Residue Reviews: Residues of Pesticides and Other Contaminants in the Total Environment

164 Pages·1975·6.435 MB·English

by  G. D. Paulson (auth.), Francis A. Gunther, Jane Davies Gunther (eds.)

RESIDUE REVIEWS
VOLUME 58
RESIDUE REVIEWS
Residues of Pesticides and Other
Contaminants in the Total Environment
Editor
FRANCIS A. GUNTHER
Assistant Editor
JANE DAVIES GUNTHER
Riverside, California
ADVISORY BOARD
F. BAR, Berlin, Germany· F. BRO-RAsMUSSEN, Sj1Sborg, Denmark
D. G. CROSBY, Davis, California· S. DORMAL-VAN DEN BRUEL, Bruxelles, Belgium
C. L. DUNN, Wilmington, Delaware· H. EGAN, London, England
H. FREHSE, Leverkusen-Bayerwerk, Germany· K. FUKUNAGA, Saitama, Japan
H. GEISSBiiRLER, Basel, Switzerland· G. K. KOHN, Richmond, California
H. F. LINSKENS, Nijmegen, The Netherlands· N. N. MELNIKOV, Moscow, U.S.S.R.
R. MESTRES, Montpellier, France· P. DE PIETIU-TONELLI, Milano, Italy
1. S. TAYLOR, Melbourne, Australia· R. TRUHAUT, Paris, France
I. ZIEGLER, Munchen, Germany
VOLUME 58
SPRINGER-VERLAG
NEW YORK HEIDELBERG BERLIN
1975
Coordinating Board of Editors
FRANCIS A. GUNTHER, Editor
Residue Reviews
Department of Entomology
University of California
Riverside, California 92502
JOHN W. HYLIN, Editor
Bulletin of Environmental Contamination and Toxicology
Department of Agricultural Biochemistry
University of Hawaii
Honolulu, Hawaii 96822
WILLIAM E. WESTLAKE, Editor
Archives of Environmental Contamination and Toxicology
P.O. Box 1225
Twain Harte, California 95383
All rights reserved. No part of this book may be translated or reproduced in
any form without written permission from Springer-Verlag.
© 1975 by Springer-Verlag New York Inc.
Library of Congress Catalog Card Number 62-18595.
Softcover reprint of the hardcover 1st edition 1975
The use of general descriptive names, trade names, trade marks, etc. in this
publication, even if the former are not especially identified, is not to be taken
as a sign that such names, as understood by the Trade Marks and Merchandise
Marks Act, may accordingly be used freely by anyone.
New York: 175 Fifth Avenue, New York, N.Y. 10010
Heidelberg: 6900 Heidelberg 1, Postfach 1780, West Germany
ISBN-13: 978-1-4613-9396-2 e-ISBN-13: 978-1-4613-9394-8
DOl: 10.1007/978-1-4613-9394-8
Preface
That residues of pesticide and other contaminants in the total environ
ment are of concern to everyone everywhere is attested by the reception
accorded previous volumes of "Residue Reviews" and by the gratifying
enthusiasm, sincerity, and efforts shown by all the individuals from whom
manuscripts have been solicited. Despite much propaganda to the con
trary, there can never be any serious question that pest-control chemicals
and food-additive chemicals are essential to adequate food production,
manufacture, marketing, and storage, yet without continuing surveillance
and intelligent control some of those that persist in our foodstuffs could
at times conceivably endanger the public health. Ensuring safety-in-use
of these many chemicals is a dynamic challenge, for established ones are
continually being displaced by newly developed ones more acceptable to
food technologists, pharmacologists, toxicologists, and changing pest
control requirements in progressive food-producing economies.
These matters are of gennine concern to increasing numbers of gov
ernmental agencies and legislative bodies around the world, for some of
these chemicals have resulted in a few mishaps from improper use. Ade
quate safety-in-use evaluations of any of these chemicals persisting into
our foodstuffs are not simple matters, and they incorporate the considered
judgments of many individuals highly trained in a variety of complex
biological, chemical, food technological, medical, pharmacological, and
toxicological disciplines.
It is hoped that "Residue Reviews" will continue to serve as an
integrating factor both in focusing attention upon those many residue
matters requiring further attention and in collating for variously trained
readers present knowledge in specific important areas of residue and
related endeavors involved with other chemical contaminants in the total
environment. The contents of this and previous volumes of "Residue
Reviews" illustrate these objectives. Since manuscripts are published in
the order in which they are received in final form, it may seem that some
important aspects of residue analytical chemistry, biochemistry, human
and animal medicine, legislation, pharmacology, physiology, regulation,
and toxicology are being neglected; to the contrary, these apparent omis
sions are recognized, and some pertinent manuscripts are in preparation.
However, the field is so large and the interests in it are so varied that the
editors and the Advisory Board earnestly solicit suggestions of topics and
authors to help make this international book-series even more useful and
informative.
vi Preface
"Residue Reviews" attempts to provide concise, critical reviews of
timely advances, philosophy, and significant areas of accomplished or
needed endeavor in the total field of residues of these and other foreign
chemicals in any segment of the environment. These reviews are either
general or specific, but properly they may lie in the domains of analytical
chemistry and its methodology, biochemistry, human and animal medicine,
legislation, pharmacology, physiology, regulation, and toxicology; certain
affairs in the realm of food technology concerned specifically with pesti
cide and other food-additive problems are also appropriate subject matter.
The justification for the preparation of any review for this book-series is
that it deals with some aspect of the many real problems arising from
the presence of any "foreign" chemicals in our surroundings. Thus, manu
scripts may encompass those matters, in any country, which are involved
in allowing pesticide and other plant-protecting chemicals to be used
safely in producing, storing, and shipping crops. Added plant or animal
pest-control chemicals or their metabolites that may persist into meat and
other edible animal products (milk and milk products, eggs, etc.) are also
residues and are within this scope. The so-called food additives (sub
stances deliberately added to foods for flavor, odor, appearance, etc., as
well as those inadvertently added dming manufacture, packaging, dis
tribution, storage, etc.) are also considered suitable review material. In
addition, contaminant chemicals added in any manner to air, water, soil or
plant or animal life are within this purview and these objectives.
Manuscripts are normally contributed by invitation but suggested
topics are welcome. Preliminary communication with the editors is neces
sary before volunteered reviews are submitted in manuscript form.
Department of Entomology F.A.G.
University of California J.D.G.
Riverside, California
October 6, 1975
Table of Contents
Metabolic fates of herbicides in animals
By C. D. PAULSON • • • . • • • 1
The metabolism of contact insecticides in stored grains.
III. 1970-1974
By D. C. ROWLANDS 113
Subject Index . . . 157
Metabolic fates of herbicides in animals
By
G. D. PAULSON"
Contents
I. Introduction 1
II. Dinitroaniline herbicides _______________________________________ _ 2
III. Substituted uracil herbicides ___________________________________ _ 7
IV. Benzoic acid and related herbicides _____________________________ _ 13
V. Nitrile and related herbicides _________________________________ _ 19
VI. Halogenated aliphatic acid herbicides ___________________________ _ 24
VII. Carbamate and related herbicides _______________________________ _ 24
VIII. Thiocarbamate herbicides _____________________________________ _ 38
IX. Aunide herbicides _____________________________________________ _ 40
X. Bypyridilium herbicides _______________________________________ _ 41
XI. Triazole herbicides ___________________________________________ _ 49
XII. Diphenyl ether herbicides _____________________________________ _ 50
XIII. Phenol herbicides _____________________________________________ _ 50
XIV. Triazine herbicides ___________________________________________ _ 60
XV. Urea herbicides _______________________________________________ _ 75
XVI. Phenoxy herbicides ___________________________________________ _ 89
XVII. Miscellaneous herbicides ______________________________________ _ 95
XVIII. General discussion ____________________________________________ _ 97
XIX. Herbicides cited ______________________________________________ _ 100
Summary ____________________________________________________________ _
104
References ___________________________________________________________ _
105
I. Introduction
The rapid increase in the worldwide production and usage of her
bicides during the past three decades has been discussed and documented
by ASHTON and CRAFTS (1973) and others. The increased agricultural
production made possible by these compounds continues to provide the
"Metabolism and Radiation Research Laboratory, United States Department of
Agriculture, Agricultural Research Service, Fargo, ND 58102. Mention of a trade
name, proprietary product, or specific equipment does not constitute a guarantee or
warranty by the U. S. Department of Agriculture and does not imply its approval to
the exclusion of other products that may be suitable.
© 1975 by Springer-Verlag New York Inc.
2 C. D. PAULSON
economic stimulus to encourage the development and sale of new herbi
cides. ASHTON and CRAFTS (1973) indicated that there are now more
than 150 compounds that are currently being used as herbicides.
Along with the expanding use and development of herbicides, there
has been a growing concern for possible untoward effects of herbicides
in the environment. Because animals are likely to become exposed to
herbicides, there has been concern for the possible effect of these com
pounds on animals and especially for the possibility that these compounds
and/or their metabolites might contaminate products used for human
consumption. One of the results of this concern has been a proliferation
in the number of studies and reports concerning the metabolic fate of
herbicides in animals. This review summarizes the literature on the
animal metabolism of herbicides, with emphasis on publications from 1962
through 1973.
There are, of course, many ways to classify such a diverse group of
compounds as the herbicides. However, for the purpose of this review,
these compounds were grouped on the basis of similar structural types.
To a large degree, the classification scheme of ASHTON and CRAFTS (1973)
was used. A tabular listing of all compounds cited, as well as the section
and table where each compound is discussed, has been included (Table
XIII). Common names assigned by the Weed Science Society of America
(WSSA) were used when available. When a common name had not been
assigned by WSSA, the code number or other term in current usage was
used to designate that compound. The reader is referred to publications
by FREAR (1968), MARTIN (1971), and THOMPSON (1964) which give
cross-referenced information concerning common names, trade names,
and code numbers of herbicides.
The literature search relied primarily on Chemical Abstracts to obtain
all pertinent information published from 1962 through 1973. However,
some publications were probably overlooked and, therefore, were not
included in this review. The author would like to emphasize that any
omissions of information were unintentional.
II. Dinitroaniline herbicides
Dinitroaniline herbicides apparently are metabolized, at least in part,
by pathways involving reduction of the nitro groups and removal of the
N-alkyl groups in both ruminant and monogastric animals. The literature
does not indicate that the trifluoromethyl group of trifluralin or of benefin
was altered. The dinitroaniline herbicides that have been studied are
rapidly converted to polar metabolites and "nonextractable" metabolites
(GOLAB et al. 1969, GOLAB et al. 1970, EM:M:ERSON and ANDERSON 1966,
WILLIAMS and FEIL 1971).
EM:M:ERSON and ANDERSON (1966) gave rats an oral dose of [14CF 3]
trifluralin. Within five days after dosing, approximately 78% of the 14C
was eliminated in the feces and 22% in the urine. They found that 19%
Fates of herbicides in animals 3
of the HC given to rats as [N-propyl-14C]triHuralin was expired as HC0
2;
.thus, N-dealkylation clearly had occurred. GOLAB et al. (1969) gave a
lactating goat a single oral dose of [phenyl-14C]triHuralin and reported
that 17.8% of the 14C was eliminated in the urine and 81.2% in the feces
within 15 days after dosing. Most of the activity was eliminated during
the first four days after dosing. After a subcutaneous dose of trifluralin,
rats very slowly eliminated the compound or its metabolites (EMMERSON
and ANDERSON 1966). Carbon-14 was reportedly absent from the milk of a
goat that had been dosed with (14C]triHuralin (GOLAB et al. 1969). There
was no indication of trifluralin or its metabolites in liver, kidney, fat,
small intestine, large intestine, and stomach 14 days after dosing a goat
with 20.8 p.Ci (1.53 mg) of [HC]triHuralin. EMMERSON and ANDERSON
(1966) gave rats [14CFa]trifluralin and then observed that 11 to 14% of
the HC was excreted in the bile within 24 hr. However, intact rats given
an equal oral dose of [14CF ]trifluralin excreted nearly 60% of the 14C
a
in the feces during the same time period. These results suggested that a
low degree of absorption was the most reasonable explanation for the fact
that the feces were the primary route of elimination of trifluralin and/or
its metabolites.
EMMERSON and ANDERSON (1966) isolated from rat feces triHuralin
and a metabolite formed by the reduction of one nitro group (Table I).
These compounds accounted for approximately 16% of the 14C given.
The other HC-labeled metabolites in the feces were not identified. Three
minor metabolites in the urine (accounting for approximately 2.5% of
the HC given) were identified. These compounds resulted from N
dealkylation and/or reduction of nitro groups (Table I). Ten other 14C_
labeled metabolites in the urine were not identified.
GOLAB et al. (1969) identified one 14C-Iabeled metabolite in goat
feces after a goat was dosed with [14C]triHuralin. This compound resulted
from the reduction of both nitro groups and accounted for apprOximately
2.6% of the activity in the feces (Table I). Five radioactive metabolites
were isolated from goat urine. These compounds that resulted from
N-dealkylation and/or reduction of one or both nitro groups (Table I)
accounted for approximately 6.9% of the 14C in the urine.
Trifluralin was rapidly metabolized to a variety of nonpolar and polar
metabolites by rumen fluid (GOLAB et al. 1969) and by some rumen
microbial cultures (WILLIAMS and FElL 1971). GOLAB et al. (1969) iso
lated and characterized four nonpolar triHuralin metabolites that resulted
from N-dealkylation and/or reduction of nitro groups (Table I) from
rumen fluid. WILLIAMS and FElL (1971) isolated and identified five radio
active nonpolar triHuralin metabolites from rumen microbial cultures, all
resulting from N-dealkylationand/or N0 reduction (Table I). The
2
abundant polar trifluralin metabolites produced by rumen microorganisms
(GoLAB et al. 1969, WILLIAMS and FElL 1971) were not identified.
GOLAB et al. (1970) gave a lactating goat [14C]benefin and found that
10.8% of the HC was eliminated in the urine and 89.1% in the feces
"'" 0 l:J ~~
6) 6) 6)
66 6
99 9
Reference SON ANDERSON (1& SON ANDERSON (1& et al. (1969) et al. (1969) MS FEIL (1971) & al. et (1969) al. et (1969) al. et (1969) MS FElL (1971) & al. et (1969) MS FElL (1971) & SON ANDERSON ( 1& al. et (1969) al. et (1969) & MS FEIL (1971)
EMMEREMMERGOLAB GOLAB WILLIA GOLAB GOLAB GOLAB WILLIA GOLAB WILLIA EMMER GOLAB GOLAB WILLIA
e
herbicide metabolism in animals. Metabolites Evidence for structurSource at feces Compo IR Comp.IR og feces Compo IR oat urine umen fluid Compo TLC, GLC umen microbial Compo IR cultures oat feces Comp.TLC oat urine Compo TLC umen fluid TLC, GLC Compo umen microbial Compo IR cultures umen fluid TLC Compo umen microbial IR Compo cultures at urine Compo MP, X-ray dif. oat urine Compo TLC umen fluid Compo TLC umen microbial IR Compo cultures
e RDGRR GGRR RR R GRR
n
nili
a
Dinitroable I. osed structure H,-N-C,H, H~NO' CF, H,-N-C,H, H'Q-NH' CF, H-N-C,H, o,-Q-NO' CF, H-N-C,H, NIL O'-Q- CF,
T op C, N C, N N N
r
P
arent compounds and names C,H,-N-C,H, N~N~ CF, TriflJIralin rifluoro-2,6-dinitro-propyl-p-toluidine
P a,a-tN-di
a,N,