soils.
Soil Sci. Soc. Am. Proc, 39(3) :470-473.
Piper, W.N., J.Q. Rose, M.L. Leng, and P.J. Gehring.
1973. The fate of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)
following oral administration to rats and dogs. Toxicol. Appl.
Pharmacol., 26:339-351.
Plapp, F.W. , Jr.
1973. Comparison of insecticide absorption and detoxification in
larvae of the bollworm, Heliothis zea, and the tobacco budworm.
Pest. Biochem. Physiol., 2(4) :447-455.
Plimmer, J.R., and U.I. Klingebiel.
1971. Riboflavin photosensitized oxidation of 2,4-dichlorophenol :
Assessment of possible chlorinated dioxin formation. Science,
174:407-408.
354
Plimmer, J.R., and U.I. Klingebiel.
1974. Photochemistry of N-sec-butyl-4-tert-butyl-2,6-dinitroani line.
J. Agric. Food Chem. , 22(4) :689-693.
Plimmer, J.R., and U.I. Klingebiel, D.G. Crosby, and A.S. Wong.
1973. Photochemistry of dibenzo-p-dioxins. Adv. Chem. Ser.,
120:44-55.
Polles, S.G.
1971. The fate of C11+-labeled endrin in tobacco budworm (Heliothis
virescens (Fabricius) larvae. Diss. Abstr. , 31B(7):4115.
Pont, V., H.J. Jarczyk, G.F. Collet, and R. Thomas.
1974. Identification de Metabolites du Dimethyl-1 ,3(benzothiazolyl-
2)-3-uree et Etude de sa Stabilite In Vitro. Phytochemistry,
13:785-792.
Poore, R.E., andR.A. Neal.
1972. Evidence for extrahepatic metabolism of parathion. Toxicol.
Appl. Pharmacol., 23:759-768.
Portig, J., P. Kraus, S. Sodomann, and G. Noack.
1973. Biodegradation of alpha-hexachlorocyclohexane. I. Gluta-
thi one-dependent conversion to a hydrophilic metabolite by a rat
liver cytosol. Naunyn-Schmiedeberg's Arch. Pharmacol., 279:185-198.
Potter, J.C., A.C. Boyer, R.L. Marxmiller, R. Young, and J.E. Loeffler.
1973a. Radioisotope residues and residues of dichlorvos and its
metabolites in pregnant sows and their progeny dosed with dichlorvos-
14C or dichlorvos-36Cl formulated as PVC pellets. J. Agric. Food
Chem., 21(2):734-738.
Potter, J.C., J.E. Loeffler, R.D. Collins, R. Young, and A.C. Page.
1973b. Carbon-14 balance and residues of dichlorvos and its
metabolites in pigs dosed with dichlorvos-14C. J. Agric. Food
Chem., 21(2): 163-166.
Pree, D.J., and J.L. Saunders.
1974. Metabolism of carbofuran in mugho pine. J. Agric. Food
Chem., 22(4):620-625.
Preuss, P.W., A.G. Lemmens, and L.H. Weinstein.
1968. Studies on f luoro-organic compounds in plants. I.
Metabolism of 2-14C-f luoroacetate. Contrib. Boyce Thompson Inst.,
24:25-31.
Prince, R.H., G.M. Sheldrick, D.A. Stotter, and R. Taylor.
1975. Cobaloxime and DDT. X-ray crystal structure of an unexpected
vinyl-cobalt (III) complex. J. Chem. Soc. Chem. Commun., 854-855.
Prince, R.H., and D.A. Stotter.
1974. Alkyl-cobalt mediation of DDT hydrolysis. Nature, 249:286-287.
Prouty, R.M., J.E. Peterson, L.N. Locke, and B.M. Mulhern.
1975. DDD poisoning in a loon and the identification of the hydroxy-
lated form of DDD. Bull. Environ. Contam. Toxicol., 14(4) :385-388.
Puech, A. A., and J.C. Crane.
1975. Translocation of ethephon in fig (Ficus carica L.) shoots.
J. Amer. Soc. Hort. Sci., 100(4) :443-446.
355
Rabenstein, D.L., C.A. Evans, M.C. Tourangeau, and M.T. Fairhurst.
1975. Methylmercury species of equilibria in aqueous solution.
Anal. Chem., 47(2) :338-341 .
Radwan, M.A., and W.E. Dodge.
1970. Fate of radioactive tetramine in small mammals and its
possible use as a seedling protectant. Northwest Sci., 44(1):
25-30.
Ragab, M.T.H.
1974. Simazine persistence in soil and effects of its residue
on crops. Can. J. Plant Sci., 54:713-716.
Raig, P. , and R. Ammon.
1972. Nachweis einiger neuer phenol ischer Stoffwechselprodukte
des Biphenyls. Arzneim-Forsch. , 22(8): 1399-1403.
Ramsey, J.C., J.Q. Rose, W.H. Braun, and P.J. Gehring.
1974. Fate of 6-chloropicolinic acid following oral administration
in rats. J. Agric. Food Chem., 22(5) :870-873.
Ray, T.B., and C.C. Still.
1975. Propanil metabolism in rice: A comparison of propanil
amidase activities in rice plants and callus cultures. Pest.
Biochem. Physiol., 5:171-177.
Reddy, G., and M.A.Q. Khan.
1974. In vitro metabolism of [14C]photodieldrin by microsomal
mixed-function oxidase of mouse, rat, and houseflies. J. Agric.
Food Chem., 22(5) :910-912.
Reddy, G., and M.A.Q. Khan.
1975a. Metabolism of photodieldrin in rabbits. Abstracts
170th ACS Meeting, PEST 7, Aug. 25-29.
Reddy, G., and M.A.Q. Khan.
1975b. Fate of photodieldrin under various environmental
conditions. Bull. Environ. Contam. Toxicol., 13(l):64-72.
Reddy, G., and M.A.Q. Khan.
1975c. Metabolism, excretion, and tissue distribution of [ C]
photodieldrin in male rabbits, following single oral and
intraperitoneal administration. J. Agric. Food Chem.,
23(5):861-866.
Refsvik, T., and T. Norseth.
1975. Methyl mercuric compounds in rat bile. Acta Pharmacol.
Toxicol . , 36:67-78.
Reif, V.D., B.C. Littleton, and J.E. Sinsheimer.
1975. In vitro biotransformations of 1 -(o-chlorophenyl )-
l-(p-chTorophenyl-2,2-dichloroehtane (o^jT-DDD) and 1,1-
bis?£-chlorophenyl )-2,2-dichloroehtane (£,£>' -DDD) by bovine
adrenal. J. Agric. Food Chem., 23(5) :996-999.
Reif, V.D., and J.E. Sinsheimer.
1975. Metabolism of l-(o-chlorophenyl )-l-(p-chlorophenyl )-
2,2-dichloroethane (o,£'-DDD) in rats. Drug Metab. Dispos.,
3(l):15-25.
356
Rhodes, R.C., and J.D. Long.
1974. Run-off and mobility studies on benomyl in soils and
turf. Bull. Environ. Contam. Toxicol., 12(4) :385- 393.
Rice, C.P.
1972. Degradation of DDT by selected fresh water algae. Diss.
Abstr., 33B(4):1427.
Rice, C.P., and H.C. Sikka.
1973a. Fate of dieldrin in selected species of marine algae.
Bull. Environ. Contam. Toxicol., 9(2) : 11 6-123.
Rice, C.P., and H.C. Sikka.
1973b. Uptake and metabolism of DDT by six species of marine
algae. J. Agric. Food Chem., 21(2): 148-152.
Rice, C.P., H.C. Sikka, and R.S. Lynch.
1974. Persistence of dichlobenil in a farm pond. J. Agric.
Food Chem., 22(3) :533-534.
Rieck, C.E.
1970. Microbial degradation of 4-amino-3,5,6-trichloropicolinic
acid in soild and in pure cultures of soil isolates. Diss. Abstr.,
30B(9):3945.
Ross, J. A., and B.G. Tweedy.
1973. Malonic acid conjugation by soil microorganisms of a pesti-
cide-derived aniline moiety. Bull. Environ. Contam. Toxicol.,
10(4):234-236.
Ross, R.D., and D.G. Crosby.
1973. Photolysis of ethylenethiourea. J. Agric. Food Chem.,
21(3):335-337.
Ross, R.D., and D.G. Crosby.
1975. The photooxidation of aldrin in water. Chemosphere, 4(5):
277-282.
Ross, R.T., and F.J. Biros.
1975. A study of intermolecular complexes of bis(p-chlorophenyl )
acetic acid and some biologically significant compounds. Mass
Spectrometry and NMR Spectroscopy in Pesticide Chemistry. R. Haque
and F.J. Biros, eds., pp. 263-272.
Rouchaud, J. P., J.R. Decallonne, and J. A. Meyer.
1974. Metabolic fate of methyl-2-benzimidazole carbamate in melon
plants. Phytopathology, 64(12) : 1513-1517.
Rowland, I.R., M.J. Davies, and P. Grasso.
1975. The methyl ati on of mercury by the gastro-intestinal contents
of the rat. Biochem. Soc. Trans., 3:502-504.
Rowlands, D.G.
1971. The metabolism of contact insecticides in stored grains.
II. 1966-1969. Residue Rev., 34:91-161.
Rozman, K., W. Mueller, M. Iatropoulos, F. Coulston, and F. Korte.
1975. Ausscheidung, Koerpervertei lung und Metabol isierung von
Hexachlorbenzol nach Oraler Einzeldosis in Ratten und Rhesusaffen.
Chemosphere, 4(5) :289-298.
357
Rummens, F.H.A.
1975. Separation and structural assignment of the cj[s and trans
isomers of S-(2,3-dichloroal lyl )diisopropylthiocarbamate. Weed
Sci., 23(1 ):7-10.
Rusiecki, W., and A. Osicka.
1972. Distribution and excretion of mercury in rats intoxicated
with methylmercury dicyandiamide. Acta Pol. Pharm. , 29(6) :623-628.
Rusness, D.G., and G.G. Still.
1975. S-Cysteinyl-hydroxychlorpropham formation in oat. Abstracts,
170th ACS Meeting, PEST 21.
Ruzo, L.O., S. Safe, and M.J. Zabik.
1975. Photodecomposition of unsymmetrical polychl orobi phenyl s.
J. Agric. Food Chem., 23(3) :594-595.
Ruzo, L.O., and M.J. Zabik.
1975. Polyhalogenated biphenyls: Photolysis of hexabromo and
hexachlorobiphenyls in methanol solution. Bull. Environ. Contam.
Toxicol., 13(2):181-182.
Ruzo, L.O., M.J. Zabik, and R.D. Schuetz.
1972. Polychlorinated biphenyls: Photolysis of 3,4,3' ,4' -tetra-
chl orobi phenyl and 4,4'-dichlorobiphenyl in solution. Bull.
Environ. Contam. Toxicol., 8(4) : 21 7-21 8.
Ruzo, L.O., M.J. Zabik, and R.D. Schuetz.
1973. Photochemistry of bioactive compounds, kinetics of selected
s-triazines in solutions. J. Agric. Food Chem. , 21 (6) : 1 047-1 049-
Ruzo, L.O., M.J. Zabik, and R.D. Schuetz.
1974a. Photochemistry of bioactive compounds: Photoproducts and
kinetics of polychlorinated biphenyls. J. Agric. Food Chem.,
22(2) :199-202. "
Ruzo, L.O., M.J. Zabik, and R.D. Schuetz.
1974b. Photochemistry of bioactive compounds. Photochemical process
of polychlorinated biphenyls. J. Am. Chem. Soc, 96:3809-3813.
Ruzo, L.O., M.J. Zabik, and R.D. Schuetz.
1974c. Photochemistry of bioactive compounds. l-(4-Chlorophenyl )-
3-(2,6-dihalobenzoyl)ureas. J. Agric. rood Chem. , 22(6) : 1 106-1 1 08.
Saeki, S., A. Tsutsui, I. Oguri, H. Yoshimura, and M. Hamana.
1971. The isolation and structure elucidation of the main com-
ponents of kanechlor-400 (chlorobiphenyls). Fukuoka Acta Medica,
62(1 ):20-24.
Safe, S., and 0. Hutzinger.
1971. Polychlorinated Biphenyls: Photolysis of 2,4,6,2' ,4' ,6' -
Hexachlorobiphenyl. Nature, 232:1541-642.
Safe, S., 0. Hutzinger, and D. Ecobichon.
1974. Identification of 4-chloro-4'-hydroxybiphenyl and 4,4'-
dichloro-3-hydroxybiphenyl as metabolites of 4-chloro- and 4,4'-
dichl orobi phenyl fed to rats. Experientia, 30(7) : 720-721 .
Safe, S., 0. Hutzinger, D.J. Ecobichon, and A. A. Grey.
1975a. The metabolism of 4'-chloro-4-biphenylol in the rat. Can.
J. Biochem., 53(4) :41 5-420
358
Safe, S., 0. Hutzinger, and D. Jones.
1975c. The mechanism of chlorobiphenyl metabolism. J. Agric.
Food Chem., 23(5) :851 -853.
Safe, S., N. Platonow, and 0. Hutzinger.
1975b. Metabolism of chlorobiphenyls in the goat and cow. J.
Agric. Food Chem., 23(2) :259-261 .
Saha, J.G.
1974. The fate of lindane-11+C in wheat flour under normal con-
ditions in bread making. J. Inst. Can. Sci. Technol. Aliment.,
7(2):101-104.
Saha, J.G., R.H. Burrage, Y.W. Lee, M. Saha, and A.K. Sumner.
1974. Insecticide residue in soil, potatoes, carrots, beets,
rutabagas, wheat plants and grain following treatment of the soil
with dyfonate. Can. J. Plant Sci., 54:717-723.
Saha, J.G. , and Y.W. Lee.
1974. Degradation of lindane-11+C by wheat grain. Environ. Lett.,
7(4):359-366.
Saltzman, S., B. Yaron, and U. Mingelgrin.
1974. The surface catalyzed hydrolysis of parathion on kaolinite.
Soil Sci. Soc. Am. Proc, 38(2) : 231 -234.
Sanborn, J.R., and C.-C. Yu.
1973. The fate of dieldrin in a model ecosystem. Bull. Environ.
Contam. Toxicol., 10(6) :340-346.
Sanders, H.O., and D.F. Walsh.
1975. Toxicity and residue dynamics of the lampricide 3-trifluoro-
methyl-4-nitrophenol (TFM) in aquatic invertebrates. Investigations
in Fish Control. No. 59. U. S.D.I. Fish and Wildlife Service.
Washington, D.C. 9 pages.
Sandrock, K., D. Bienieck, W. Klein, and F. Korte.
1974. Beitrage zue Okologischen Chemie. LXXXVI. Isolierung und
Strukturaufklarung von Kelevan-11+C-metabol iten und Bilanz in
Kartoffeln und Boden. Chemosphere, 3(5):199-204.
Satch, T.
1973. A liver arylamidase extremely sensitive to organophosphorus
compounds. Life Sci., 13:1181-1188.
Schafer, D.E., and E.H. Stobbe.
1973. Translocation and metabolism of benazolin in wild mustard
and rape species. Weed Sci., 21(1):48-51.
Schlagbauer, B.G.L., and A.W.J. Schlagbauer.
1972. Part I. The metabolism of carbamate pesticides--A liter-
ature analysis. Residue Rev., 42:1-90.
Schoor, W.P.
1973. In vivo binding of p,p'-DDE to human serum proteins. Bull.
Environ. Contam. Toxicol., 9(2):70-74. Schottel , J., A. Mandal ,
Schottel, J., A. Mandal, D. Clark, and S. Silver.
1974. Volatilisation of mercury and organomercurials determined
by inducible R-factor systems in enteric bacteria. Nature, 251:
335-337.
359
Schrauzer, G.N., J.H. Weber, T.M. Beckham, and R.K.Y. Ho.
1971. Alkyl group transfer from cobalt to mercury: The reaction
of alkylcobalamins, alkylcobaloximes and of related compounds with
mercuric acetate. Tetrahedron Lett., 3:275-277.
Schulte, E., and L. Acker.
1974. Identifizierung und Metabol isierbarieit von polychlorierten
Biphenylen. Naturwissenschaften, 61(2):79-80.
Schumacher, H.G., H. Parlar, W. Klein, and F. Korte.
1973. Photochemische Reaktionen von Endosulfan. Chemosphere,
2:65-68.
Schuphan, I., and K. Ballschmiter.
1972. Metabolism of polychlorinated norbornenes by Clostridium
butyricum. Nature, 237:100-101.
Schutte, H.R., and U. Stephan.
1969. Abbau des Herbizids Chloralhydrat im Boden. Z.
Pflanzenernahr., Dung., Bodenkd. , 123(3) :212-219.
Segall, H.J., and J.M. Wood.
1974. Reaction of methyl mercury with plasmalogens suggests a
mechanism for neurotoxicity of metal -alkyl s. Nature, 248:456-458.
Seidler, H., R.M. Macholz, M. Hartig, M. Kujawa, and R. Engst.
1975. Untersuchungen uber den Metabolismus einiger Insektizide
und Fungizide in der Ratte. 4. Mitt. Verteilung, Abbau und
Ausscheidung von 14-C-markiertem Lindan. Die Nahrung, 19(5/6):
473-482.
Sell, J.L., and K.L. Davison.
1975. Metabolism of mercury, administered as methyl merucric
chloride or merucric chloride, by lactating ruminants. J. Agric.
Food Chem., 23(4) :803-808.
Sellers, L.G.
1971. Distribution, metabolism and localization of dieldrin in
the adult house fly, Musca domesti ca (L.). Diss. Abstr. ,
32B(2):999.
Sethunathan, N.
1972. Diazinon degradation in submerged soil and rice-paddy water.
Adv. Chem. Ser., 111:244-255.
Sethunathan, N.
1973. Degradation of parathion in flooded acid soils. J. Agric.
Food Chem"., 21 (4) :602-604.
Sethunathan, N., and T. Yoshida.
1973. Parathion degradation in submerged rice soils in the
Philippines. J. Agric. Food Chem., 21 (3) :504-506.
Seto, H., N. Otake, and H. Yonehara.
1966. Biological transformation of blasticidin S by Aspergillus
fumigalus sp. Agric. Biol. Chem., 30(9) :877-886.
Sharpee, K.W., J.M. Duxbury, and M. Alexander.
1973. 2,4-Dichlorophenoxyacetate metabolism by Arthrobacter sp.:
Accumulation of chlorobutenolide. Appl . Microbiol., 26(3) :445-447.
360
Shatoury, H.H.
1972. Fate of internal doses of DDT. Experientia, 28(9) :1062-1063.
Shcherbakov, Y.A., and I.V. Pol uboyari nova.
1970. Stability of the butyl ester of 2,4-D. Edsp. Vod. Toksikol.
Mater. Vses. Simp., 1:32-35.
Sherman, J.C., T.A. Nevin, and J. A. Lasater.
1974. Hydrogen sulfide production from ethion by bacteria in
lagoonal sediments. Bull. Environ. Contam. Toxicol., 12(3):
359-365.
Shida, T. , Y. Homma, and T. Misato.
1973. Bacterial degradation of N-lauroyl-L-valine. Agric. Biol.
Chem., 37(5):1027-1033.
Shimabukuro, R.H., G.L. Lamoureux, H.R. Swanson, W.C. Walsh,
L.E. Stafford, and D.S. Frear.
1973a. Metabolism of substituted di phenyl ether herbicides in
plants. II. Identification of a new fluorodifen metabolite,
S-(2-nitro-4-trifluoromethylphenyl glutathione in peanut.
Pest. Biochem. Physiol., 3(4) :483-494.
Shimabukuro, R.H., W.C. Walsh, G.L. Lamoureux, and L.E. Stafford.
1973b. Atrazine metabolism in sorghum: Chloroform-soluble
intermediates in the N-dealkylation and glutathione conjugation
pathways. J. Agric. Food Chem., 21 ( 6) : 1 031 -1 036 .
Shindy, W.W., L.S. Jordan, V.A. Jolliffe, C.W. Coggins, Jr., and
J. Kumamoto.
1973. Metabolism of [ll+C]naphthaleneacetic acid in Kinnow
Mandarin. J. Agric. Food Chem. , 21 (4) :629-631 .
Shono, T.
1974a. Studies on the mechanism of resistance in diazinon
resistant Hokota strain of houseflies. II. In vitro degradation
of diazoxon. Botyu-Kagaku, 39{ II): 54-59.
Shono, T.
1974b. Studies on the mechanism of resistance in diazinon
resistant Hokota strain of houseflies. III. Diazinon degradation
by glutathione-S-transferase. Botyu-Kagaku, 39( 1 1 1 ) : 75-80.
Shono, T.
1974c. Studies on the mechanism of resistance in diazinon
resistant Hokota strain of houseflies. IV. Diazinon metabolism
by mixed-function oxidase. Botyu-Kagaku, 39( III) :80-84.
Siddaramappa, R., K.P. Rajaram, and N. Sethunathan.
1973. Degradation of parathion by bacteria isolated from flooded
soil. Appl. Microbiol., 26(6) :846-849.
Siegel, M.R.
1975. Benomyl-soil microbial interactions. Phytopathology, 65(2):
219-220.
Siegel, M.R., and A.J. Zabbia, Jr.
1972. Distribution and metabolic fate of the fungicide benomyl in
dwarf pea. Phytopathology, 62(6) :630-634.
361
Sikka, H.C., D. Ford, and R.S. Lynch.
1975. Uptake, distribution, and metabolism of endothall in fish.
J. Agric. Food Chem. , 23(5) :849-851 .
Sikka, H.C., R.S. Lynch, and M. Lindenberger.
1974. Uptake and metabolism of dichlobenil by emersed aquatic
plants. J. Agric. Food Chem. , 22(2) :230-234.
Sikka, H.C., and J. Saxena.
1973. Metabolism of endothall by aquatic microorganisms. J. Agric.
Food Chem., 21 (3) :402-406.
Silk, P.J., and I. Unger.
1972. The photodecomposition of 1 ,1 -dichloro-2,2-bis(5' -chloro-2' -
methoxyphenyl ) ethylene (MPE), an analogue of DDE. Int. J. Environ.
Anal. Chem., 1:301-306.
Silk, P.J., and I. Unger.
1973. The photochemistry of carbamates. I. The photodecomposition
of Zectran. Int. J. Environ. Anal. Chem., 2:2131-220.
Sink, J.D., H. Varela-Alvarez, and C. Hess.
1972. Metabolism of 14C-DDT by ovine rumen fluid in vitro. J.
Agric. Food Chem., 20(l):7-9.
Sirons, G.J., R. Frank, and T. Sawyer.
1973. Residues of atrazine, cyanazine, and their phytotoxic
metabolites in clay loam soil. J. Agric. Food Chem., 21(6):
1016-1020.
Slade, M. , G.T. Brooks, H.K. Hetnarski, and C.F. Wilkinson.
1975. Inhibition of the enzymatic hydration of the epoxide HEOM in
insects. Pest. Biochem. Physiol., 5:35-46.
Sloan, J. P., J.A.J. Thompson, and P. A. Larkin.
1974. The biological half-life of inorganic mercury in the
Dungeness crab (Cancer magister). J. Fish. Res. Board Can., 31(10):
1571-1576.
Smelt, J.H., and M. Leistra.
1974. Conversion of metham-sodium to methyl isothiocyanante and
basic data on the behaviour of methyl isothiocynate in soil. Pestic.
Sci., 5:401-407.
Smith, A.E.
1971. Degradation of bromoxynil in Regina heavy clay. Weed Res.,
11:276-282.
Smith, A.E.
1972. The hydrolysis of 2,4-dichlorophenoxyacetate esters to
2,4-dichlorophenoxyacetic acid in Saskatchewan soils. Weed Res.,
12:364-372.
Smith, A.E.
1973a. Transformation of dicamba in Reqina heavy clay. J. Agric.
Food Chem., 21 (4) :708-7l0.
Smith, A.E.
1973b. Degradation of dicamba in prairie soils. Weed Res.,
13:373-378.
Smith, A.E.
1974. Breakdown of the herbicide dicamba and its degradation
product 3,6-dichlorosalicylic acid in prairie soils. J. Agric.
Food Chem., 22(4) : 601 -605.
362
Smith, A.E., and D.R. Cul limore.
1974. The vn vitro degradation of the herbicide bromoxynil.
Can. J. MicrobToTTT 20(5) :773-776.
Smith, A.E., and D.R. Cullimore.
1975. Microbiological degradation of the herbicide dicamba in
moist soils at different temperatures. Weed Res., 15:59-62.
Smith, A.E., andR.E. Wilkinson.
1974. Differential absorption, translocation and metabolism of
metribuzin [4-amino-6-tert-butyl -3- (methyl thio)-as-triazine-
5(4H)one] by soybean cultivars. Physiol. Plant., 32:253-257.
Smith, B.R., W.C. Dauterman, and E. Hodgson.
1974. Selective inhibition of the metabolism of diazinon and
diazoxon J_n vitro by piperonyl butoxide, NIA 16824, and
l-(2-isopropyl phenyl ) imidazole. Pest. Biochem. Physiol.,
4:337-345.
Smith, L.W., and F.-Y. Chang.
1973. Aminotriazole metabolism in Cirsium arvense (L.) Scop.
and Pi sum sativum L. Weed Res., 13(4) :339-350.
Smith, R.A., W.S. Belles, K.-W. Shen, and W.G. Woods.
1973. The degradation of dinitramine (N3,N3 -diethyl 2,4-dinitro-
6-trifluoromethyl-m-phenylenedi amine) in soil. Pest. Biochem.
Physiol., 3(3):278-288.
Snell, M., and L.V. Edgington.
1970. Uptake, translocation and decomposition of systemic oxathiin
fungicides in bean. Phytopathology, 60(1 2) :1 708-1 716-
Soderquist, C.J., and D.G. Crosby.
1975. Dissipation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in
a rice field. Pestic. Sci., 6:17-33.
Soderquist, C.J., D.G. Crosby, K.W. Moilanen, J.N. Sieber, and
J.E. Woodrow.
1975. Occurrence of trifluralin and its photoproducts in air.
J. Agric. Food Chem. , 23(2) :304-309.
Solel, Z., J.M. Schooley, and L.V. Edgington.
1973. Uptake and translocation of benomyl and carbendazim (methyl
benzimidazol-2-yl carbamate) in the symplast. Pestic. Sci.,
4:713-718.
Sorensen, D.O.
1971. Kolorimetrisch bestimmbare Herbizide: Analyse, Abbau,
Toxikologie. Vom Wasser, 38:17-26.
Spangler, W.J., J.L. Spigarelli, J.M. Rose, R.S. Flippin, and
H.H. Miller.
1973a. Degradation of methylmercury by bacteria isolated from
environmental samples. Appl. Microbiol., 25(4) :488-493.
Spangler, W.J., J.L. Spigarelli, J.M. Rose, and H.M. Miller.
1973b. Methylmercury: Bacterial degradation in lake sediments.
Science, 180:192-193.
363
Spear, R.C., W.J. Popendorf, J.T. Leffingwell, and D. Jenkins.
1975. Parathion residues on citrus foliage. Decay and composition
as related to worker hazard. J. Agric. Food Chem., 23(4) :808-810.
Spencer, W.F., M.M. Cliath, W.J. Farmer, and R.A. Shepherd.
1974. Volatility of DDT residues in soil as affected by flooding
and organic matter applications. J. Environ. Qual., 3( 2) : 1 26-1 29-
Spengler, D., and A. Jumar.
1969. Modellunterschunger uber den Abbau des herbiziden Wirkstoffes
Proximpham. Arch. Pflanzenschutz, 5(6) :445-453.
Spitznagle, L.A.
1970. Metabolism and residue properties of the plant growth
regulator, 2,3,5-triiodobenzoic acid in field-growth soybeans.
Diss. Abstr., 30B(9) :401 6-401 7.
Sprankle, P., W.F. Meggitt, and D. Penner.
1975a. Rapid inactivation of glyphosate in the soil. Weed Sci.,
23(3):224-228.
Sprankle, P., W.F. Meggitt, and D. Penner.
1975b. Adsorption, mobility, and microbial degradation of
glyphosate in soil. Weed Sci., 23(3) :229-234.
St. John, L.E., Jr., and D.J. Lisk.
1973. Metabolic studies with chloropropylate acaricide in the
dairy cow. J. Agric. Food Chem., 21 (4) :644-646.
St. John, L.E., Jr., and D.J. Lisk.
1974a. Feeding studies with randox in the dairy cow. Bull.
Environ. Contam. Toxicol., 11 (6) : 529-531 .
St. John, L.E., Jr., and D.J. Lisk.
1974b. Feeding studies with supracide in the dairy cow. Bull.
Environ. Contam. Toxicol., 12(5) :594-598.
St. John, L.E., Jr., and D.J. Lisk.
1975. A feeding study with the herbicide, Kerb (N-(l ,1 -dimethyl -
propynyl )-3,5-dichlorobenzamide, in the dairy cow. Bull. Environ.
Contam. Toxicol., 13(4) :433-435.
Staiff, D.C., S.W. Comer, J.F. Armstrong, and H.R. Wolfe.
1975. Persistence of azinphosmethyl in soil. Bull. Environ.
Contam. Toxicol., 13(3): 362-368.
Stanton, R.H., and M.A.Q. Khan.
1973. Mixed-function oxidase activity toward cyclodiene insecticides
in bass and bluegill sunfish. Pestic. Biochem. Physiol., 3:351-357.
Starr, R.I.
1972. The absorption, translocation, and metabolism of lt+C-4-
aminopyridine in corn and sorghum: Its movement and degradation
in soil systems. Diss. Abstr., 33B(6) :2443-2444.
Starr, R.I., and D.J. Cunningham.
1974a. Phytotoxicity, absorption and translocation of 4-amino-
pyridine in corn and sorghum growing in treated nutrient cultures
and soils. J. Agric. Food Chem., 22(3) :409-413.
364
Starr, R.I., and D.J. Cunningham.
1974b. Dearadation of "^C-labeled mesurol in soil and water.
Abstracts 168th ACS Meeting, Atlantic City, NJ, Sept. 9-13, PEST 59.
Starr, R.I., and D.J. Cunningham.
1975a. Leaching and degradation of 4-aminopyridine-lttC in several
soil systems. Arch. Environ. Contam. Toxicol., 3(l):72-83.
Starr, R.I., and D.J. Cunningham.
1975b. Degradation of 4-aminopyridine-11+C in corn and sorghum
plants. J. Agric. Food Chem. , 23(2) :279-281 .
Steller, W.A., and W.W. Brand.
1974. Analysis of dimethoate-treated grapes for the N-hydroxy-
methyl and de-N-methyl metabolites and for their sugar adducts.
J. Agric. Food Chem., 22(3) :445-449.
Stenerson, J., A. Gilman, and A. Vardanis.
1973. Carbofuran: Its toxicity to and metabolism by earth worm
(Lumbricus terrestris). J. Agric. Food Chem. , 21 (2) :166-171 .
Stephan, U., and H.R. Schutte.
1970. About the metabolism of chloroethyl trimethylammoniumchloride
in higher plants. Biochem. Physiol. Pflanz., 161:499-510.
Stephenson, G.R., L.R. Baker, and S.K. Ries.
1971. Metabolism of Pyrazon in susceptible species and inbred
lines of tolerant red beet (Beta vulgaris L.). J. Am. Soc. Hortic.
Sci., 96(2):145-147.
Stewart, D.K.R., and K.G. Cairns.
1974. Endosulfan persistence in soil and uptake by potato tubers.
J. Agric. Food Chem., 22(6) :984-986.
Stewart, D.K.R., and D. Chisholm.
1971. Long-term persistence of BHC, DDT and chlordane in a sandy
loam soil. Can. J. Soil Sci., 51:379-383.
Still, G.G., and E.R. Mansager.
1973a. Soybean shoot metabolism of isopropyl -3-chlorocarbanilate:
Ortho and para aryl hydroxylation. Pest. Biochem. Physiol., 3(1):
87-95.
Still, G.G., and E.R. Mansager.
1973b. Metabolism of isopropyl carbanilate by soybean plants.
Pest. Biochem. Physiol., 3(3) : 289-299.
Still, G.G., and E.R. Mansager.
1973c. Metabolism of isopropyl-3-chloracarbanilate by cucumber
plants. J. Agric. Food Chem., 21(5): 787-791 .
Still, G.G., and E.R. Mansager.
1974. Metabolism of isopropyl -3-chlorocarbanialte by alfalfa
plants. Abstracts, 168th ACS Meeting, PEST 1.
Still, G.G., E.R. Mansager, and G.D. Paulson.
1974a. Alfalfa metabolites of isopropyl-3-chlorocarbanilate
(chlorpropham) : Their fate in rats and sheep. Abstracts, 168th
ACS Meeting, PEST 2.
365
Still, G.G., D.G. Rusness, and E.R. Mansager.
1974b. Carbanilate herbicides and their metabolic products-
their effect on plant metabolism. Abstracts, 167th ACS Meeting,
PEST 40.
Stillwell, W.G., M.J. Carman, L. Bell, and M.G. Horning.
1974. The metabolism of safrole and 2' ,3' -epoxysafrole in the
rat and quinea pig. Drug Metab. Dispos., 2(6) :489-498.
Stoller, E.W., L.M. Wax, L.C. Haderlie, and F.W. Slife.
1975. Bentazon leaching in four Illinois soils. J. Agric. Food
Chem., 23(4):682-684.
Strang, R.H., and R.L. Rogers.
1974. Behavior and fate of two phenyl pyridazi none herbicides in
cotton, corn, and soybean. J. Agric. Food Chem., 22(6) : 1 1 1 9-1 1 24-
Strobel , G.A.
1966. The fixation of hydrocyanic acid by a psychrophilic
Basidiomycete. J. Biol. Chem., 241:2618-2621.
Strobel , G.A.
1967. 4-Amino-4-cyanobutyric acid as an intermediate in glutamate
biosynthesis. J. Biol. Chem. 242:3265-3269.
Stutzenberger, F.J., and J.N. Parle.
1972. Binding of benz imidazole compounds to conidia of Pithomyces
chartarum. J. Gen. Microbiol., 73:85-94.
Subba Rao, N.V., and A.G. Pollard.
1951. Photo-decomposition of rotenone in spray deposits. III.
Kinetics of the photo-decomposition. J. Sci. Food Agric,
2:462-472.
Suffling, R., D.W. Smith, and G. Sirons.
1974. Lateral loss of picloram and 2,4-D from c forest podsol
during rainstorms. Weed Res., 14:301-304.
Sugiura, K., M. Hattori, M. Baba, and M. Goto.
1975a. Accumulation and excretion of PCB's in the mouse.
Chemosphere, 4(3) : 181 -187-
Sugiura, K., S. Sato, and M. Goto.
1975b. Adsorption-diffusion mechanism of BHC-residues. A consid-
eration based on bacteria experiments as models. Chemosphere,
4(3):189-194.
Sumida, S., Y. Hisada, A. Kometani , and J. Miyamoto.
1973a. Biotransformation of 3-(3' ,5' -dichlorophenyl )5,5- dimethyl
oxazolidine-2,4-dione. Part 1. Metabolism in the rats. Agric.
Biol. Chem., 37(9) :2127-2136.
Sumida, S., R. Yoshihara, and J. Miyamoto.
1973b. Degradation of 3-(3,5-dichlorophenyl )-5,5-dimethyl
oxazolidine-2,4-dione by plants, soil and light. Agric. Biol.
Chem., 37(12) :2781-2790.
Summers, A.O., and E. Lewis.
1972. Volatilization of mercuric chloride by mercury-resistant
plasmid-bearing strains of Escherichia coli , Staphylococcus aureus,
and Pseudomonas aeruginosa. J. Bacterid., 113(2) : 1 070-1 072.
366
Summers, A.O., and S. Silver.
1972. Mercury resistance in plasmid-bearing strain of
Escherichia coli. J. Bacterid., 112(3):1228-1236.
Summers, A.O., and L.I. Sugarman.
1974. Cell -free mercury ( ID-reducing activity in plasmid-
bearing strain of Escherichia coli. J. Bacterid., 119(1):
242-249.
Sundstrom, G., and B. Jansson.
1975. The metabolism of 2,2' ,3,5' ,6-pentachlorobiphenyl in rats,
mice and quails. Chemosphere, 4(6) :361 -370.
Sundstrom, G., B. Jansson, and S. Jensen.
1975. Structure of phenolic metabolites of p,p'-DDE in rat, wild
seal and guillemot. Nature, 255:627-628.
Sundstrom, G., and C.A. Wachmeister.
1975. Structure of a major metabolite of 2,2' ,4,5,5' -pentachloro-
bi phenyl in mice. Chemosphere, 4(1): 7-1 1 -
Sutherland, D.J., M. Siewierski, A.H. Marei, and K. Helrich.
1970. The effect on mosquitoes of sublethal exposure to
insecticides II. DDT metabolism. Mosq. News, 30(1):8-11.
Suzuki, M., Y. Yamato, and T. Watanabe.
1974. Photodieldrin residues in field soils. Bull. Environ.
Contam. Toxicol., 12(3) : 275-280.
Suzuki, T., K. Furukawa, and K. Tonomura.
1968. Studies on the removal of inorganic mercurial compounds in
waste by the cell -reused method of mercury-resistant bacterium.
J. Ferment. Technol . , 46(12) :1048-1055.
Suzuki, T. , and J. Miyamoto.
1973. Metabolism of tetramethrin in houseflies and rats In vitro.
Pestic. Biochem. Physiol., 4:86-97.
Suzuki, T., and M. Uchiyama.
1975. Pathway of nitro reduction of parathion by spinach
homogenate. J. Agric. Food Chem. , 23(2) :281-285.
Syversen, T.L.M.
1974a. Biotransformation of Hg-203 labeled methyl mercuric
chloride in rat brain measured by specific determination of
Hg2+. Acta Pharmacol. Toxicol., 35:277-283.
Syversen, T.L.M.
1974b. Distribution of mercury in enzymatically characterized
subcellular fractions from the developing rat brain after
injections of methyl mercuric chloride and diethyl mercury.
Biochem. Pharmacol., 23:2999-3007.
Tadjer, G.S., and M.N. Egyed.
1974. Detection of cyolane in alfalfa pellets and rumen content
of a cow. Bull. Environ. Contam. Toxicol., 12(2) : 1 73-1 76 .
Takase, I., and H. Nakamura.
1974. The fate of ethyl thiometon (0,0-diethyl S-[2-(ethyl thio)
ethyl ]phosphorodithioate) in paddy soil. J. Agric. Chem. Soc.
Jap., 48(1 ):29-34.
367
Takase, I., K.E. Tan, and K. Ishuzuka.
1973. Metabolic transformation and accumulation of 0-ethyl S,S-
diphenyl phosphorodithiolate (Hinosan) in rice plants. Agric.
Biol. Chem. , 37(7) : 1 563-1571 .
Takase, I., H. Tsuda, and Y. Yoshimoto.
1972. The fate of disyston active ingredient in soil.
Pflanzenschutz-Nachr. , 25(1 ) :43-63.
Talekar, N.S., and E.P. Lichtenstein.
1973. Influence of mineral nutrients on the penetration, trans-
location, and metabolism of [1<+C]dyfonate in pea plants. J.
Agric. Food Chem., 21 (5):851-855.
Tanabe, M. , R.L. Dehn, and R.R. Bramshall.
1974. The photochemistry of imidan in diethyl ether. J. Agric.
Food Chem., 22(l):54-56.
Temizer, A.
1970. Metabolisme de L'Aldrine Chez la Mouche de L'Oignon.
Phytiatr.-Phytopharm. , 19(1) :9-18.
Terranova, A.C.
1969. The residual fate of N,N,N' ,N'-tetramethyl-£-piperidino-
phosphonic diamide after injection, tarsal contact, and topical
application to the boll weevil. J. Econ. Etomol . , 62(1 ) :821 -823.
Tewfik, M.S., and Y.A. Hamdi.
1975. Metabolism of fluorodifen by soil microorganisms. Soil
Biol. Biochem., 7:79-82.
Thomas, K.P., and D.G. Rowlands.
1975. The uptake and degradation of pirimiphos-methyl by Cheshire
cheese. J. Stored Prod. Res., 11:53-56.
Thomason, I.J., and M.V. McKenry.
1974. Part I. Movement and fate as affected by various conditions
in several soils. Hilgardia, 42(11 ) :393-421.
Thompson, A.R.
1971. Stonefly metabolism and the effects of DDT. Diss. Abstr. ,
32B(4):2373.
Thompson, A.R., and W.W. Sans.
1973. Effects of soil insecticides in southwestern Ontario on
non-target invertebrates: Earthworms in pasture. Environ.
Entomol., 3(2) :305-308.
Thompson, L. , Jr.
1972. Metabolism of chloro s-triazine herbicides by Panicum and
Setaria. Weed Sci., 20(6): 584-587.
Thorn, G.D.
1973. Uptake and metabolism of chloroneb by Phaseolus vulgaris.
Pestic. Biochem. Physiol., 3(2):137-140.
Tiedje, J.M.
1969. Metabolism of 2,4-dichlorophenoxyacetic acid by enzymes of
an Arthrobacter sp. Diss. Abstr., 29B(11 ) :4298-4299.
368
Tiedje, J.M,. and M.L. Hagedorn.
1975. Degradation of alachlor by a soil fungus, Chaetomium
globosum. J. Agric. Food Chem., 23(1):77-81.
Tillman, R.W., M.R. Siegle, and J.W. Long.
1973. Mechanism of action and fate of the fungicide chlorothalonil
(2,4,5,6-tetrachloroisophthaloni trile) in biological systems.
Pestic. Biochem. Physiol., 3(2) : 160-167.
Tisdale, M.J., and K.A. Lord.
1973. Uptake and distrubution of thiabendazole by seed potatoes.
Pestic. Sci. , 4:121-130.
Tocco, D.J., R.P. Buhs, H.D. Brown, A.R. Matzuk, H.E. Mertel,
R.E. Harman, and N.R. Trenner.
1964. The metabolic fate of thiabendazole in sheep. J. Med.
Chem., 7:399-405.
Tomlin, A.D.
1972. The toxicity, penetration and metabolism of gardona in gypsy
moth larvae. Diss. Abstr. , 33B(4):1410.
Tomoyeda, M. , H. Horitsu, and T. Azuma.
1973. Isolation of phenyl mercuric-, and mercuric acetate-tolerant
microorganism and the incorporation of their compounds into cells
of the microorganism (Studies on recovery of heavy metal compounds
by microorganism Part II). J. Agric. Chem. Soc. Jap., 47(1 ) :51 -55.
Torgeson, D.C., and H. Mee.
1967. Microbial degradation of bromacil. Proc. Northeast. Weed
Contr. Conf. , 21:584.
Torstensson, N.T.L., J. Stark, and B. Goransson.
1975. The effect of repeated applications of 2,4-D and MCPA on
their breakdown in soil. Weed Res., 15:159-164.
Townsend, M.G., E.M. Odam, and J.M.J. Page.
1975. Studies of the microsomal drug metabolism system in
warfarin-resistant and -susceptible rats. Biochem. Pharmacol.,
24:729-735.
Tripathi, R.K., and R.D. O'Brien.
1973. Insensitivity of acetylcholinesterase as a factor in
resistance of houseflies to the organophosphate rabon. Pestic.
Biochem. Physiol., 3(4) :495-498.
Tseng, Y.-C. L., and R.E. Menzer.
1974. Effect of hepatic enzyme inducers on the In vivo and
in vitro metabolism of dicrotophos, dimethoate, and phosphamidon
in mice. Pestic. Biochem. Physiol., 4:425-437.
Tucker, D.P., and R.L. Phillips.
1969. Movement and degradation of herbicides in Florida citrus
soils. Proc. Fl a. State Hortic. Soc, 81:72-75.
Turner, J.C.
1969. Cyanide detoxi cation in the opossum (Trichosurus vulpecula).
N. Z. J. Sci., 12:569-575.
369
Uchiyama, M. , H. Abe, R. Sato, M. Shimura, and T. Watanabe.
1973. Fate of 3-allyloxy-l ,2-benzisothiazole 1,1 -dioxide
(oryzemate). Agric. Biol. Chem. , 37(4) :737-745.
Udagawa, T., T. Miyata, and T. Saito.
1974. Metabolism of continuous three weeks administered
ll4C-pyridafenthion, 0,0-diethyl-0-(3-oxo-2-phenyl -2H-pyridazine-
6-yl )phosphorothioate, in mouse. Botyu-Kagaku, 39:15-18.
Ueda, K., L.C. Gaughan, J.E. Casida.
1974. Photodecomposition of resmethrin and related pyrethroids.
J. Agric. Food Chem., 22(2) :21 2-220.
Ueda, K., L.C. Gaughan, and J.E. Casida.
1975a. Metabolism of (+)-trans- and (+)-cis-resmethrin in rats.
J. Agric. Food Chem., 23(1 ):106-115.
Ueda, K., L.C. Gaughan, and J.E. Casida.
1975b. Metabolism of four resmethrin isomers by liver microsomes.
Pestic. Biochem. Physiol., 5:280-294.
Ueyama, I., and I. Takase.
1975. Metabolic behavior of 0-ethyl S,S-diphenyl phosphoro-
dithiolate (edifenphos) in female goat. Agric. Biol. Chem.,
39(9) :1 719-1727.
Ueyama, I., Y. Uesugi , C. Tomizawa, and T. Murai.
1973. Metabolic fate of 0-ethyl S,S-diphenyl phosphorodithiolate
(Hinosan) in rice plant. Agric. Biol. Chem., 37(7) : 1543-1 551 .
Unlu, M.Y., M. Heyrand, and S. Keckes.
1972. Mercury as a hydrospheric pollutant. I. Accumulation and
excretion of 203HgCl2 in Tapes decussatus L. p. 292. In M. Ruivo
(ed.) Marine pollution and sea life. FTshing News (BoolTs), London.
Valenta, J.R., C.J. DiCuollo, L.R. Fare, J. A. Miller, and J.F. Pagano.
1974. Microbial transformation of methyl 5(6) -butyl -2-benzimid-
azolecarbamate. Appl . Microbiol., 28(6) :995-998.
Valentine, J. P., and S.W. Bingham.
1974. Influence of several algae on 2,4-D residues in water.
Weed Sci., 22:358-363.
VanAlfen, N.K., and T. Kosuge.
1974. Microbial metabolism of the fungicide 2,6-dichloro-4-
nitroaniline. J. Agric. Food Chem. , 22(2) :221-224.
Van Dijk, H.
1974. Degradation of 1 ,3-dichloropropenes in the soil.
Agro-Ecosystems, 1:193-204.
Van Miller, J. P., I.C. Hsu, and J.R. Allen.
1975. Distribution and metabolism of 3H-2,5,2' ,5' -tetrachloro-
biphenyl in rats. Proc. Soc. Exper. Biol. Med., 148:682-687.
Varela-Alvarez, H.J., D. Sink, and L.L. Wilson.
1973. Certain physiological factors affecting organochlorine
pesticide metabolism in ovine females. J. Agric. Food Chem.,
21(3):407-409.
370
Voerman, S., and A.F.H. Besemer.
1975. Persistence of dieldrin, lindane, and DDT in a light sandy
soil and their uptake by grass. Bull. Environ. Contam. Toxicol.,
13(4) :501 -505.
Vonk, J.W., and A.K. Sijpesteijn.
1973. Studies on the methylation of mercuric chloride by pure
cultures of bacteria and fungi. Antonie van Leeuwenhoek J.
Microbiol. Serol . , 39(3) :505-513.
Walker, C.H., A.C.C. Craven, and M. Kurukgy.
1975. The metabolism of organochlorine compounds by microsomal
enzymes of the shag (Phalacrocorax aristotelis). Environ.
Physiol. Biochem., 5:58-64.
Walker, C.H., and G.A. El Zorgani.
1973. Metabolism of a dieldrin analogue - secondary oxidation
by liver microsomes. Life Sci., 13:585-593.
Walker, C.H., and G.A. El Zorgani.
1974. The comparative metabolism and excretion of HCE, a
biodegradable analogue of dieldrin, by vertebrate species.
Arch. Environ. Contam. Toxicol., 2(2): 97-1 16-
Walker, W.W.
1972. Degradation of malathion by indigenous soil microorganisms.
Diss. Abstr., 33B(4):1347.
Wall cave, L, and R. Gingell.
1974. Species differences in the acute toxicity and tissue
distribution of DDT in mice and hamsters. Toxicol. Appl.
Pharmacol., 28(3) :384-394.
Wallnofer, P.R., G. Engelhardt, S. Safe, and 0. Hutzinger.
1973a. Microbial hydroxylation of 4-chlorobiphenyl and 4,4'-
dichlorobiphenyl . Chemosphere, 2:69-72.
Wallnofer, P.R., M. Koniger, S. Safe, and 0. Hutzinger.
1972. The metabolism of the systemic fungicide carboxin (vitavax)
by Rhizopus japonicus. Int. J. Environ. Anal. Chem. , 2:37-43.
Wallnofer, P.R., S. Safe, and 0. Hutzinger.
1973b. Microbial hydroxylation of the herbicide M-(3,4-dichloro-
phenyl )methacryl amide (dicryl). J. Agric. Food CHem. , 21(3):
502-504.
Wallnofer, P.R., S. Safe, and 0. Hutzinger.
1973c. Microbial demethylation and debutynylation of four
phenylurea herbicides. Pestic. Biochem. Physiol., 3(3) :253-258.
Ward, P.F.V., and N.S. Huskisson.
1972. The metabolism of fluoroacetate in lettuce. Biochem. J.,
130:575-587.
Ware, G.W., W.P. Cahill, and B.J Estesen.
1975. Volatization of DDT and related materials from dry and
irrigated soils. Environ. Contam. Toxicol., 14(l):88-96.
Ware, G.W., D.M. Whitacre, and J.B. Dobie.
1973. Apparent increase of DDT residues in wafered hay. Bull.
Environ. Contam. Toxicol., 9(3): 173-1 78.
371
Waring, R.H.
1973. The metabolism of vitavax by rats and rabbits. Xenobiotica,
3(2):65-71.
Wathana, S.
1971. Absorption, translocation, and metabolism of 4-(2,4-
dichlorophenoxy) butyric acid in soybean and cocklebur. Diss.
Abstr., 31B(12)(Part I):7029.
Watson, M., B. Pharoah, J. Wyllie, and W.W. Benson.
1975. Metabolism of low oral doses of DDT and DDE by tame mule
deer fawns. Bull. Environ. Contam. Toxicol., 13(3) : 31 6-323.
Watts, R.R., R.W. Storherr, and J.H. Onley.
1974. Effects of cooking on ethylenebisdithiocarbamate degradation
to ethylene thiourea. Bull. Environ. Contam. Toxicol., 12(2):
224-226.
Wauchope, R.D., and R. Haque.
1973. Effects of pH, light and temperature on carbaryl in aqueous
media. Bull. Environ. Contam. Toxicol., 9-( 5) : 257-260.
Webb, R.G., and A.C. McCall.
1972. Identities of polychlorinated biphenyl isomers in aroclors.
J. Assoc. Off. Anal. Chem. , 55(4) :746-752.
Weisgerber, I., D. Bieniek, J. Kohl i , and W. Klein.
1975a. Isolation and identification of three unreported photo-
dieldrin-1I+C metabolites in soil. J. Agric. Food Chem., 23(5):
873-877.
Weisgerber, I., J. Kohl i , R. Kaul , W. Klein, and F. Korte.
1974. Fate of aldrin-11+C in maize, wheat, and soils under outdoor
conditions. J. Agric. Food Chem. , 22(4) :609-612.
Weisgerber, I., W. Tomberg, W. Klein, and F. Korte.
1975b. Beitrage Zur Okologischen Chemie. XCV. Isolierung und
Strukturaufklarung Einiger Hydrophiler Isodrin-11+C-Metaboliten aus
Weisskohl. Chemosphere, 4(2):99-104.
Welling, W. , A.W. deVries, and S. Voerman.
1974. Oxidative cleavage of a carboxyester bond as a mechanism of
resistance to malaoxon in houseflies. Pestic. Biochem. Physiol.,
4:31-43.
Wells, M.R., J.L. Ludke, and J.D. Yarbrough.
1973. Epoxidation and fate of [11+C]aldrin in insecticide-
resistant and susceptible populations of mosquitofish (Gambusia
affinis). J. Agric. Food Chem. , 21 (3) :428-429.
Werner, R.A.
1974. Distribution and toxicity of root-absorbed lt+C-orthene and
its metabolites in loblolly pine seedlings. J. Econ. Entomol.,
67(5): 588- 591.
West, H.D., J.R. Lawson, I.H. Miller, and G.R. Mathura.
1956. The fate of diphenyl in the rat. Arch. Biochem. Biophys.,
60:14-20.
372
Westmacott, D., and S.J.L. Wright.
1975. Studies on the breakdown of p-chlorophenyl methyl carbamate.
II. In cultures of a soil Arthrobacter sp. Pestic. Sci., 6:61-68.
Wheeler, L., and A. Strother.
1973. In vitro metabolism of 11+C-pesticidal carbamates by fetal and
maternal- brain, liver, and placenta of the rat. Drug Metab.
Dispos., 2(6) :533-538.
Whitacre, D.M.
1970. Endosulfan metabolism in temperature-stressed rats. Diss.
Abstr., 30B(9):4435-4436.
White, E.R., E.A. Bose, J.M. Ogawa, B.T. Manji, and W.W. Kilgore.
1973. Thermal and base-catalyzed hydrolysis products of the
systemic fungicide, benomyl . J. Agric. FoodChem., 21 (4) : 61 6-61 8.
White, J.F., and A. Rothstein.
1973. The interaction of methyl mercury with erythrocytes.
Toxicol. Appl . Pharmacol., 26:370-384.
Whitten, C.J., and D.L. Bull.
1974a. Fate of 3,3-dimethyl -1 -(methyl thio)-2-butanone 0-(methyl-
carbamoyl )oxime (Diamond Shamrock DS-15647) in cotton plants and
soil. J. Agric. FoodChem., 22(2) :234-238.
Whitten, C.J., and D.L. Bull.
1974b. Comparative toxicity, absorption, and metabolism of
chlorpyrifos and its dimethyl homologue in methyl parathion-
resistant and -susceptible tobacco budworms. Pest. Biochem.
Physiol., 5:266-274.
Wichman, J.R., and W.R. Byrnes.
1975. Uptake, distribution, and degradation of simazine by black
walnut and yellowpoplar seedlings. Weed Sci., 23(6) :448-453.
Wiedmann, J.L., and G.G. Ecke.
1975. Synthesis and isolation of 1 -hydroxy- 2-p ropy 1-3' -chloro-
carbanilate from soybean plants treated with isopropyl-3-
chlorocarbanilate. Abstracts, 170th ACS Meeting, PEST 20.
Wiese, M.V., and J.M. Vargas, Jr.
1973. Interconversion of chloroneb and 2,5-dichloro-4-methoxyphenol
by soil microorganisms. Pest. Biochem. Physiol., 3(2) : 21 4-222.
Willis, D.E., and R.F. Addison.
1974. Hydroxylation of bi phenyl vn vitro by tissue preparations of
some marine organisms. Comp. Gen. Pharmacol., 5:77-81.
Wilson, D.M., and P.C. Oloffs.
1973. Residues in alfalfa following soil treatment with high purity
chlordane (Velsicol HCS-3260). Bull. Environ. Contam. Toxicol.,
9(6):337-344.
Wimmer, J.
1974. Untersuchungen Uber die Wanderung und Auswaschung von
Quecksilber im Boden. Die Bodenkultur. , 25(4) :369-379.
Winterlin, W. , J.B. Bailey, L. Langbehn, and C. Mourar.
1975. Degradation of parathion applied to peach leaves. Pestic.
Monit. J., 8(4):263-269.
373
Winterlin, W. , C. Mourer, and J.B. Bailey.
1974. Degradation of four organophosphate insecticides in grape
tissues. Pestic. Monit. J., 8(1): 59-65.
Wolcott, R.M.
1971. Studies on the mechanism of metabolism of dialkyl aryl
phosphorothionate insecticides. Diss. Abstr. , 31 B ( 1 0) : 5806.
Wolf, D.C., and J. P. Martin.
1974. Microbial degradation of 2-carbon-14 bromacil and terbacil.
Soil Sci. Soc. Am. Proc. , 38(6) :921 -925.
Wolfe, H.R., D.C. Staiff, J.F. Armstrong, and S.W. Comer.
1973. Persistence of parathion in soil. Bull. Environ. Contain.
Toxicol., 10(1 ):1 -9.
Wolfe, N.L., R.G. Zepp, J. A. Gordon, and G.L. Baughman.
1975a. Kinetic investigation of malathion degradation in water.
Bull. Environ. Contam. Toxicol., 13(6): 707-71 3.
Wolfe, N.L., R.G. Zepp, J. A. Gordon, and G.L. Baughman.
1973. Chemistry of methyl mercurials in aqueous solution.
Chemosphere, 2(4) : 1 47-152-
Wolfe, N.L., R.G. Zepp, J. A. Gordon, and R.C. Fincher.
1975b. N-Mitrosoatrazine: Formation and degradation. Abstracts,
170th ACS Meeting, PEST 23.
Wong, P.T.S., and K.L.E. Kaiser.
1975. Bacterial degradation of polychlorinated biphenyls. II.
Rate studies. Bull. Environ. Contam. Toxicol., 13(2) :249-256.
Wood, J.M.
1971. Environmental pollution by mercury. Adv. Environ. Sci.
Technol., 2:39-56.
Wood, J.M.
1974. Biological cycles for toxic elements in the environment.
Science, 183:1049-1051.
Woodham, D.W., C.A. Bond, E.H. Ahrens, and J.G. Medley.
1975. The cumulation and disappearance of mirex residues. III.
In eggs and tissues of hens fed two concentrations of the
insecticide in their diet. Bull. Environ. Contam. Toxicol.,
14(1 ) :98-104.
Woodham, D.W., J.C. Hatchett, and C.A. Bond.
1974. Comparison of dimethoate and dimethoxon residues in citrus
leaves and grapefruit following foliar treatment with dimethoate
wetable powder with and without surfactant. J. Agric. Food Chem. ,
22(2):239-242.
Woodrow, J.E., J.N. Seiber, D.G. Crosby, K.W. Moilanen, C. Mourer,
C.J. Soderquist, and W.L. Winterlin.
1975. Breakdown of parathion in the air and on leaves and soil of
a treated orchard. Abstracts, 170th ACS Meeting, PEST 125.
Woods, R.J., and S. Akhtar.
1974. Radiation-induced dechlorination of chloral hydrate and
1 ,1 ,1 -trichloro-2,2-bis(£-chlorophenyl )ethane (DDT). J. Am. Chem.
Soc, 22:1132-1133.
374
Woolson, E.A., and P.C. Kearney.
1973. Persistencae and reactions of 14C-cacodylic acid in soils.
Environ. Sci. Technol., 7(1) :47-50.
Wright, F.C., J.S. Palmer, and J.C. Riner.
1973. Retention of mercury in tissues of cattle and sheep given
oral doses of a mercurial fungicide, Ceresan M. J. Agric. Food
Chem., 21(4):614-615.
Wustner, D.A., and T.R. Fukuto.
1974. Affinity and phosphonylation constants for the inhibition
of cholinesterases by the optical isomers of 0-2-butyl S-2(di-
methylammonium)ethyl ethylphosphonothioate hydrogen oxalate.
Pest. Biochem. Physiol., 4:365-376.
Yaklich, R.W.
1970. The metabolism of the herbicide N,N-dimethyl -2, 2-diphenyl-
acetamide by corn root. Diss. Abstr. , 31 B(6) :3215-3216.
Yaklich, R.W., S.J. Karczmarczyk, and R.M. Devlin.
1974. Metabolism of 11+C-San-6706 and 14C-Norflurazon in cranberry
plants. Weed Sci., 22(6):595-599.
Yamaguchi, I., H. Shibata, H. Seto, and T. Misato.
1975. Isolation and purification of blasticidin S deaminase from
Aspergillus terreus. J. Antibiot., 28(1):7-14.
Yamamoto, H., C. Tomizawa, Y. Uesugi, and T. Murai.
1973. Absorption, translocation and metabolism of 0,0-diisopropyl
S-benzyl phosphorothiolate (Kitazin P) in rice plant. Agric. Biol.
Chem., 37(7) :1553-1 561 -
Yamamoto, H., and H. Yoshimura.
1973. Metabolic studies on polychlorinated biphenyls. III.
Complete structure and acute toxicity of the metabolites of
2,4,3' ,4'-tetrachlorobiphenyl. Chem. Pharm. Bull., 21(10):
2237-2242.
Yang, R.S.H.
1971. Comparative studies on the vn vitro metabolism of diazinon
and diazoxon in the rat and the housefly. Diss. Abstr., 31 B( 1 0) :
5858.
Yang, R.S.H. , W.C. Dauterman, and E. Hodgson.
1969. Enzymatic degradation of diazinon by rat liver microsomes.
Life Sci., 8(Part l):667-672.
Yaron, B., B. Heuer, and Y. Birk.
1974. Kinetics of azinphosmethyl losses in the soil environment.
J. Agric. Food Chem., 22(3) :439-441 .
Yoshimura, H. , and M. Oshima.
1971. Studies on the tissue distribution and elimination of
several components of KC-400 (chlorobiphenyls) in mice. Fukuoka
Acta Med., 62(1 ) :5-l 1 .
Yoshimura, H., and H. Yamamoto.
1973. Metabolic studies on polychlorinated biphenyls. I.
Metabolic fate of 3,4,3' ,4' -tetrachlorobiphenyl in rats. Chem.
Pharm. Bull., 21 (5) :1 168-1 169.
375
Yoshimura, H., and H. Yamamoto.
1975. A novel route of excretion of 2,4,3' ,4'-teterachlorobiphenyl
in rats. Bull. Environ. Contam. Toxicol., 13(6) :6fal-688.
Yoshimura, H., H. Yamamoto, J. Nagai, Y. Yae, H. Uzawa, Y. Ito,
A. Notomi , S. Minakami, A. Ito, K. Kato, and H. Tsuji.
1971. Studies on the tissue distribution and the urinary and fecal
excretion of 3H-Kanechlor (chlorobiphenyls) in rats. Fukuoka Acta
Med., 62(1):12-19.
Yoshimura, H., H. Yamamoto, and S. Saeki.
1973. Metabolic studies on polychlorinated biphenyls. II.
Metabolic fate of 2,4,3' ,4'-tetrachlorobiphenyl in rats. Chem.
Pharm. Bull., 21 (10):2231-2236.
Yu, C.-C, G.M. Booth, D.J. Hansen, and J.R. Larsen.
1974a. Fate of carbofuran in a model ecosystem. J. Agric. Food
Chem., 22(3):431-434.
Yu, C.-C, G.M. Booth, D.J. Hansen, and J.R. Larsen.
1974b. Fate of bux insecticide in a model' ecosystem. Environ.
Entomol., 3(6) :975-977.
Yu, C.-C, G.M. Booth, and J.R. Larsen.
1975a. Fate of triazine herbicide cyanazine in a model ecosystem.
J. Agric. Food Chem. , 23(5) : 1014-1015.
Yu, C.-C, D.J. Hansen, and G.M. Booth.
1975b. Fate of dicamba in a model ecosystem. Bull. Environ.
Contam. Toxicol., 1 3( 3) : 280-283.
Yule, W.N.
1973. Intensive studies of DDT residues in forest soil. Bull.
Environ. Contam. Toxicol., 9:57-64.
Yule, W.N.
1974. The persistence and fate of fenitrothion insecticide in a
forest environment. II. Accumulation of residues in balsam fir
foliage. Bull. Environ. Contam. Toxicol., 12(2):249-252.
Yule, W.N., and J.R. Duffy
1972. The persistence and fate of fenitrothion insecticide in a
forest environment. Bull. Environ. Contam. Toxicol., 8:10-18.
Zayed, S.M.A., I.M.I. Fakhr, and M.R.E. Bahig.
1973. Metabolism of organophosphorus insecticides-XII. Biochem.
Pharmacol., 22:285-292.
Zemskaya, V.A., Y.V. Rakitin, L.M. Chernikova, and Z.V. Kalibernaya.
1971. Kinetics of the process of 2,4-D bonding by proteins in
maize leaf tissues. Fiziol. Rast. , 18(4) :738-745.
Zepp, R.G., N.L. Wolfe, G.L. Baughman, and J. A. Gordon.
1974. Dynamics of 2,4-D esters in the aquatic environment:
Hydrolysis and photodegradation. Abstracts, 168th ACS Meeting,
Atlantic City, NJ, Sept. 9-13, PEST 68.
Zepp, R.G., N.L. Wolfe, R.C Fincher, and J. A. Gordon.
1975. Chemical and light-induced decomposition of methoxychlor.
Abstracts, 170th ACS Meeting, PEST 129.
376
Zepp, R.G., N.L. Wolfe, and J. A. Gordon.
1973. Photodecomposition of phenyl mercury compounds in sunlight.
Chemosphere, 2(3):93-99.
Zettler, J.L.
1974. Esterases in malathion-susceptible and a malathion resistant
strain of Plodia interpunctella. J. Ga. Entomol. Soc, 9(4):
207-213.
Zinck, M.E., and R.F. Addison.
1974. The fate of 2-, 3-, and 4-chlorobiphenyl following intra-
venous administration to the thorny skate (Raja radiata) and the
winter skate (Raja ocellata). Arch. Environ. Contam. Toxicol.,
2(l):52-fal.
Zoro, J. A., J.M. Hunter, G. Eglinton, and G.C. Ware.
1974. Degradation of p_,£'-DDT in reducing environments. Nature,
247(5438):235-237.
Zulalian, J., D.A. Champagne, R.S. Wayne, and R.C. Blinn.
1975. Absorption, excretion, and metabolism of 1,3-bis
(D_-chlorobenzyl ideneamino)guanidine hydrochloride (Robenz
robenidine hydrochloride) in the chicken. J. Agric. Food
Chem., 23(4):724-730.
Zulalian, J., ana P.E. Gatterdam.
1973. Absorption, excretion, and metabolism of robenz, robenidine
hydrochloride [1 ,3-bis(p_-chlorobenzylideneamino)guanidine hydro-
chloride], in the rat. J. Agric. Food Chem. , 21 (5) :794-797.
377
Bibliography - Addendum
Chapman, A.H., and J.W. Price.
1972. Degradation of tri phenyl tin acetate by ultra-violet light.
Int. Pest. Contr., 14(1):11-12.
Kapoor, I. P., R.L. Metcalf, A.S. Hirwe, P.-Y. Lu, J.R. Coats, and
R.F. Nystrom.
1972. Comparative metabolism of DDT, methylchlor, and ethoxychlor
in mouse, insects, and in a model ecosystem. J. Agric. Food. Chem. ,
20(l):l-6.
Kearney, P.C., E.A. Woolson, and C.P. Ellington, Jr.
1972. Persistence and metabolism of chlorodioxins in soils.
Environ. Sci. Technol., 6:1017-1019.
378
Appendix I
Effect of Temperature on Carbamate Insecticides
Heat of
Molarity of
Ki
K2
Activation
Compound
C
NaOH
(Min-r
)
l-min^md-1
Qio
(kCal mol"1)
Carbaryl
3
0.009
2.18 x
10-2
2.42
x 10
13
6.22 x
io-2
6.91
x 10
23
1.84 x
io-1
2.04
x IO2
2.9
16.9
33
4.84 x
IO"1
5.37
x IO2
Baygon
5
0.01
7.30 x
IO"2
7.37
10
1.12 x
IO"1
1.12
x 10
20
3.04 x
io-1
3.04
x 10
2.49
15.8
30
7.59 x
IO"1
7.59
x 10
40
1.16
1.16
x IO2
Pyrolan
5
0.1
2.00 x
IO"3
2.00
x IO"2
10
3.20 x
io-3
3.20
x IO"2
20
7.00 x
io-3
7.00
x IO"1
222
13.7
30
1.49 x
IO"2
1.49
x IO"1
40
2.99 x
IO"2
2.99
x IO"1
Dimetilan
10
0.5
1.65 x
IO"4
3.40
x IO"3
20
1.65 x
IO"3
3.40
x IO"3
1.91
14.0
30
3.25 x
io-3
6.50
x IO"3
40
7.14 x
io-3
1.43
x 10
(Aly and El-Dib, 1971)
379
Appendix II
In Vivo Inhibition of Liver Arylamidase
Dose
(mq/kq i.p.)
Percent Inhibition
Compound
Ma
le
Female
Parathion
0.05
9.2
+
7.58
22.6
± 1.69
0.2
19.0
+
6.57
33.1
± 7.42
0.4
64.9
+
4.40
81.5
± 2.01
0.8
97.9
+
0.87
98.9
±0.52
Paraoxon
0.05
39.3
± 7.05
0.2
26.5
+
8.51
67.3
± 3.78
0.4
67.7
+
4.07
86.0
± 1.90
0.8
97.0
+
0.69
98.8
± 0.48
EPN
0.4
20.3
+
2.27
22.5
± 6.70
1.0
53.2
+
2.77
57.3
± 5.95
4.0
95.9
+
1.12
98.1
± 0.32
Folex
1
41.8
+
7.61
50.2
± 3.82
5
83.3
+
1.04
88.6
± 0.96
10
96.0
+
0.89
96.0
± 0.45
20
98.5
+
0.22
98.2
± 0.50
Sumithion
0.5
28.0
+
0.78
36.8
± 3.55
2
42.8
+
2.98
50.6
± 5.95
10
59.5
+
5.17
66.0
± 2.75
50
61.7
+
1.59
68.8
± 2.62
100
67.7
+
1.26
81.4
± 1.75
Malathion
2
22.4
+
2.71
0
± 7.72
10
50.1
+
4.35
49.4
± 5.65
50
70.2
+
1.71
73.6
± 7.44
100
84.4
+
1.78
84.2
± 1.29
TOTP
1
36.8
+
5.09
31.0
± 2.20
5
83.5
+
4.18
57.5
± 1.90
10
98.3
+
0.39
77.1
± 1.42
20
100.0
+
0.00
98.0
± 0.43
(Satch,
1973)
380
Appendix III
Effect of Substitution in Parathion Analogs
Hydrolysis
Uoh min'1)
Inhibition (kj M^min"1)
Substituent
[pH
.5)
Fly ACh
E
Bovine I
\Ch E
H
6.14
X
10-"
1.14
X
I06
2.44
X
I05
3-F
1.34
X
TO"3
2.88
X
I06
2.32
X
I05
3-C1
1.69
X
10-3
7.17
X
I06
1.90
X
I05
3-Br
1.74
X
10-3
2.02
X
I07
2.53
X
I05
3-1
1.49
X
IO-3
4.51
X
I07
6.61
X
I05
3-CF3
3.12
X
10-3
2.69
X
I07
5.94
X
10"
3-CH3
4.15
X
10-"
1.26
X
I06
3.79
X
10"
2-F
2.27
X
TO"3
1.21
X
I07
3.36
X
I05
2-C1
2.67
X
TO"3
7.82
X
I06
1.87
X
I05
2-CF3
3.84
X
10-3
3.56
X
O5
1.27
X
I03
2-CH3
4.61
X
10""
1.78
X
I05
1.43
X
I03
2.5-C12
3.42
X
10-3
3.22
X
I06
7.94
X
I03
3,5-Cl2
2.26
X
TO"3
8.59
X
I06
8.34
X
10"
2,5-(CH3)2
2.56
X
10-"
1.48
X
I05
2.8
X
I02
3,5-(CH3)2
2.20
X
10-"
1.49
X
I05
6.2
X
I02
(Metcalf and Metcalf, 1973)
381
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