Pesticide and Xenobiotic Metabolism in Aquatic Organisms

430 Pages·1979·6.59 MB·English

by  M. A. Q. Khan

Pesticide and Xenobiotic
Metabolism in Aquatic Organisms
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
Pesticide and Xenobiotic
Metabolism in Aquatic Organisms
M. A. Q. Khan, EDITOR
University of Illinois
John J. Lech, EDITOR
Medical College of Wisconsin
Julius J. Menn, EDITOR
Stauffer Chemical Company
Based on a symposium
sponsored by the Division
of Pesticide Chemistry at the
176th Meeting of the
American Chemical Society,
Miami Beach, Florida,
September 11-17, 1978.
99
ACS S Y M P O S I U M SERIES
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C. 1979
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
Library of Congress CIP Data
Pesticide and xenobiotic metabolism in aquatic orga
nisms.
(ACS symposium series; 9
Includes bibliographies and
1. Pesticides and wildlife—Congresses. 2. Xenobiotic
metabolism—Congresses. 3. Aquatic animals, Effect of
water pollution on—Congresses.
I. Khan, Mohammed Abdul Quddus, 1935- . II.
Lech, John J. III. Menn, Julius J. IV. American Chem
ical Society. Division of Pesticide Chemistry. V. Series:
American Chemical Society. ACS symposium series; 99.
[DNLM: 1. Pesticides—Metabolism—Congresses. 2.
Biotransformation—Congresses. 3. Water pollution,
Chemical—Congresses. 4. Marine biology—Congresses.
5. Water—Analysis—Congresses. WA240 P4735
1979]
QH545.P4P478 574.2'4 79-4598
ISBN 0-8412-0489-6 ASCMC 8 99 1-436 1979
Copyright © 1979
American Chemical Society
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PRINTED IN THE UNITED STATES OF AMERICA
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
ACS Symposium Series
Robert F. Gould, Editor
Advisory Board
Kenneth B. Bischoff James P. Lodge
Donald G. Crosby John L. Margrave
Robert E. Feeney Leon Petrakis
Jeremiah P. Freeman F. Sherwood Rowland
E. Desmond Goddard Alan C. Sartorelli
Jack Halpern Raymond B. Seymour
Robert A. Hofstader Aaron Wold
James D. Idol, Jr. Gunter Zweig
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
FOREWORD
The ACS SYMPOSIUM SERIES was founded in 1974 to provide
a medium for publishin
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that in order to save time the
papers are not typeset but are reproduced as they are sub
mitted by the authors in camera-ready form. Papers are re
viewed under the supervision of the Editors with the assistance
of the Series Advisory Board and are selected to maintain the
integrity of the symposia; however, verbatim reproductions of
previously published papers are not accepted. Both reviews
and reports of research are acceptable since symposia may
embrace both types of presentation.
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
PREFACE
TPVuring the 1960's considerable research effort was directed towards
elucidating the metabolism and fate of foreign compounds in mam
mals, notably therapeutic agents and pesticides. However, little attention
was paid to the processes involved in the biotransformation and elimina
tion of xenobiotic chemicals in aquatic species. During this period some
studies in the literature indicate
able to metabolize foreign compounds. Despite this finding, the con
sensus was that fish do not have nor do they need the ability to biotrans-
form xenobiotic substances. Several pivotal studies in the late Sixties
and early Seventies indicated conclusively that fish have the capacity to
both oxidize and conjugate xenobiotic substances. These observations,
along with a growth in concern for the aquatic environment from both
the ecological and human health points of view, led to interest in the
metabolism of xenobiotic chemicals in aquatic species. The expansion of
research on biotransformation and disposition of xenobiotic chemicals in
fish, along with studies of the effects of these chemicals on aquatic
organisms, has led to the rapid development of aquatic toxicology re
search in the past five years.
Monitoring for the presence of xenobiotic chemicals in aquatic orga
nisms may pertain to both ecological and human health interests. Since
many xenobiotic chemicals ultimately find their way into aquatic species,
knowledge of the location and concentration of these chemicals is ger
mane to both protection of these species and assurance of a safe food
supply for humans. In addition, monitoring the state of chemical con
tamination of the aquatic environment itself is of great importance. Since
it is now known that fish and other aquatic organisms can carry out a
variety of biotransformation reactions, any surveillance program, regard
less of its ultimate purpose, is incomplete unless procedures are designed
to take into account the chemical in question and its metabolic products.
This is important for two reasons : first, chemical residues may be present
in the form of biotransformation products and the identification of these
xenobiotic substances in a given aquatic species will not be valid unless
the nature and quantity of metabolic product is known; secondly, because
it is now known that several biotransformation processes lead to the
ix
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
creation of chemicals which may be more toxic than the parent com­
pounds, it is necessary to know the nature and number of metabolites
which are formed when this situation arises.
The formation of polar metabolites from nonpolar materials may
actually facilitate monitoring programs—in many cases the polar chemi­
cals are highly concentrated in certain body fluids such as bile and urine.
On the other hand, materials such as certain cyclodienes and polychlori-
nated biphenyls, which are very lipid soluble and resistant to metabolism,
may accumulate and these chemicals may persist in the environment and
may be transferred via the food chain to man. There is also interest in
these biotransformation processes in lower organisms since the simplicity
of these systems may lead to a better understanding of the phylogenetic
development of xenobiotic metabolism.
If in the future unforesee
determining the precise toxicity of all the chemicals which may enter
into the aquatic environment, as opposed to knowing which chemicals
are formed and where and how long they persist, the latter may be more
pertinent. While the former is important, a knowledge of precise toxicity
of chemicals to many organisms in all situations may not be feasible,
either economically or within a specified time frame. However, knowl­
edge of the toxicokinetic properties of chemicals and their biotransforma­
tion pathways in aquatic organisms will lead to surveillance programs
reflecting the state of contamination of the aquatic environment. It is
possible that this knowledge will aid in averting an ecological or human
health crisis in the future.
This international symposium presents research from laboratories
concerned with the metabolism and disposition of pesticides and other
xenobiotic substances in aquatic organisms. The studies were not re­
stricted to pesticides since current interest concerns a wide variety of
chemicals and their disposition in aquatic organisms both in vivo and
in vitro. This book is in two sections, one dealing with the in vivo metabo­
lism of chemicals in aquatic organisms and the other describing primarily
mechanisms of metabolism and disposition of xenobiotic chemicals in
these species. Some of the papers overlap these two sections but were
placed in one or the other as a matter of convenience. The authors wish
to acknowledge the cooperation and efforts of the contributors both in
oral presentations at the 176th ACS Meeting in Miami, Florida in Sep­
tember 1978, and in the preparation of the manuscripts comprising this
book.
The authors wish to thank Ms. Cheryl Beyer, Ginger Marlow, and
Pat Kelley for their typing and clerical assistance in planning for the
symposium and book. Activities of the editors related to the symposium
χ
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
and book were supported by NIEHS Grants #ES 01080 and ES 01985
(J.J.L.)> EPA Grant #R803971-010 (J.J.L.)> NIEHS Grant #01479
(M.A.Q.K.), and by the Stauffer Chemical Company (J.J.M.).
University of Illinois M. A. Q. KHAN
Chicago, IL 60680
Medical College of Wisconsin J. J. LECH
Milwaukee, WI 53233
Stauffer Chemical Company J. J. MENN
Mountain View, CA 94042
January 16, 1979
xi
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
1
Metabolism of Organophosphorus Insecticides in Aquatic
Organisms, with Special Emphasis on Fenitrothion
JUNSHI MIYAMOTO, YOSHIYUKI ΤΑΚΙΜΟΤΟ, and KAZUMASA MIHARA
Research Department, Pesticides Division, Institute for Biological Science,
Sumitomo Chemical Co., Ltd., 4-2-1 Takatsukasa, Takarazuka, Hyogo 665, Japan
The organophosphoru
insecticides, and a certai
the aquatic environment resulting either from the actual use on
paddy fields or from unavoidable transmittance to waterways.
However, possibly because of its relatively shorter persistence,
the translocation and transformation of organophosphorus compounds
in the aquatic environment has not been extensively investigated
as compared with more persistent organοchlorine compounds.
Fenitrothion, O,O-dimethyl O-(3-methyl-4-nitrophenyl) phos-
phorothioate, is widely used for the control of paddy field
insects and forest protection in several countries, and since it
is rather highly toxic to some aquatic organisms (LC 50 after 48hr
exposure, 1.28 ppm for rainbow trout, 2.72 ppm for bluegill, 4.4
ppm for carp, LC 50 after 3 hr exposure, 0.0092 ppm for daphnia
and no-effect dosage after 4 week exposure, 0.02 ppm for carp) (1,
2), the knowledge on degradation and metabolism of the compound in
the aquatic environment is important for assessing short-term and
long-term impacts on the non-target aquatic organisms.
In this article metabolism and bioaccumulation of fenitro­
thion in several aquatic species are dealt with under laboratory
conditions.
Metabolism in vitro
To acquire information on the intrinsic metabolic activity
of aquatic organisms, liver of carp (Cyprinus carpio Linnaeus),
rainbow trout (Salmo gairdneri) and freshwater snail (Cipango-
paludina japonica Martens) was dissected out, homogenized in 0.1M
phosphate buffer, pH 7.5, and centrifuged at 105,000 g for 60 min
to obtain the microsome-equivalent (described as the microsomal
fraction hereafter) fraction. The protein content of microsomal
and sub microsomal (supernatant fractions by Lowry's method, micro­
somal P-450 content (3), activity of aniline hydroxylase (4) and
aminopyrine N-demethylase (_5) were determined.
Table I shows the results which reveal that the drug-
0-8412-0489-6/79/47-099-003$05.00/0
© 1979 American Chemical Society
In Pesticide and Xenobiotic Metabolism in Aquatic Organisms; Khan, M., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1979.