INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY
ENVIRONMENTAL HEALTH CRITERIA 130
ENDRIN
This report contains the collective views of an international group of
experts and does not necessarily represent the decisions or the stated
policy of the United Nations Environment Programme, the International
Labour Organisation, or the World Health Organization.
Published under the joint sponsorship of
the United Nations Environment Programme,
the International Labour Organisation,
and the World Health Organization
First draft prepared by Dr G. T. van Esch, Bilthoven,
Netherlands, and Dr E. A. H. van Heemstra-Lequin,
Laren, Netherlands.
World Health Orgnization
Geneva, 1992
The International Programme on Chemical Safety (IPCS) is a
joint venture of the United Nations Environment Programme, the
International Labour Organisation, and the World Health
Organization. The main objective of the IPCS is to carry out and
disseminate evaluations of the effects of chemicals on human health
and the quality of the environment. Supporting activities include
the development of epidemiological, experimental laboratory, and
risk-assessment methods that could produce internationally
comparable results, and the development of manpower in the field of
toxicology. Other activities carried out by the IPCS include the
development of know-how for coping with chemical accidents,
coordination of laboratory testing and epidemiological studies, and
promotion of research on the mechanisms of the biological action of
chemicals.
WHO Library Cataloguing in Publication Data
Endrin.
(Environmental health criteria ; 130)
1.Endrin - toxicity 2.Environmental exposure
I.Series
ISBN 92 4 157130 6 (NLM Classification: WA 240)
ISSN 0250-863X
The World Health Organization welcomes requests for permission
to reproduce or translate its publications, in part or in full.
Applications and enquiries should be addressed to the Office of
Publications, World Health Organization, Geneva, Switzerland, which
will be glad to provide the latest information on any changes made
to the text, plans for new editions, and reprints and translations
already available.
(c) World Health Organization 1992
Publications of the World Health Organization enjoy copyright
protection in accordance with the provisions of Protocol 2 of the
Universal Copyright Convention. All rights reserved.
The designations employed and the presentation of the material
in this publication do not imply the expression of any opinion
whatsoever on the part of the Secretariat of the World Health
Organization concerning the legal status of any country, territory,
city or area or of its authorities, or concerning the delimitation
of its frontiers or boundaries.
The mention of specific companies or of certain manufacturers'
products does not imply that they are endorsed or recommended by the
World Health Organization in preference to others of a similar
nature that are not mentioned. Errors and omissions excepted, the
names of proprietary products are distinguished by initial capital
letters.
CONTENTS
1. SUMMARY AND EVALUATION; CONCLUSIONS; RECOMMENDATIONS
1.1 Summary and evaluation
1.1.1 Exposure
1.1.2 Uptake, metabolism, and excretion
1.1.3 Effects on organisms in the environment
1.1.4 Effects on experimental animals and in vitro
1.1.5 Effects on human beings
1.2 Conclusions
1.3 Recommendations
2 IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES,
ANALYTICAL METHODS
2.1 Identity
2.2 Physical and chemical properties
2.3 Conversion factors
2.4 Analytical methods
3. SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE
3.1 Natural occurrence
3.2 Man-made sources
3.2.1 Production levels and processes, uses
3.2.1.1 World production figures
3.2.1.2 Manufacturing processes
4. ENVIRONMENTAL TRANSPORT, DISTRIBUTION, AND TRANSFORMATION
4.1 Transport and distribution between media
4.1.1 Air
4.1.2 Water
4.1.3 Soil
4.1.4 Soil-plants
4.2 Abiotic degradation
4.3 Biotransformation
4.3.1 Biodegradation
4.3.2 Bioaccumulation and biomagnification
5. ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE
5.1 Environmental levels
5.1.1 Air
5.1.2 Soil, sediments, and sewage sludge
5.1.2.1 Soil
5.1.2.2 Sediments
5.1.2.3 Sewage sludge
5.1.3 Water
5.1.3.1 Surface water
5.1.3.2 Rain and snow
5.1.3.3 Drinking-water
5.1.3.4 Groundwater
5.1.4 Organisms in the environement
5.1.4.1 Birds
5.1.4.2 Fish and shellfish
5.1.4.3 Mixed species
5.1.5 Other food and feed
5.1.5.1 Cereals
5.1.5.2 Fruit and vegetables
5.1.5.3 Meat, poultry, and chicken eggs
5.1.5.4 Milk and milk products
5.1.5.5 Fat and oils
5.1.5.6 Animal feed
5.1.6 Miscellaneous products
5.2 Exposure of the general population
5.2.1 Total-diet studies
5.2.2 Levels in human tissues
5.2.2.1 Adipose tissue
5.2.2.2 Organs
5.2.2.3 Blood
5.2.2.4 Breast milk
5.2.2.5 Appraisal of exposure of the general
population
5.3 Occupational exposure during manufacture, formulation,
and use
5.3.1 Manufacture and formulation
5.3.2 Application
5.3.3 Appraisal of occupational exposure
6. KINETICS AND METABOLISM
6.1 Absorption, distribution, and elimination
6.1.1 Laboratory animals
6.1.1.1 Oral administration
6.1.1.2 Intravenous administration
6.1.2 Domestic animals
6.1.3 Human beings
6.1.4 Systems in vitro
6.2 Biotransformation
6.2.1 Experimental animals
6.2.2 Human beings
6.2.3 Microorganisms
6.2.4 Plants
7. EFFECTS ON ORGANISMS IN THE ENVIRONMENT
7.1 Microorganisms
7.2 Aquatic organisms
7.2.1 Invertebrates
7.2.2 Fish
7.2.2.1 Acute toxicity
7.2.2.2 Short-termtoxicity
7.2.2.3 Studies of resistance
7.2.2.4 Interaction with other chemicals
7.2.2.5 Special studies
7.2.3 Amphibia
7.3 Terrestrial organisms
7.3.1 Honey bees
7.3.2 Birds
7.3.2.1 Acute toxicity
7.3.2.2 Short-term toxicity
7.3.2.3 Studies of reproduction
7.3.2.4 Interaction with other chemicals
7.3.2.5 Special studies
7.3.2.6 Behavioural studies
7.3.3 Mammals
7.3.3.1 Toxicity
7.3.3.2 Studies of resistance
7.4 Effects in the field
7.5 Appraisal of effects on organisms in the environment
8. EFFECTS ON EXPERIMENTAL ANIMALS AND IN VITRO
8.1 Acute toxicity of technical-grade endrin
8.1.1 Oral administration
8.1.2 Dermal administration
8.1.3 Parenteral administration
8.1.4 Toxicity of metabolites and isomers
8.1.4.1 Mammalian metabolites
8.1.4.2 Isomers
8.1.5 Acute toxicity of formulated material
8.1.5.1 Oral and dermal administration
8.1.5.2 Inhalation
8.2 Short-term exposure
8.2.1 Oral administration
8.2.1.1 Mouse
8.2.1.2 Rat
8.2.1.3 Rabbit
8.2.1.4 Dog
8.2.1.5 Domestic animals
8.2.2 Inhalation
8.2.3 Dermal administration
8.3 Skin irritation
8.4 Reproduction, embryotoxicity, and teratogenicity
8.4.1 Reproduction
8.4.1.1 Mouse
8.4.1.2 Rat
8.4.2 Embryotoxicity and teratogenicity
8.4.2.1 Mouse
8.4.2.2 Rat
8.4.2.3 Hamster
8.4.2.4 Perinatal behavioural development
8.4.3 Appraisal of reproductive effects
8.5 Mutagenicity and related end-points
8.5.1 Effects on microorganisms
8.5.2 Point mutations in mammalian cells
8.5.3 Dominant lethal mutations
8.5.4 Chromosomal and cytogenetic effects
8.5.5 Host-mediated effects
8.5.6 Sister chromatid exchange
8.5.7 Effects in Drosophila melanogaster
8.5.8 Effects on DNA
8.5.9 Appraisal of mutagenicity and related end-points
8.6 Long-term exposure
8.7 Carcinogenicity
8.7.1 Oral administration
8.7.1.1 Mouse
8.7.1.2 Rat
8.7.1.3 Tumour promotion
8.7.2 Appraisal of carcinogenicity
8.8 Special studies
8.8.1 Nervous system
8.8.1.1 Electrophysiological studies
8.8.1.2 Histopathological studies
8.8.1.3 Neurotransmitter systems
8.8.1.4 Appraisal of effects on the nervous
system
8.8.2 Cardiovascular system
8.8.3 Effects on liver enzymes
8.8.3.1 Mouse
8.8.3.2 Rat
8.8.3.3 Guinea-pig
8.8.3.4 In-vitro studies
8.8.4 Miscellaneous studies
8.8.5 Factors that influence toxicity
8.8.5.1 Nutrition
8.8.5.2 Potentiation
9. EFFECTS ON HUMAN BEINGS
9.1 Exposure of the general population
9.1.1 Acute toxicity
9.1.2 Poisoning incidents
9.2 Occupational exposure
9.2.1 Factory workers
9.2.2 Dose-response relationships
9.2.3 Exposures to mixtures
9.2.4 Appraisal of effects of occupational exposures
10. PREVIOUS EVALUATIONS BY INTERNATIONAL BODIES
REFERENCES
ANNEX I Chemical names of endrin and its metabolites
ANNEX II Medical treatment of endrin poisoning
ANNEX III Management of major status epilepticus in adults
RESUME
RESUMEN
WHO TASK GROUP ON ENVIRONMENTAL HEALTH CRITERIA
FOR ENDRIN
Members
Dr L.A. Albert, Consultores Ambientales Asociados, Xalapa, Veracruz,
Mexico
Dr V. Benes, Department of Toxicology and Reference Laboratory,
Institute of Hygiene and Epidemiology, Prague, Czechoslovakia
Dr S. Dobson, Institute of Terrestrial Ecology, Monks Wood
Experimental Station, Huntingdon, United Kingdom
Dr G.J. van Esch, Bilthoven, Netherlands (Rapporteur)
Dr E.A.H. van Heemstra-Lequin, Laren, Netherlands (Rapporteur)
Dr S.K. Kashyap, National Institute of Occupational Health,
Ahmedabad, India
Dr Yu.I. Kundiev, Research Institute of Labour Hygiene and
Occupational Diseases, Kiev, Ukraine (Vice-Chairman)
Dr Y. Osman, Ministry of Health, Riyadh, Saudi Arabia
Dr H. Spencer, United States Environmental Protection Agency,
Washington DC, USA (Chairman)
Dr C. Winder, National Institute of Occupational Health and Safety,
Forest Lodge, New South Wales, Australia
Secretariat
Dr K.W. Jager, International Programme on Chemical Safety, World
Health Organization, Geneva, Switzerland (Secretary)
Ms B. Labarthe, International Register of Potentially Toxic
Chemicals, United Nations Environment Programme, Geneva,
Switzerland
Dr T.K. Ng, Office of Occupational Health, World Health
Organization, Geneva, Switzerland
NOTE TO READERS OF THE CRITERIA MONOGRAPHS
Every effort has been made to present information in the Criteria
monographs as accurately as possible without unduly delaying their
publication. In the interest of all users of the Environmental Health
Criteria monographs, readers are kindly requested to communicate any
errors that may have occurred to the Director of the International
Programme on Chemical Safety, World Health Organization, Geneva,
Switzerland, in order that they may be included in corrigenda.
* * *
A detailed data profile and a legal file can be obtained from the
International Register of Potentially Toxic Chemicals, Palais des
Nations, 1211 Geneva 10, Switzerland (Telephone no. 7988400 or
7985850).
* * *
The proprietary information contained in this monograph cannot
replace documentation for registration purposes, because the latter
has to be closely linked to the source, the manufacturing route, and
the purity/impurities of the substance to be registered. The data
should be used in accordance with paragraphs 82-84 and recommendations
paragraph 90 of the Second FAO Government Consultation (1982).
ENVIRONMENTAL HEALTH CRITERIA FOR ENDRIN
A WHO Task Group on Environmental Health Criteria for Endrin and
Isobenzan met at the World Health Organization, Geneva, from 23 to 27
July 1990. Dr K.W. Jager, IPCS, welcomed the participants on behalf of
Dr M. Mercier, Director of IPCS, and the three IPCS cooperating
organizations (UNEP, ILO, WHO). The Group reviewed and revised the
draft Criteria monographs and Health and Safety Guides and made an
evaluation of the risks to human health and the environment from
exposure to endrin and isobenzan.
The first drafts of these monographs were prepared in cooperation
between Dr E.A.H. van Heemstra-Lequin and Dr G.J. van Esch of the
Netherlands. Dr van Esch prepared the second drafts, incorporating the
comments received following circulation of the first drafts to the
IPCS contact points for Environmental Health Criteria monographs.
Dr K.W. Jager of the IPCS Central Unit was responsible for the
scientific content of the monographs, and Mrs E. Heseltine, St
Léon-sur-Vézère, France, for the editing.
The fact that Shell Oil Co. made available to IPCS and the Task
Group proprietary toxicological information on their products is
gratefully acknowledged. This allowed the Task Group to base their
evaluation on more complete data.
The effort of all who helped in the preparation and finalization
of the monographs is gratefully acknowledged.
* * *
Partial financial support for the publication of this Criteria
monograph was kindly provided by the United States Department of
Health and Human Services, through a contract from the National
Institute of Environmental Health Sciences, Research Triangle Park,
North Carolina, USA, a WHO Collaborating Centre for Environmental
Health Effects.
1. SUMMARY AND EVALUATION; CONCLUSIONS; RECOMMENDATIONS
1.1 Summary and evaluation
1.1.1 Exposure
Endrin is an organochlorine insecticide which has been used since
the 1950s against a wide range of agricultural pests, mostly on cotton
but also on rice, sugar-cane, maize, and other crops. It is also used
as a rodenticide. It is available commercially as dusts, granules,
pastes, and an emulsifiable concentrate.
Endrin enters the air mainly by volatilization and aerial drift.
In general, volatilization takes place after application to soils and
crops and depends on many factors, such as the organic matter and
moisture content of the soil, humidity, air flow, and the surface area
of plants.
The most important route of contamination of surface water is
run-off from soil. Contamination from precipitation in the form of
snow or rain is negligible. Local contamination of the environment may
occur from industrial effluents and careless application practices.
The major source of endrin in soil is from direct application to
soil and crops. Endrin can be retained, transported, or degraded in
soil, depending on a number of factors. The greatest retention occurs
in soils with a high content of organic matter. The persistence of
endrin is highly dependent upon local conditions; its half-life in
soil can range up to 12 years. Volatilization and photodecomposition
are the primary factors in the disappearance of endrin from soil
surfaces. Under the influence of sunlight (ultraviolet light), the
isomer delta-ketoendrin is formed. In intense summer sun, about 50% of
endrin was isomerized to this ketoendrin within 7 days. Microbial
transformation (in fungi and bacteria) takes place, especially under
anaerobic conditions, to give the same product.
Aquatic invertebrates and fish take up endrin rapidly from water,
but exposed fish transferred to uncontaminated water lose the
pesticide rapidly. Bioconcentration factors of 14-18 000 have been
recorded after continuous exposure. Soil invertebrates may also take
up endrin readily.
The occasional presence of low levels of endrin in air and in
surface and drinking-water in agricultural areas is of little
significance from the point of view of public health. The only
exposure that may be relevant is dietary intake. In general, however,
the reported intake levels are far below the acceptable daily intake
of 0.0002 mg/kg body weight established in 1970 (FAO/WHO, 1971).
1.1.2 Uptake, metabolism, and excretion
Unlike dieldrin, its stereoisomer, endrin is metabolized rapidly
by animals, and very little is accumulated in fat in comparison with
compounds of similar chemical structure.
Both uptake and excretion after oral administration are rapid in
rats, and its biological half-life is 1-6 days, depending on the dose
level. A steady state, at which the excreted amount equals the daily
intake, is reached after 6 days. A sex difference is observed, in that
males excrete endrin and metabolites via the bile much faster than
females, resulting in less accumulation in male adipose tissue. Rats
excrete this compound mainly in the faeces as endrin,
anti-12-hydroxyendrin, and a hydroxylated endrin derivative within
the first 24 h (70-75%); a third metabolite, 12-ketoendrin,
accumulates in tissues. Rabbits excrete 50% of the metabolites of
endrin in urine, whereas in rats only 2% are excreted by this route;
only unchanged endrin is found in the faeces of rabbits.
Cows administered endrin at 0.1 mg/kg of diet for 21 days
excreted up to 65% as metabolites in urine, 20% in faeces, partly as
unchanged endrin, and 3% in milk, also mainly as endrin. These cows
had residue levels of 0.003-0.006 mg/litre in milk, 0.001-0.002 mg/kg
in meat, and 0.02-0.1 mg/kg in fat.
Laying hens fed endrin showed residue levels (depending on the
doses given) of up to 0.1 mg/kg in meat, 1 mg/kg in fat, 0.1-0.2 mg/kg
in eggs (yolk), 0.4 mg/kg in kidney, and 0.5 mg/kg in liver. Except in
liver and kidney, the residues found were mainly unchanged endrin.
About 50% of the administered endrin was excreted in faeces, mainly as
metabolites.
In human beings, rats, rabbits, cows, and hens, the major
biotransformed metabolite of endrin is anti-12-hydroxyendrin,
together with its sulfate and glucuronide conjugates. Four other
metabolites were found but in only minor quantities. Mainly unchanged
endrin is found in body tissues and milk. After this pesticide was
applied to plants, unchanged endrin and two hydrophilic transformation
products were identified.
1.1.3 Effects on organisms in the environment
The effect of endrin on soil bacteria and fungi is minimal. Dose
levels of 10-1000 mg/kg of soil had no effect on decomposition of
organic matter, denitrification, or generation of methane. Endrin is
very toxic to fish, aquatic invertebrates, and phytoplankton: the 96-h
LC50 values are mostly below 1.0 µg/litre. The lowest observed
adverse effect level in a life cycle test on the mysid shrimp,
Mysidopsis bahia, was established at 30 ng/litre.
The reported tests on the acute toxicity of endrin in aquatic
organisms were conducted in aquaria without sediment; the presence of
sediment would be expected to attenuate the effect of endrin. Heavily
contaminated sediment had little effect on species living in open
water, suggesting that sediment-bound endrin has low bioavailability.
Tests have not been conducted on aquatic animals living in sediment.
The LD50 for terrestrial mammals and birds is in the order of
1.0-10.0 mg/kg body weight. Mallard ducks fed up to 3.0 mg/kg body
weight for 12 weeks showed no effect on egg production, fertility, or
hatchability.
Certain species of aquatic invertebrates, fish, and small mammals
have been reported to be resistant to the toxicity of endrin, and
exposure to several different organochlorine pesticides led to
selection of strains resistant to endrin.
Fish kills were observed in areas of agricultural run-off and
industrial discharge; and declining populations of brown pelicans (in
Louisiana, USA) and of sandwich terns (in the Netherlands) have been
attributed to exposure to endrin in combination with other halogenated
chemicals.
1.1.4 Effects on experimental animals and in vitro
Endrin is a highly toxic pesticide, the signs of intoxication
being neurotoxic. The oral LD50 of technical-grade endrin for
laboratory animals is in the range of 3-43 mg/kg body weight; the
dermal LD50 for rats is 5-20 mg/kg body weight. No substantial
difference in acute oral or dermal toxicity was found between
technical-grade and formulated (emulsifiable concentrate and wettable
powder) products.
Short-term experiments for oral toxicity have been carried out
using mice, rats, rabbits, dogs, and domestic animals. In mice and
rats, the maximum tolerated doses for 6 weeks were 5 and 15 mg/kg diet
(equivalent to 0.7 mg/kg body weight), respectively. Rats survived a
16-week exposure to 1 mg/kg diet (equivalent to 0.05 mg/kg body
weight); rabbits died after receiving repeated doses of 1 mg/kg body
weight. In dogs, a dose of 1 mg/kg of diet (approximately equivalent
to 0.025 mg/kg body weight), given over 2 years, was without effect.
The neurological basis of the observed signs of intoxication is
inhibition of gamma-aminobutyric acid (GABA) function at low doses.
Like other chlorinated hydrocarbon insecticides, endrin also affects
the liver, and stimulation of enzyme systems involved in the
metabolism of other chemicals is evident, as shown by, for instance,
decreased hexobarbital sleeping time in mice.
Doses of 75-150 mg/kg applied dermally as a dry powder for 2 h
daily caused convulsions and death in rabbits but did not result in
skin irritation. Production of systemic toxicity without irritation at
the site of contact is noteworthy.
Long-term studies of toxicity and carcinogenicity have been
performed in mice and rats. No carcinogenic effect was found, but
these studies had shortcomings, including poor survival of the
animals. The no-observed-effect level for toxicity in a two-year study
in rats was 1 mg/kg of diet (equivalent to about 0.05 mg/kg body
weight). Tumour promoting effects were not demonstrated when endrin
was tested in combination with subminimal quantities of chemicals
known to be carcinogenic to animals. The Task Group concluded that the
data are insufficient to indicate that endrin is a carcinogenic hazard
to humans.
Endrin was found to be nonmutagenic in several studies.
In most studies, it was not teratogenic to mice, rats, or
hamsters, even at doses that caused maternal or fetotoxicity. The
no-observed-adverse-effect level was 0.5 mg/kg body weight in mice and
rats and 0.75 mg/kg body weight in hamsters. Endrin did not induce
reproductive effects in rats over three generations when given at a
dose of 2 mg/kg of diet (about 0.1 mg/kg body weight).
A number of the metabolites of endrin have similar or higher
acute toxicities than the parent compound. The transformation product,
delta-ketoendrin, is less toxic than endrin, but 12-ketoendrin is
considered to be the most toxic metabolite of endrin in mammals, with
an oral LD50 in rats of 0.8-1.1 mg/kg body weight.
1.1.5 Effects on human beings
Several episodes of fatal and non-fatal accidental and suicidal
poisoning have occurred. Cases of acute non-fatal intoxication due to
accidental over-exposure were observed in workers in an endrin
manufacturing plant. The oral dose that causes death has been
estimated to be approximately 10 mg/kg body weight; the single oral
dose that causes convulsions was estimated to be 0.25-1.0 mg/kg body
weight.
The primary site of action of endrin is the central nervous
system. Exposure of humans to a toxic dose may lead within a few hours
to such signs and symptoms of intoxication as excitability and
convulsions, and death may follow within 2-12 h after exposure if
appropriate treatment is not administered immediately. Recovery from
non-fatal poisoning is rapid and complete.
Endrin does not accumulate in the human body to any significant
degree. No long-term adverse effects were reported in 232
occupationally exposed workers (length of exposure, 4-27 years) under
medical supervision (observation time, 4-29 years). The only effect
observed was indirect evidence of a reversible stimulation of drug
metabolizing enzymes.
Endrin was detected in virtually none of a large number of
samples of adipose tissue, blood, and breast milk analysed in many
countries. The Task Group attributed the absence of endrin in human
samples to the low exposure of the general population to this
pesticide and to its rapid metabolism.
Endrin was detected in blood (at up to 450 µg/litre) and in
adipose tissue (at 89.5 mg/kg) in cases of fatal accidental poisoning.
No endrin was found in workers under normal circumstances. The
threshold level of endrin in blood, below which no sign or symptom of
intoxication occurs, has been estimated to be 50-100 µg/litre. The
half-life of endrin in blood may be in the order of 24 h.
1.2 Conclusions
Endrin is an insecticide with high acute toxicity. It may cause
severe poisoning in cases of over-exposure caused by careless handling
during its manufacture and use or by consumption of contaminated food.
The general public is exposed to endrin mainly as its residues in
food; however, the reported intake of endrin is generally far below
the acceptable daily intake established by FAO/WHO. Such exposures
should not constitute a health hazard to the general population. When
good work practices, hygiene measures, and safety precautions are
enforced, endrin is unlikely to present a hazard to exposed workers.
It is clear that uncontrolled discharges of endrin during its
manufacture, formulation, and use can result in acute environmental
problems associated with its high toxicity. The effects on wildlife of
its agricultural use are less clear, although fish and fish-eating
birds are at risk from surface run-off. Declines in the populations of
some avian species have been associated with the presence of high
levels of residues of various organochlorines in the tissues of adults
and in eggs. Endrin has been measured in some of these species;
however, it is very difficult to separate the effects of the different
organochlorines present.
1.3 Recommendations
1. Endrin should not be used unless it is indispensable and
only when no less toxic alternative is available.
2. For the health and welfare of workers and the general
population, the handling and application of endrin should be
entrusted only to competently supervised, well-trained operators
who will follow adequate safety measures and apply endrin
according to good agricultural practices.
3. The manufacture, formulation, agricultural use, and disposal
of endrin should be managed carefully to minimize contamination
of the environment, particularly surface water.
4. People exposed regularly to endrin should undergo periodic
health evaluations.
5. Epidemiological studies of exposed worker populations should
be continued.
6. In countries where endrin is still used, food should be
monitored for endrin residues.
7. If the use of endrin continues, more information should be
obtained on the presence, ultimate fate, and toxicity of
12-ketoendrin and delta-ketoendrin.
2. IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES, ANALYTICAL METHODS
2.1 Identity
CAS chemical name: (1a-alpha,2ß,2aß,3-alpha,6-alpha,6aß,
7ß,7a-alpha)-3,4,5,6,9.9-hexachloro
1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-
dimethanonaphth[2,3-b]oxirene
(9CI-CAS)
Former CAS chemical name: 1,2,3,4,10,10-hexachloro-6,7-epoxy-
1,4,4a,5,6,7,8,8a-octahydro-1,4-
endo,endo-5,8-dimethanonaphthalene
IUPAC chemical name: 1 R,4 S,4a S,5 S,6 S,7 R,8 R,8a
R)-1,2,3,4,10,10-hexachloro-
1,4,4a,5,6,7,8,8a-octahydro-6,7-
epoxy-1,4:5,8- dimethanonaphthalene
Chemical structure:
Endrin is the endo,endo stereoisomer of dieldrin
Empirical formula: C12H8Cl6O
Relative molecular mass: 380.93
Common name: Endrin
CAS registry number: 72-20-8
RTECS registry number: I01575000
Synonyms: Endrex, Experimental Insecticide 269,
Hexadrin, Nendrin, NCI-COO157,
ENT17251, OMS 197, and Mendrin
Trade name: Endrin
Purity: Not less than 92%. Impurities include
dieldrin (0.42%), aldrin (0.03%),
isodrin (0.73%), endrin half-cage
ketone (1.57%), endrin aldehyde
(0.05%), and heptachloronorbornene
(0.09%) (Donoso et al., 1979).
2.2 Physical and chemical properties
Table 1. Physical and chemical properties of endrin
Physical state Crystalline solid
Colour White to light-tan
Odour Mild chemical
Melting-point 226-230 °C
(decomposes at above 245 °C)
Flash-point None (dry powder is non-flammable,
but commercial solutions contain
inflammable liquids with flash-points
as low as 27 °C)
Explosion limits Non-explosive
Specific gravity
(density) 1.64 g/ml at 20 °C
Vapour pressure 2.7 x 10-7 mmHg at 25 °C
(36 µPa at 25 °C)
Solubility in water Practically insoluble
(0.23 mg/litre at 25 °C)
Solubility in organic Sparingly soluble in alcohol and
solvents petroleum hydrocarbons; moderately
soluble in aliphatic hydrocarbons;
and quite soluble in solvents such
as acetone, benzene, carbon
tetrachloride, and xylene
Log P octanol/water 5.34
partition coefficient
Stability: Technical-grade endrin is stable in storage at ambient
temperatures. Endrin is stable in formulations with
basic reagents, alkaline oxidizing agents, emulsifiers,
wetting agents, and solvents. It isomerizes under the
influence of ultraviolet light. It reacts with
concentrated mineral acids, acid catalysts, acid
oxidizing agents and active metals. When mixed with
certain catalytically active carriers, endrin tends to
decompose; however, most active dust carriers can be
deactivated by the addition of hexamethylenetetramine
and form stable mixtures with endrin. When heated to
above 200 °C, endrin undergoes molecular rearrangements
to form delta-ketoendrin, a compound that is less active
as an insectide (IARC, 1974; Donoso et al., 1979).
2.3 Conversion factors
1 ppm = 16 mg/m3 at 20 °C
1 mg/m3 = 0.063 ppm at 20 °C
2.4 Analytical methods
Most of the analytical procedures used since the early 1960s have
been based on the following steps:
(i) extraction using a suitable solvent;
(ii) clean-up by liquid/liquid partition followed by column
chromatography;
(iii) further separation from co-extractives by gas
chromatography (GC); and
(iv) quantification using an electron-capture, coulometric, or
Hall electrolytic detector
General procedures based on these steps are not specific for
endrin; therefore, its identity must be confirmed in environmental
samples. This can be achieved by chemical derivatization and mass
spectrometry (Chau & Cochrane, 1969, 1971; Belisle et al., 1972; Chau,
1974; Safe & Hutzinger, 1979).
Roos et al. (1987) used size exclusion chromatography to clean-up
pesticides after extraction with ethyl acetate from fish oils, animal
fat, cereals, vegetables, fruit, and liver. The recoveries of endrin
were 90-95%, at a limit of detection of 0.02 mg/kg. This method was
found to be adequate for screening and requires only 15% of the amount
of solvents normally used.
Gübeli & Clerc (1988) described a relatively simple gas-liquid
chromatography method for the detection and approximate quantification
of chlorinated pesticides in ethanolic extracts of medicinal plants
(tinctures). The method was based on extraction with hexane and
capillary GC/63Ni-electron-capture detection. The limit of detection
for endrin was 0.005 mg/kg with a recovery of 77.5%.
Suzuki et al. (1974) separated many pesticides from extracts of
crops and soil into different groups by column chromatography prior to
thin-layer chromatography to obtain systematic identification and
determination. Silica gel was used for the column chromatography and
for the thin-layer plates; glass columns packed with different
absorbents were used for GC separation. Determination was done using
electron-capture detection with a 63Ni source.
To improve the separation by heat of 28 organochlorine
insecticides, including endrin, using gas-liquid chromatography with
electron capture detection, Suzuki & Morimoto (1986) tested three
chemically bonded, fused silica capillary columns. The column prepared
with OV-17 performed best. The method was used with minimal clean-up
and gave good results in the analysis of extracts of several soil
samples, avoiding the disadvantages of low resolution of peaks in
packed columns, handling of glass capillary columns and the high cost
of GC-mass spectrometry systems.
Kiang & Grob (1986) developed a screening procedure for the
determination of 49 pollutants of high priority, including endrin, in
soil or sludge. Methylene chloride at two pH values was used in the
extraction procedure, which was followed by capillary GC. No clean-up
procedure was carried out. Separation and identification were
performed with a GC-mass spectrometry system involving a 30-m fused
silica column; a 60-m column was used for quantification. Recovery of
endrin from soil in the base-neutral extract was 92 ± 14% from 2.04
mg/kg but only 70 ± 8% from 20.4 mg/kg.
Japenga et al. (1987) described a rapid clean-up procedure for
the simultaneous determination of groups of micropollutants in
sediment. The samples were pretreated with acid, mixed with silica,
and extracted on a Soxhlet column with a mixture of benzene and
hexane. Humic substances and elemental sulfur were removed by passing
the extract through a chromatographic column containing basic alumina
on which sodium sulfite and sodium hydroxide were absorbed. After
silica fractionation, the concentrations of polycyclic aromatic
hydrocarbons, polychlorinated biphenyls, and chlorinated pesticides
were determined by GC. The recovery of endrin was reported to
fluctuate between 93 and 103%.
The efficiency of clean-up with sulfuric acid and confirmation
with potassium hydroxide-ethanol hydrolysis was studied for 22
organochlorine pesticides and polychlorinated biphenyls in water
samples (Hernandez et al., 1987); analysis was by GC/electron-capture
detection, and the pesticides were extracted by partition with 15%
diethyl ether in hexane. After clean-up with sulfuric acid, only 4.9%
of the endrin was recovered; however, with the potassium
hydroxide-ethanol treatment, 97-100% was recovered, depending on the
endrin concentration and the length of treatment.
Method 8080 of the US Environmental Protection Agency (EPA)
(Manual, SW-846) was evaluated in a single laboratory study by Lopez-
Avila et al. (1988). Since the Florisil clean-up procedure recommended
does not separate organochlorine pesticides from polychlorinated
biphenyls, GC analysis on a packed column may result in false
identifications; therefore, silica gel was substituted for Florisil,
a capillary glass column was used instead of the packed column, and a
procedure to remove elemental sulfur incorporated. Detection limits
for liquid matrices ranged from 0.02 to 0.09 µg/litre for
organochlorine pesticides; for solid matrices, a range of 1-6 µg/kg
was found. The recovery of endrin in liquid waste was up to 102% at a
spiked concentration of 1.0 µg, but for a sandy loam soil it varied
from 47 to 74%.
Donahue et al. (1988) compared two techniques for quantifying
environmental contaminants in human serum: peak area matching and
linear regression. No statistically significant difference was seen in
the results obtained by these two methods when the concentration of
chlorinated pesticides was > 0.5 µg/litre.
The sampling and determination of endrin in air were described in
detail by NIOSH (1989).
A method for determining residues of the metabolite
anti-12-hydroxy-endrin, present as the ß-glucuronide, in urine was
described by Baldwin & Hutson (1980). Following oxidation with sodium
metaperiodate and hydrolysis with a mild base, the metabolite is
determined by gas-liquid chromatography with electron-capture
detection.
Polychlorinated biphenyls and 21 chlorinated pesticides,
including endrin, were analysed in samples of water, soil, and
sediment in six laboratories using uniform calibration solutions,
analytical methods, and special software operating on minicomputers to
control the operation of the mass spectrometer. The results obtained
for solid samples with four combinations of methods for extraction and
clean-up were compared; although no combination was optimal for all
samples, shaker and sonicator extraction, both with Florisil clean-up,
gave the best results. Several factors that affected the quality of
the results were identified, including errors in computation and
transcription and inadequate review of data (Alford-Stevens et al.,
1988).
Seventeen laboratories participated in an international
comparison of analyses for organochlorine compounds (Holden, 1970).
The results for endrin, summarized in Table 2, were more variable than
those for other insecticides. In an inter-laboratory collaborative
study reported by a Committee of the Ministry of Agriculture,
Fisheries, and Food of the United Kingdom (Anon., 1979) for the
determination of endrin in pork fat (fortified to 0.019 mg/kg), the
mean recovery in 11 laboratories was 84%, but the range was 5-131%.
Table 2. Results for endrin of an inter-laboratory study of
the analysis of organochlorine compounds (Holden, 1970)
Type of No. of laboratories Mean concentration Standard Coefficient Range
sample with results for (mg/litre or mg/kg) deviation of variation
endrin (%)
Solution 17 5.929b 1.01 17.1 4.9-8.2
in hexanea
Cod liver 14 0.02 - - NDc-0.20d
oil
Chicken 16 0.136 0.073 54 0.07-0.3e
egg
Sprat 14 0.132 0.039 29 0.09f-0.21
a Containing endrin and five other organochlorine insecticides
b True (nominal, fortified) value, 7.05 mg/litre
c Twelve laboratories reported no detectable residue
d Value reported to be suspect
e Excluding one laboratory that reported suspected presence of endrin
f Excluding one laboratory that reported a 'trace' of endrin
Table 3. Methods for the analysis of endrin
Sample type Extraction Clean-up Detection and Recovery Limit of Reference
quantificationa (%) detection
Adipose tissue Acetone:hexane Fractionation by Capillary column > 100 Lebel & Williams
(15:85 v/v) gel permeation gas chromatography (1986)
chromatography with columns of different
methylene polarity, GC-MS
chloride-cyclo-hexane
Florisil column
Air Hexylene glycol/ Florisil GLC/ECD 77 0.1 ng/m3 Stanley et al.
Greenburg Smith column (1971)
impinger; alumina
column
Air Toluene - GLC/ECD (63Ni) - 0.02µg/ NIOSH (1989)
sample
Water Hexane:ethyl ether - GLC/ECD 65-97 0.002 Lichtenberg
µg/litre et al. (1970)
Soil/sediment Acetone:hexane Alumina GLC/ECD 83 0.1 µg/kg Goerlitz & Law
column (1974)
Soil/sediment Acetone:petroleum Alumina GLC/ECD 90 0.01 mg/kg Wegman & Hofstee
ether column (1982)
Soil/sediment Hexane Alumina/ GLC/ECD - 0.01 mg/kg McIntyne & Lester
silver nitrate + (1984)
silica gel
column
Table 3 (contd)
Sample type Extraction Clean-up Detection and Recovery Limit of Reference
quantificationa (%) detection
Crops Hexane:isopropanol; Carbon absorption GLC/ECD 93-107 - Kathpal & Dewan
or acetonitrile (Nuchar C-190N) (1975)
Fatty foods, Hexane:acetone Alumina GLC/ECD 68-100 5-10 µg/kg Telling et al.
vegetable oils, column (1977)
fish oils
Viscera Diethyl ether Celite GLC/ECD 72-92 - Kurhekar et al.
column (1975)
Birds' brain Petroleum ether: Florisil GLC/ECD 70 0.05 mg/kg Ludke (1976)
samples ethyl ether column
Cows' milk Diethyl ether: Silica gel GLC/ECD 90 0.0001 mg/kg Baldwin et al.
hexane + ether (1976)
Hens' eggs Hexane:acetone Silica gel GLC/ECD 76 0.05 mg/kg Baldwin et al.
(yolks) (1976)
Crops, soil, Hydrocarbon Florisil:Celite + Reduction with 75-100 1 mg/kg Terriere (1964)
milk, animal solvent magnesia column, metallic sodium;
tissues (Skellysolve after alkaline phenyl azide
B) + isopropanol hydrolysis, if colorimetry
appropriate
-a GC-MS, gas chromatography-mass spectometry; GLC-ECD, gas-liquid chromatography-electron capture detection
Thier & Stijve (1986) reported a comparative study among 53
laboratories in Switzerland on the analysis of a vegetable fat spiked
with 13 organochlorine and five organophosphorus compounds. Endrin was
present at a concentration of 0.08 mg/kg and was identified by 77% of
the laboratories.
Some of the methods that are used for the analysis of endrin are
summarized in Table 3; the estimates given of the accuracy of the
procedures and the limits of detection refer to the specific
investigations and are not absolute values. The percentage recoveries
are an indication of the accuracy of the methods; the precision of
individual method is of interest particularly in regard to
inter-laboratory comparisons.
The many publications on specific procedures are reviewed in the
Codex Alimentarius Commission publication Recommendations for Methods
of Analysis of Pesticide Residues, CAC/PR8-1986 (FAO/WHO, 1986a).
That review lists 14 individual publications; it also lists the
following compendia of methods, which may be consulted.
-- Official Methods of Analysis of the Association of Official
Analytical Chemists, 14th Edition, 1984
-- Pesticide Analytical Manual, Washington DC, Food and Drug
Administration
-- Manual on Analytical Methods for Pesticide Residues in Foods,
Ottawa, Health Protection Branch, Health and Welfare Canada, 1985
-- Methodensammlung zur Rückstandsanalytik von
Pflanzenschutzmitteln (Methods for Analysing Residues of Plant
Protection Agents), Weinheim, Verlag Chemie GmbH, 1984
-- Chemistry Laboratory Guidebook, Washington DC, US Department
of Agriculture
Whatever procedure is adopted should be carried out following the
requirements of the Codex Alimentarius Commission publication Codex
Guidelines on Good Laboratory Practice in Pesticide Residue Analysis,
CAC/PR7-1984 (FAO/WHO, 1984).
3. SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE
3.1 Natural occurrence
Endrin does not occur naturally.
3.2 Man-made sources
3.2.1 Production levels and processes, uses
Endrin is a foliar insecticide which acts against a wide range of
agricultural pests at doses of the active material of 0.2-0.5 kg/ha.
It has a broad spectrum of control and is particularly effective
against Lepidoptera. It is used mainly on cotton but also against
pests of rice, sugar cane, maize, and other crops. It is also used as
a rodenticide (IARC, 1974). An endrin emulsion of 2% killed 40% of
Achatina fulica snails, an agricultural pest, in India (Singh,
1988).
A general indication of the possible uses of endrin can be
derived from the maximal residue limits recommended by FAO/WHO (1986b;
see section 10).
3.2.1.1 World production figures
Endrin was developed by J. Hyman & Co. and licensed to be
manufactured by Shell International Chemical Co. and Velsicol Chemical
Co. in 1950 (Thompson, 1976). It was made in the USA by Shell and
Velsicol and in the Netherlands by Shell. Its use has been banned in
many countries and severely restricted in others (Donoso et al., 1979;
Gips, 1987; Pearce, 1987). Shell discontinued manufacture of endrin in
1982; it is still manufactured in Mexico.
Whetstone (1964) estimated that 2.3-4.5 million kg of endrin were
sold in the USA in 1962. Imports of endrin into Japan in 1970 were 72
000 kg. The annual quantities of endrin that were used in paddy rice
production in Bali over the period 1963-72 varied from 171 to 10 700
kg (Machbub et al., 1988). After 1972, endrin was no longer used.
3.2.1.2 Manufacturing process
Endrin is produced by condensing vinyl chloride with
hexachloro-cyclopentadiene, dehydrochlorinating the adduct, and
subsequent reaction with cyclopentadiene to form isodrin, which is
epoxidized by peracetic or perbenzoic acid (Whetstone, 1964). The
intermediate isodrin can be manufactured via 1,2,3,4,7,7-
hexachloronorbornadiene (US EPA, 1985).
4. ENVIRONMENTAL TRANSPORT, DISTRIBUTION, AND TRANSFORMATION
4.1 Transport and distribution between media
4.1.1 Air
Endrin can enter the air by volatilization, evaporation, and
aerial drift during application, and as a vapour from manufacturing
and formulating plants. Most studies showed rapid volatilization
following application to soils and crops, the extent of vaporization
depending upon a large number of factors, including soil organic
matter, moisture content, air humidity, air flow, and surface area of
plants (Donoso et al., 1979).
4.1.2 Water
Endrin can reach surface water by several routes, including
effluents and waste disposal from endrin manufacturing and formulating
plants and careless aerial application, but by far the most important
route of contamination is surface run-off from soil and crops. Run-off
is affected by numerous, complex factors, such as intensity of
precipitation, irrigation practices, soil permeability, topographic
relief, organic content of the soil, and the degree of vegetative
cover. Soils of low permeability and low organic content allow copious
run-off after heavy precipitation (Donoso et al., 1979). Contamination
of surface water by industrial effluents and careless practices and
disposal (such as washing of drums and spray equipment in streams)
results in regional effects.
In 1961, studies were conducted in the Bayou Yokely basin in
Louisiana, USA, where 3300 acres (1335 ha) of sugar-cane were treated
with nearly 2000 lb (907 kg) of endrin between June and August. Of 18
water samples taken between April and November, six contained endrin
at levels of 0.001-0.36 µg/litre, with an average of 0.1 µg/litre. In
1964, the area was treated with 1200 lb (544 kg) of endrin, and the
pattern of residues was the same. The mean residue levels in samples
taken in September were 0.44 µg/litre in grab samples and 0.53
µg/litre in carbon adsorption samples; after three months, the average
levels were 0.03 and 0.04 µg/litre, respectively. Sediment samples
contained 165 µg/kg; after three months, this level had decreased to
70 µg/kg (Lauer et al., 1966).
Another, less important source of water contamination is run-off
from endrin-coated seeds. Marston et al. (1969) found that although
approximately 11% of the initial amount was washed off by water under
laboratory conditions, in field conditions the loss was smaller. The
total amount detected in the watershed 6 days after aerial application
of endrin-coated seed was 0.12% of the applied dose. The highest
concentration found in the water was 0.07 µg/litre.
A third possible source of contamination is fall-out by
precipitation in the form of rain and snow, but the measured levels
are negligible (see section 5.1.3.2).
4.1.3 Soil
The major source of endrin in soil is from direct application to
soil and crops. The amount of endrin that reaches the soil depends on
the type of crop and the method of application. The fate of endrin in
soil determines the degree to which the rest of the environment (water
and atmosphere) is contaminated. In soil, endrin can be retained,
transported, or degraded, depending on a large number of interrelated
factors (Donoso et al., 1979). When endrin was applied to tall, dense
crops such as tobacco, no residue appeared in the soil; when it was
applied to soil, the amount that remained depended on the retentive
ability of the soil. Although endrin has strong absorptive properties
in soils such as clay and sandy loam, limited residues were found. Far
greater retention was found in soils with a high organic content, in
which it was adsorbed quickly and was difficult to remove. The degree
to which endrin was retained in the soil depended not only on the soil
type but on numerous other factors such as volatilization, leaching,
wind erosion, surface run-off, and crop uptake (Harris et al., 1966).
In general, the persistence of endrin is highly dependent upon local
conditions, and residue levels can range from traces to milligrams per
kilogram. Its half-life in soil can be as long as 12 years (Donoso et
al., 1979).
The factors that affect the degree to which endrin is retained in
soil (Donoso et al., 1979) can be generalized as follows:
(a) Endrin appears to be less persistent if it is applied to the
soil surface or to crops rather than being mixed into the
soil.
(b) Volatilization and photodecomposition are the primary routes
for the disappearance of endrin from soil surfaces.
(c) Microbial degradation of endrin occurs anaerobically and is
accelerated by conditions such as flooding and soil depth.
(d) Soil cultivation and crop rotation accelerate the
dissipation of endrin.
(e) When the percentage of organic matter is high, as in muck -
soils, the persistence of eldrin is greater. In sandy soils,
volatilization is high and persistence is low.
4.1.4 Soil-plants
River and basin sediment was brought on land near Rotterdam, the
Netherlands, after dredging. Once the sediment had settled for several
years, the land was used for agriculture. Some of the sediment came
from a basin near a pesticide manufacturing plant and was contaminated
with many organochlorine hydrocarbons, including the pesticides
hexachlorobenzene, aldrin, dieldrin, and endrin. The mean
concentration of endrin in the sediment of the basin near the plant
(expressed in mg/kg on a dry weight basis) was 0.48 (range, 0.01-2.6)
in 1976 and 0.59 (< 0.01-3.6) in 1977. In crops, the concentration of
endrin ranged from none detected to 0.06 mg/kg of product; in carrots,
however, levels up to 0.73 mg/kg were found (Wegman et al., 1981).
4.2 Abiotic degradation
When endrin was heated to above 200 °C, as can occur during
gas-liquid chromatography at 230 °C, the molecule was isomerized to a
ketone, delta-ketoendrin (1, Fig. 1) and an aldehyde (3). A minor
product of the thermal rearrangement was an isomeric alcohol (4).
Endrin is also transformed to delta-ketoendrin (1) under
acid-catalysed conditions (Phillips et al., 1962).
Irradiation with ultraviolet light for 48 h also results in
rearrangement to this ketone (37%) and, to a much lesser extent, to
the aldehyde (9%) (Rosen et al., 1966; Plimmer, 1972; Mukerjee, 1985).
Endrin underwent a photolytic reaction in hexane and in cyclohexane
after irradiation at 253.7 and 300 nm, resulting in a half-cage
ketone, pentachloro photoproduct (2), in 80% yield. This photolytic
product has also been identified in the field and was found to be
highly resistant to oxidation and reduction (Plimmer, 1972; Zabik et
al., 1971; Mukerjee, 1985). When an acetone solution of endrin was
irradiated with light from a mercury lamp in a quartz cell for 24 h,
three metabolites were formed by the loss of one chlorine atom from
the initially produced delta-ketoendrin; one of these was compound 2
(Dureja et al., 1987).
Endrin has been reported to isomerize to delta-ketoendrin during
5 years' storage in the dark at room temperature (Plimmer, 1972.
In sunlight, mainly the ketone is formed (Soto & Deichmann, 1967;
Rosen, 1972); approximately 50% isomerization to the ketone took place
within 7 ± 2 days with exposure to intense summer sun (Burton &
Pollard, 1974).
The photochemical products are important as terminal residues:
delta-ketoendrin was found on cotton plants and on cabbage and apple
leaves after application of endrin (Plimmer, 1971; Mukerjee, 1985).
4.3 Biotransformation
The mechanisms by which endrin is removed from the environment
include photodecomposition and bacterial degradation. These factors
and their effects on the persistence of endrin have been reviewed by
the US Environmental Protection Agency (Donoso et al., 1979).
4.3.1 Biodegradation
Microbial degradation of endrin depends on the presence of an
appropriate microbial species and suitable soil conditions; it occurs
under anaerobic conditions (Donoso et al., 1979). Biodegradation is
aided by fungi and bacteria such as Trichoderma, Pseudomonas, and
Bacillus. The major transformation product is delta-ketoendrin
(Patil et al., 1970).
About 150 isolates from various soil samples were screened to
investigate the role of these microorganisms in degrading endrin; 25
of the 150 isolates were active. At least seven metabolites were
found, but conversion of endrin into the ketoendrin was common
throughout (Matsumura et al., 1971).
4.3.2 Bioaccumulation and biomagnification
The bioconcentration factors cited below are simple ratios of the
exposure concentration and the concentration in organic tissues. They
should be used with caution as indicators of bioaccumulation
potential: a high bioconcentration factor can represent little uptake
of a low concentration, and a low bioconcentration factor can be found
with considerable uptake of a high concentration. The bioconcentration
factor should therefore always be cited with the pertinent exposure
concentration of endrin.
Soil invertebrates such as slugs and earthworms had
bioconcentration factors of 14 to 103. Bioconcentration factors in a
number of aquatic organisms are given in Table 4. These ratios differ
extensively between different types of aquatic organisms.
Bioconcentration factors of 140 to 222 were found for four blue-green
algae (Microcystis aeruginosa, Anabaena cylindrica, Scenedesmus
quadricauda, and an Oedogonium species) after 7 days' exposure to
endrin at a concentration of 1 mg/litre of water( Vance & Drummond,
1969). In a study of the accumulation of endrin in stoneflies
(Pteronarcys dorsata) exposed to 0.03, 0.07, and 0.15 µg/litre of
water, the bioconcentration factor ranged from 1130 to 348, decreasing
with increasing water concentrations over the 28-day exposure period
(Anderson & DeFoe, 1980). In bullheads (Ictalurus melas), the
bioconcentration factor was 3700 after exposure for 4 days to 0.60
µg/litre and 6200 after exposure for 7 days to 0.26 µg/litre (Anderson
& DeFoe, 1980). The bioconcentration factors for endrin in sub-adults
of leopard frogs (Rana sphenocephala) exposed to 0.01, 0.012, 0.016,
0.022, and 0.030 mg/litre were 71.4, 34.4, 51.8, 59.4, and 94.3,
respectively. Sub-adults exposed to 0.01, 0.012, and 0.016 mg/litre
for 96 h and sacrificed 60 h later had bioconcentration factors of
6.1, 4.8, and 1.2, respectively (Hall & Swineford, 1980), indicating
a relatively rapid elimination of residues. In daphnids and molluscs,
a direct linear relationship was found between the logarithm of the
equilibrium bioconcentration factor (and the reciprocal clearance rate
constant) and the log P octanol/water partition coefficient for
non-degradable, lipophilic compounds with partition coefficients
ranging from 2 to 6. This relationship permits calculation of the
times required for equilibrium and for significant bioconcentration of
lipophilic chemicals, which were found to be shorter for molluscs than
for daphnids. The equilibrium biotic concentration for both molluscs
and daphnids decreased with increasing chemical hydrophobicity. The
relationship between the bioconcentration factor and log P
octanol/water partition coefficient was linear for compounds that did
not attain equilibrium within a finite exposure time (Hawker &
Connell, 1986).
In a study of the bioaccumulation of endrin from food by lobsters
(Homarus americanus), endrin dissolved in methanol was added to sea
water, and mussel tissue was soaked in the solution for 2 h to provide
a concentration of endrin of 4.7 mg/kg wet weight. Lobsters were fed
the prepared food every other day for 2 weeks, and excretion was
followed for an additional 4 weeks during which time the lobsters were
fed uncontaminated tissue. Liver and muscle were analysed from two or
three lobsters sampled after feedings 1, 2, 3, 5, and 7, and from one
or two lobsters sampled during the excretion phase at 1, 2, and 4
weeks. The concentration of endrin reached a maximum of 1.95 mg/kg wet
weight in the liver after 2 weeks of feeding; this level declined by
about 65% after 4 weeks of excretion. The time to 90% equilibrium
(uptake) was 15 weeks, and the time to 50% clearance (excretion) was
4 weeks (McLeese et al., 1980).
Bluegill sunfish (Lepomis macrochirus) exposed to water
containing 14C-labelled endrin at 1 µg/litre at temperatures of
20-22 °C rapidly absorbed the radioactivity, and, within 48 h, 91% of
the radioactive endrin had been taken up (6% was lost by
volatilization from a control tank without fish). Within 8 days after
the fish had been replaced in clean water, less than 15% of the
absorbed label had been eliminated; for three fish left for a longer
period, the half-life of loss was about 4 weeks, the loss curve being
linear (Sundershan & Khan, 1980). Endrin accumulated rapidly in the
tissues of channel catfish (Ictalurus punctatus) exposed to nominal
concentrations of 0.04, 0.4, or 4.0 mg/kg of diet for 198 days. After
that time, all groups were fed an endrin-free diet. Endrin was not
detected 28 days later in fish that had received 0.04 or 0.4 mg/kg,
and the level in the group that had received 4.0 mg/kg decreased to
0.011 mg/kg of tissue in 28 days and was below the limit of detection
within 41 days (Argyle et al., 1973). Similar results were obtained
for Leiostomus xantharus exposed to 0.05 µg/litre of water: at the
end of the study at 5 months, a residue level of 78 µg/kg tissue was
found, and no endrin was detected in fish after 18 days in
uncontaminated water (Lowe, 1966). Endrin thus seems to disappear
rapidly from tissues. In 20 Tilapia zilli (Alexandria strain) fry
(3.36 cm, 825 mg) exposed to 0.025 µg/litre (one-tenth of the 96-h
LC50) for 28 days, the total content of endrin was 327.4, 167.4,
297.6, 446.5, and 595.4 µg/kg after 4, 7, 14, 21, and 28 days,
respectively (El-Sebae, 1987).
Table 4. Bioconcentration factors for endrin in aquatic species
Species Concentration Length of Bioconcentration Reference
of endrin in exposure factor
water (µg/litre)
Clam 1 5 days 480 Duke & Dumas
(Mercenaria (1974)
mercenaria)
Mussel 10 24 days 38 Ryan et al.
(Hyridella (1972)
australis)
Eastern oyster 0.05 7 day 2780 Mason & Rowe
(Crassostrea (1976)
virginica)
Water flea 1.0 1 day 2600 Metcalf et al.
(Daphnia (1973)
magna)
Fathead 0.015 - 10 000 Mount & Putnicki
minnow (1966)
(Pimephales
promelas)
Spot 0.05 8 months 1340 Lowe (1966)
(Leiostomus
xanthurus)
Flag fish 0.3 - 10 000 Hermanutz
(Jordanella 0.21 15 days 7 900 (1974)
floridae) 0.29 18 400 Hermanutz et
0.39 7 100 al. (1985)
Table 4 (contd)
Species Concentration Length of Bioconcentration Reference
of endrin in exposure factor
water (µg/litre)
Mosquito 1.0 1 day 2 100 Metcalf et al.
larvae (Culex (1973)
ipiensquinque
fasciatus)
Mosquito fish 1.0 1 day 800 Metcalf et al.
(Gambusia (1973)
affinis)
Channel catfish 0.5 5-19 400-760 Argyle et al.
(Ictalurus (1973)
punctatus)
Sheepshead minnow (Cyprinodon variegatus) were exposed for 23
weeks to endrin at levels of 0.027-0.72 µg/litre of water, from the
embryonic stage through hatching until adulthood and spawning (see
section 7.2.2.2). Four-week-old juvenile fish accumulated 2500 times
the concentration in the water, adults, 6400 times, and their eggs,
5700 times (Hansen et al., 1977).
The transfer of endrin through the food chain
lichen-reindeer-humans was studied in the northern part of Sweden by
analysing lichen (Cladonia alpestris), a major food source for
reindeer during the winter, together with samples of tissues from
reindeer, which are eaten in considerable quantities by Lapps. One
4-year-old reindeer was slaughtered in 1979 and a 3-year-old in 1981,
and muscle and liver were taken for analysis. The annual uptake by
reindeer was 2.0 mg. The average level of endrin in lichen was 1.91
(range, 1.27-2.78) µg/kg; 1.45 and 2.4 µg/kg were found in the muscle
samples from the two reindeer and 0.55 and 0.72 µg/kg in liver. The
calculated transfer of endrin from lichen to reindeer was 0.7%. The
estimated annual consumption of reindeer muscle by Lapps was 70 kg for
males and 32 kg for women; consumption of liver was 3 and 1.1 kg,
respectively. The annual intake of endrin was thus 30.3 µg for males
and 13.8 µg for females (Villeneuve et al.,1985).
5. ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE
Many of the data reported in this chapter are measurements taken
at a time when endrin was used much more widely than at present or
with little control or restriction. They are therefore a reflection of
a historical situation in many countries. These data are included in
the document as an indication of the result of indiscriminate use and
disposal of endrin. Data from countries where endrin may still be used
are scarce or unavailable.
5.1 Environmental levels
The levels of residues associated with the use of endrin in
agriculture or with the discharge of industrial effluents containing
endrin are summarized in Tables 5-9; the levels of residues less
easily associated with specific uses or discharges are given in Table
10.
5.1.1 Air
A critical summary of studies on the atmospheric levels of
pesticides in the USA, e.g., in community air, was made by Donoso et
al. (1979). Some of their conclusions are worth repeating: "Endrin
concentrations are highest in the atmosphere over agricultural areas
and probably reach their peak levels during the pesticide use season.
Of all urban communities those surrounded by farmlands run the highest
chance of atmospheric contamination. Urban communities far removed
from agricultural areas are unlikely to experience significant
contamination." The maximum level of endrin in air, 58.5 ng/m3, was
found in a rural town in an agricultural area in the south of the USA,
but the normal weekly variation was between 0.8 and 6.5 ng/m3
(Stanley et al., 1971). In a later study of the same town, the average
annual atmospheric levels were 3.2 ng/m3 in 1972, 2.3 ng/m3 in
1973,and 5.3 ng/m3 in 1974, with the highest levels in August; in
1974, this was 27.2 ng/m3 (Arthur et al., 1976). The results of a
national monitoring programme for pesticides in the air of various
states of the USA showed the occasional presence of endrin over
agricultural areas at levels of the same order of magnitude: mean of
positive samples (8%), 2.6 ng/m3, with a maximum value of 19.2
ng/m3 (Kutz et al., 1976).
Endrin was not found in rain-water collected at different
location in the United Kingdom, using a method with a detection level
of 1 ng/litre of water (Tarrant & Tatton, 1968), nor in atmospheric
air (Abbott et al., 1966); however, endrin has never been used
extensively in the United Kingdom.
The mean daily intake of endrin by inhalation in the western part
of the Netherlands was calculated on the basis of an air concentration
of 41 pg/m3 (maximum, 300 pg/m3) to be 0.8 µg/day or 0.3 mg/year,
on the basis of air samples taken in the period 1975-81 (Guicherit &
Schulting, 1985).
Table 5. Concentrations of endrin in organisms collected in the Netherlands, 1965-71
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samplesa
Mean Rangeb
Coast Mussel (Mystilus edulis); 22 0.029 0.009-0.056 Composites of 25 Koeman (1971)
1965 composites of flesh mussels from 22
sampling stations
Netherlands Fish, 3 species; 103 0.13 0.07-0.45 Food of the sandwich Koeman et al. (1967)
1965 whole body tern
1966 Fish, 3 species; 37 0.10 0.07 -0.29
whole body
Sandwich tern
(Sterna sandvincensis)
1965 Liver 8 0.23 0.07-0.80 Shot or killed
1965-66 Liver 25 0.49 0.10-1.3 Found dead
1965-66 Egg 33 0.19 0.08-0.36
Wadden Sea Mussel (2 species); 20/4 LD LD Limit of detection, Koeman (1971)
1969 composites of flesh 0.005 mg/kg
Coast Mussel (Mytilus edulis); 199/8 < 0.016 LD-0.024 Koeman (1971)
1970 composites of flesh
Wadden Sea Zooplankton (marine) 1 LD LD Koeman (1971)
1969-70
Shrimp (Crangon 50/1 LD LD
vulgaris)
Table 5. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samplesa
Mean Rangeb
Marine fish (4 species); 37/5 0.014 0.008-0.034
composites of whole
body
1967 Freshwater fish 28 LD LD-0.02 Measurable concentration
(3 species) (0.02 mg/kg) in one fish
only; limit of detection,
0.005 mg/kg
1970 Pike (whole body) 10 LD LD Limit of detection,
0.005 mg/kg
1971 Roach (whole body) 6 LD LD
1968-69 Hawks and falcons 16 < 0.1 LD-0.16 Birds found
dead or dying; Koeman et al. (1969)
(4 species); liver measurable concentration
(0.16 mg/kg) in one hawk
(buzzard)
Owls (2 species); liver 3 < 0.1 LD-0.13 Measurable concentration
(0.13 mg/kg) in one
long-eared owl; limit of
detection not specified
1970 Sandwich tern eggs 10 LD LD Limit of detection, Koeman (1971)
0.02-0.008 mg/kg
1971 Grey heron 27/4 LD LD
(Ardea cinerea);
composite of eggs
Table 5. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samplesa
Mean Rangeb
1969-71 Sparrowhawk 28/3 LD LD
(Accipiter nisus);
composite of eggs
a Sample numbers expressed as n/m correspond to n individuals sampled in m composites analysed
b LD, limit of detection
Table 6. Concentrations of endrin in samples collected in North America
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samplesa
Mean Rangeb
Mississippi River
USA
December 1963 Channel catfish; blood 3 0.44 0.41-0.56 Found dead or dying in areas Anon. (1964)
of extensive fish kills
December 1963 Fish, various species; 24 0.18 0.14-0.26
blood
January- Fish, various species; 82 0.06 LD-0.21 Caught alive; limit of
February 1964 blood detection not specified
July 1964- Water 12 < 0.01 LD-0.01 4 samples contained Novak & Rao (1965)
June 1965 measurable concentrations
(0.01 mg/kg or litre)
Mud 12 < 0.01 LD-0.01
Oysters 12 LD LD Limit of detection,
0.005 mg/kg or litre
Shrimp 12 LD LD
Fish (2 species) 24 < 0.01 LD-0.02 9 samples of fish contained
measurable concentrations:
8 of 0.01 mg/kg and 1 of
0.02 mg/kg
Mississippi, USA Eastern oysters 470 LD LD 15 or more oysters per Butler (1973)
1965-72 (Crassostrea virginica); composite from 8 sampling
composites of flesh stations; limit of detection,
0.01 mg/kg
Table 6. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samplesa
Mean Rangeb
Bayous in the Water 148 LD LD-0.0002 4 samples contained Rowe et al. (1971)
Mississippi delta, measurable amounts
USA, October (0.00009-0.0002 mg/litre),
1968-May 1969 4 samples contained traces;
remainder less than limit of
detection
Sediment 44 LD LD-0.005 7 samples contained
measurable amounts
(0.004-0.005 mg/kg); one
sample contained a trace
Eastern oyster 111 LD LD-0.006 79 samples contained
(Crassostrea virginica) < 0.001 mg/kg
Mississippi Water 26 LD LD Samples collected from Leard et al. (1980)
stream systems 13 sampling stations in
1972-73 5 major river basins; limit
of detection, 0.0005 mg/litre
Freshwater bivalves 58 LD LD-0.1 Residues below limit of
(7 species); flesh detection (0.02 mg/kg), except
for traces (< 0.1) in 1973 in
one river which drains from an
agricultural area
Ontario, 3 Fish (9 species) LD LD Residues below limit of Miles & Harris
streams, 1971 detection, 0.01 mg/kg (1973)
Table 6. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samplesa
Mean Rangeb
Gulf coast Whole fish 139/48 < 0.02 LD-0.27 Reseidues below limit of Henderson et al.
streams, USA (various species); detection (0.001 mg/kg) (1969)
composites in 33 composites
Mississippi 657/202 < 0.01 LD-0.11 Residues in 184 composites
River system, below limit of detection
USA (0.001 mg/kg)
Louisiana, USA Brown pelican Eggs collected from nests of Blus et al. (1979)
(Pelecanus occidentalis); birds transplanted as nestlings
eggs from Florida, 1968-76; limit
1971 3 0.10 0.08-0.12 of detection not specified
1972 12 0.18 0.11-0.29
1973 21 0.16 0.03-0.46
1974 25 0.30 LD-0.73
1975 30 0.50 0.29-1.06
1976 25 0.29 LD-1.47
aSample numbers expressed as n/m correspond to n individuals sampled in m composites analysed
bLD, limit of detection
Table 7. Concentrations of endrin in organisms collected in a
cotton-growing area in the Republic of Chad in 1969
Sample No. of Concentration (mg/kg) Comments
samples Mean Range
Fish, two 31 0.02 LD-0.083 Cotton-growing area,
species endrin and DDT used
for pest control; limit
Kingfishers and 46 0.02 LD-0.075 of detection, 0.008
cormorants; liver mg/kg
Birds, non-aquatic, Birds found dead
various species soon after insecticide
Brain 12 0.51 0.10-0.77 application; deaths
Liver 12 0.88 0.13-1.42 of some birds attributed
to endrin
From Everaarts et al. (1971); LD, limit of detection
5.1.2 Soil, sediments, and sewage sludge
5.1.2.1 Soil
In the US National Soil Monitoring Program, 1486 soil samples
from 37 states were analysed in 1971. Fourteen samples were found to
contain endrin, at a geometric mean level of < 0.001 (maximum,
0.02-1.00) mg/kg dry weight (Carey et al., 1978). The mean endrin
concentration in 29 soil samples in Kyushu District, Japan, was 0.183
mg/kg (range, 0.016-0.629 mg/kg) dry matter (Suzuki et al., 1973).
5.1.2.2 Sediments
In 1964, levels in the sediment of Cypress Creek, Memphis, TN,
USA, upstream and downstream of a pesticide manufacturing plant,
reached 12 800 mg/kg dry weight. In 1967, water from the Creek
contained levels of 0.27-2.03 µg/litre and sediment contained levels
of 47.4-10 676 mg/kg dry weight (Barthel et al., 1969).
Endrin was found in 17% of samples of bottom sediment from 59
sites on the Detroit River, USA, at levels up to 43 µg/kg (limit of
detection, 1.0 µg/kg) (Hamdy & Post, 1985). No endrin was detected in
sediment samples collected in 1980-82 from riverine and pothole
wetlands at 17 locations in the north-central USA (Martin & Hartman,
1985) or in samples of sediment from 34 stations on the upper Great
Lakes in 1974 (< 1 µg/kg) (Glooschenko et al., 1976).
Table 8. Concentrations of endrin in organisms collected in a rice-growing area in Wageningen, Surinam
Date Type of sample No. of Concentration (mg/kg)b Comments
samplesa
Mean Rangeb
October 1971 Snail kite (Rostrhamus 5/1 LD LD -- Pesticides, including endrin, applied
sociabilis); brain /liver | to rice fields
|
Black vulture (Coragyps 5/1 LD LD |
astratus); brain/liver |
|
Egrets (3 species); brain/ 30/1 LD LD | Samples collected at end of growing
liver |-- season before insecticide application
| for next growing season; limit of
Purple gallinule 10/1 LD LD | detection, 0.01 mg/kg
(Porphyrula martinica); |
brain/breast muscle |
|
Spectacled caiman (Caiman 10/1 LD LD |
crocodilus); brain/liver --
November 1971 Snail (Pomocea sp.) 10/1 LD LD --
|
Frog (Pseudis paradoxa); 6/1 LD LD | Found dead after application of
whole-body composites | pentachlorophenol; lower limit of
| detection, 0.01 mg/kg
Kwi kwi (Hoplosternum 8/1 LD LD |
littorale); whole-body |
composites --
Table 8. (contd)
Date Type of sample No. of Concentration (mg/kg)b Comments
samplesa
Mean Rangeb
Srieba (Astyanax bimaculatus); 8/1 LD 0.1 -- Found dead after application
whole-body composites | of pentachlorophenol; lower
|-- limit of detection 0.01 mg/kg
|
Krobia (Cichlasoma 8/1 LD LD |
bimaculatum); whole-body |
composites --
Fish (3 species listed above); 21/3 3.36 1.96-5.35 Found dead after application
whole-body composites of endrin
28 November- Snail kite; brain 17 LD LD Found dead; deaths
4 December 1971 attributed to pentachlorophenol
poisoning
2-9 December 1971 Aquatic birds (4 species); 5 0.11 0.06-0.16 Found dead after application
brain of endrin
2-9 December 1971 Wattled jacana 1 2.71 Death attributed to endrin
(Jacana jacana) poisoning
5-11 December 1971 Common egret (Egretta alba); 2 0.23 0.14-0.32 Found dead or sick in roost
brain
2-11 December 1971 Common egret (Egretta alba); Found dead or sick in rice
Brain 9 0.25 fields; about half the total
Liver/kidney 7-9 0.08 endrin was applied during
the first half of December
From Vermeer et al. (1974)
aSample numbers expressed as n/m correspond to n individuals sampled in m composites analysed
bLD, limit of detection
Table 9. Concentrations of endrin collected in drainage water from irrigated land, California, USA
Geographical Type of sample No. of Concentration (mg/kg or mg/litre) Comments
area and year samples
Mean Range
Tule Lake and Water 44 0.000011 LD-0.0001 Limit of detection, < 0.000003 mg/litre
Klamath Lake,
National
Wild-life
Refuge,
USA, 1964
Refuge, Northern Suspended matter 8 0.011 LD-0.058 --
California, USA, Vascular plants 7 0.006 LD-0.013 |
April 1965- (two species) |-- Limit of detection, 0.005 mg/kg
February 1967 Algae (Cladophora sp.) 5 0.007 LD-0.022 |
Clam homogenates 3 0.013 LD-0.034 --
Gonidea sp.)
Fish (Siphateles sp.) 5 0.05 0.004-0.198 Samples collected at a pumping station
discharging water from irrigated land.
Peak concentrations of endrin occurred
during the growing season when endrin
was applied.
From Godsil & Johnson (1968); LD, limit of detection
Table 10. Concentrations of endrin in environmental samples; residues not associated with particular local use or industrial
effluent
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samples
Mean Range
North America
North Carolina, Soil (tobacco fields) 19 LD LD Reeves et al.
USA,1971 Sediment (ponds) 40 LD LD Limit of detection, (1977)
Frog (Rana sp.) 13 LD LD-0.01 0.01 mg/kg
Turtle (4 species) 41 LD LD-0.01
Bluegill (Lepomis 20 LD LD
macrochirus)
Tiger beetle 23 0.02 LD-0.05
(Megacephala
carolina)
Rice-growing Invertebrates, aquatic 1313/24 LD LD-trace A total of 192 dead or Flickinger &
area, Gulf Coast, and terrestrial (various dying birds were found in King (1972)
Texas, USA, species); whole-body three rice-growing areas in
1967-71 composites of live which rice seed dressed
specimens, except for with aldrin/ceresan had
4 composites of been used. Endrin residues
crayfish attributed to use in cotton-
growing areas. Limit of
1968 Fish (4 species); 542/4 LD LD detection not defined;
whole-body composites trace found in one
composite of dead
1968 Cricket frog (Acris 18/3 LD LD crayfish
crepeitans blanchardi);
whole-body composites
1968-70 Turtles (2 species); 5/2 LD LD
whole-body composites
of live specimens
Table 10. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samples
Mean Range
Snakes (3 species); sick 3 LD LD
specimens
Bobcat (sick) and dead 2 LD LD
rice rat; brain
Great horned owl; dead 2 LD LD
specimen; brain
Rice- growing Aquatic birds (10 26 0.22 LD-0.4
area, Gulf Coast species) found dead
USA, 1967-71 or dying; brain
1967 Fulvous tree duck 14 0.1 LD-0.3
(Dendrocygna bicolor);
eggs
Galveston Bay Oyster composites 10 0.01 LD-0.02 Limit of detection, Casper (1967)
Texas, USA, 1964 0.01 mg/kg
National Monitoring Fish (various species); 400 93% of samples below Henderson et
Program: Great Lakes whole-body composites limit of detection, al. (1969)
and major river 0.001 mg/kg
basins, USA (excluding
Gulf Coast, Mississippi
River system; see
Table 6); 1967-68
Atlantic coast streams 741/141 0.002 LD-1.50
Table 10. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samples
Mean Range
Great Lakes drainage Fish (various species); 378/66 0.001 LD-0.02
whole-body composites
Hudson Bay, Canada, 51/13 LD LD
drainage
Colorado River, USA 112/24 0.008 LD-0.71
Interior basins 120/25 0.001 LD-0.01
California, USA, 90/24 0.002 LD-0.02
streams
Columbia River, USA, 246/64 0.001 LD-0.01
systems
Pacific coast, USA, 83/20 LD LD
streams
Alaska, USA, streams 105/24 LD LD
National Monitoring Fish (various species); 666/147 LD LD Limit of detection, Henderson et
Program; 50 sampling whole-body composites 0.005 mg/kg al. (1971)
stations, USA, 1969
Estuaries, Giant Pacific oyster 1656/138 0.005 LD-0.01 Measurable concentration Modin (1969)
California, USA (Crassostrea gigas); in only one oyster; limit
1966-67 Mussel (Mytilus edulis); 432/36 LD LD of detection, 0.01 mg/kg
composites of shellfish
Table 10. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samples
Mean Range
Arkansas and Catfish from commercial 108-162/54 0.06 LD-0.4 Limit of detection, Crockett et
Mississippi, USA fish farms; composites 0.01 mg/kg; 13 al. (1975)
1970 of edible portions composites contained
< 0.01 mg/kg
Intensive cotton- 0.063 (0.030- 2 composites contained
growing areas, 0.122)a > 0.3 mg/kg. Significantly
Mississippi, USA higher residues in intensive
cotton-growing areas
Less intensive cotton- 0.010 (0.005- Crockett et
growing areas, 00.019)a al. (1975)
Mississippi, USA
Major watersheds, Fish (various species); 582/58 LD LD Limit of detection not Veith et al.
USA, 1976 whole-body composites specified. Intermediate (1979)
in the manufacture of
cyclodiene insecticides
detected (mass
spectrometry) in Wabash
River, Indiana
Major watersheds Fish (various species); 138/6 LD LD Limit of detection not Veith et al.
near Great Lakes, whole-body composites specified. Endrin (1981)
USA, 1978 identified by mass
spectometry in fish from
Wabash River, Indiana,
together with manufacturing
intermediates (concentration
not quantified)
Table 10. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samples
Mean Range
Arkansas and Catfish from commercial 50 0.05 LD-0.41 Limit of detection, 0.01 Hawthorne
Mississippi, USA, fish farms, edible portion mg/kg; 14 fish contained et al. (1974)
1970 < 0.01 mg/kg
Continental rise Bathyl-demersal fish 4 LD LD Limit of detection, Meith-Avcin
south-east of (Antimora rostrata); 0.01 mg/kg. Samples et al. (1973)
Cape Hatteras, USA, liver collected by trawling at a
1972 depth of 2500 m
Lake Michigan, USA, Amphipods (Pontoporeia 24/8 0.08 0.04-0.33 Limit of detection, Peterson &
1969-72 affinis) collected from 0.005 mg/kg Ellarson
oesophagi of old squaws (1978)
December 1969 Old squaws (Clangula 37 0.18 0.1-0.2 Birds caught in fishing
hyemalis); carcasses nets or shot
March-April 1970 44 0.28 0.2-0.4
December 1970- 108 0.31 0.1-0.9
May 1971
January-February 8 0.6 0.2-1.0
1972
Northwest Territories 99 0.1 LD-0.3
and wintering areas
other than Lake
Michigan, 1971-73
Table 10. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samples
Mean Range
Canada and USA, Bald eagles (Haliaeetus 29 0.02 LD-0.1 Limit of detection, Reichel et al.
1965 leucocephalus) found 0.05 mg/kg. (1969)
dead; brain Concentration in 24
specimens below limit
of detection
Connecticut & Bald eagles found dead; 2 LD LD-0.1 Limit of detection not Reichel et al.
Florida, USA, brain, liver, carcass defined; apparent (1969)
1967-68 concentration of
0.1 mg/kg in Florida
eagle not conformed
by thin-layer
chromatography
Continental USA Bald eagle; brain Limit of detection, Mulhern et al.
1966 21 LD LD 0.05 mg/kg (1970)
1967 21 LD LD
1968 26 LD LD
1969 Bald eagle; brain 28 LD LD Limit of detection, Belisle et
0.05 mg/kg al. (1972)
1970 11 LD LD
1971-72 Bald eagle; brain 37 LD LD Limit of detection, Cromartie et
0.05 mg/kg al. (1975)
1973-74 Bald eagle; brain 81 LD LD Limit of detection, Prouty et al.
0.05 mg/kg (1977)
1975 Bald eagle; brain 49 0.07 LD-0.50 Limit of detection, Kaiser et al.
0.05 mg/kg. (1980)
Concentrations in 46
specimens < 0.05 mg/kg
Table 10. (contd)
Place and Type of sample No. of Concentration (mg/kg) Comments Reference
period samples
Mean Range
1976 50 0.08 LD-0.71 Concentrations in 44
specimens below limit of
detection. Death of one
eagle attributed to endrin
poisong
1977 69 0.08 LD-1.2 Concentrations in 64
specimens below limit of
detection. Death of one
eagle attributed to endrin
poisoning
Wisconsin, Maine, Bald eagle; eggs 26 LD LD Limit of detection, Krantz et al.
Florida, USA, 0.05 mg/kg (1970)
1968
USA, Golden eagle (Aquila 102 LD LD-0.3 Limit of detection, Reidinger &
1964-71 chrysaetos) found dead 0.1 mg/kg. Concentrations Crabtree
or dying; body fat in 97 specimens below (1974)
limit of detection
Coast of California, Gray whale 23 LD LD Wolman &
USA, 1968-69 (Eschrichtius robustus); Wilson (1970)
blubber
Sperm whale (Physeter