Endrin: Environmental Health Criteria Series No 130 (Environmental Health Criteria,)

This report contains the collective views of an international group of expertsand doesnot necessarily represent the decisions or the stated policy of the United Nations Environment Programme, the International Labour Organisation, or the World Health Organization.

Environmental Health Criteria 130

ENDRIN

First draft prepared by Dr G. T. van Esch, Bilthoven, Netherlands, and Dr E. A. H. van Heemstra-Lequin, Laren. Netherlands

Published under the joint sponsorshipof the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization

World Health Organization Geneva, 1992

The International Programme on Chemical Safety (IPCS) is a joint venture of the United Nations Environment Programme, the IntemationalLabour Organisation,and the World Health Organization. The main objectiveof IPCSis to carryout anddisseminateevaluationsof theeffectsof chemicalsonhumanhealthandthequality of theenvironment. Supporting activities include the development of epidemiological, experimentallaboratory, andrisk-assessmentmethodsthat could produce internationallycomparableresults,andthe developmentof manpowerin the field of toxicology. Other activities carried out by IPCS include the developmentofknow-howforcoping with chemicalaccidents.coordination of laboratory testing and epidemiologicalstudies, and promotion of researchon the mechanismsof the biological actionof chemicals. WHOLibrary Cataloguing in PublicationData Endrin. healthcriteria; 130) @nvironmental l.Endrin-toxicity 2.Environmental exposurel.Series (NLM Classifrcation: ISBN92 4 l57l30 6 WA 240) ISSN0250-863X The World HealthOrganizationwelcomesrequestsfor permissionto reproduceor translateits publications,in part or in full. Applicationsand enquiriesshouldbe addressedto the Office of Publications,World Health Organization,Geneva,Switzerland,which will be glad to provide the latestinformation on any changesmadeto the text, plansfor new editions, and reprints and translationsalready available. @World Health Organization 1992 Publications of the World Health Organization enjoy copyright protectionin accordance with theprovisionsof Protocol2 of theUniversal Copyright Convention.All rights reserved. The designationsemployedandthepresentationof thematerial in this publication do not imply the expressionof any opinion whatsoeveron the part of the Secretariatof the World Health Organizationconcemingthe legal statusof any country,territory, city, or areaor of its authorities,or concemingthe delimitationof its frontiersor boundaries. The mention of specific companiesor of certain manufacturers' products doesnot imply that they are endorsedor recommendedby the World Health Organization in preferenceto othersof a similar nature that arenotmentioned.Errors andomissionsexcepted,thenamesofproprietary productsaredistinguishedby initial capital letters.

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CONTENTS 1.

SI.JMMARYAND EVALUATION; CONCLUSIONS; 13 ..................."'.. RECOMMENDATIONS Summaryandevaluation "'..'..........13 1.1.1 Exposure """""."'.'......."'..13 --.-"'.' 14 1.1.2 Uptake,metabolism,andexcretion 1.1.3 Effectson organismsin theenvironment.'....."'.'..'.""'. 15 animalsandin vitro...'.."...."'. l5 1.1.4 Effectson experimental .'.."".....' 1'1 1.1.5 Effectson humanbeings........... 18 ............. L.2 Conclusions 18 .....'...'. 1.3 Recommendations..............

Ll

IDENTITY, PHYSICAL AND CIMMICAL PROPERTIES, ANALYTICAL METHODS 2.1 2.2 2.3 2.4

3.

ldentity Physicalandchemicalproperties factors............. Conversion Analyticalmethods

...'......'...""".20 .....'.".""""".'.. 2l '.....'.-"-22 ................".....'22

SOURCESOFHUMAN AND ENVIRONMENTAL 30 ..................... EXPOSURE .......,..,.....""'.'.'30 3.1 Naturaloccurrence .........................30 sources 3.2 Man-made 30 uses........................... levelsandprocesses, 3.2.1 Production ...........30 3.2.1.1Worldproductionfigures ....'.."". 3l 3.2.1.2 Manufacturingprocesses ENVIRONMENTAL TRANSPORT,DISTRIBUTION, AND ...........,....32 TRANSFORMATION............ 4.1

32 Transportanddistributionbetweenmedia............................'..' . . . . . . . . . . . . . " " '3. '2. 4.1.1 Air................ .............'........32 4.1.2 Water...........

4.2 4.3 4.3.1 Biodegradation

.......36

5.3

Occupationalexposureduringmanufacture,formulation, 84 .............."". and use '.".'..."."."' 84 5.3.1 Manufactureandformulation ....""""'."......" 85 5.3.2 Application .."".. 87 5.3.3 Appraisalof occupationalexposure

KINETICS AND METABOLISM Absorption,distributioq andelimination 6.1.1 Laboratoryanimals 6.1.1.1Oral administration administration 6.1.1.2 Intravenous 6.L.2 Domesticanimals 6.1.3 Humanbeings.................... in vitro 6.1.4 Systems 6.2 Biotransformation............. 6,2.1 Experimentalanimals 6.2.2 Humanbeings.................... 6.2.3 Microorganisrns................ 6.2.4 Plans...........

6.1

7.

......... 88 ........... 88 ............88 88 ..................... ..........90 ..............91 . . . . . . . . . . . . . . . . .9. .3. . . ................. 93 ............93 ........ 93 . . . . . . . . . . . . . . . . .9. .6. . . ..................... 97 . . . . . . . . . . . . . . . . . 9. .8. . .

EFFECTSON ORGANISMS IN TIIE EI.IVIRONMENT................ 99 ......... 99 7.1 Microorganisms................... ........................ 99 7.2 Aquaticorganisms ...................... 99 7.2.1 Invertebrates ...................... 106 7.2.2 Fish.............. .......106 7.2.2.1 Acutetoxicity ........106 7.2.2.2 Short-termtoxicity .............. ...........,....... 114 7.2.2.3Studiesof resistance 115 7.2.2.4 Interactionwith otherchemicals...................... ......116 7.2.2.5 Specialsnrdies .....118 7.2.3 Amphibia .................... 118 7.3 Terrestrialorganisms .........................118 7.3.1 Honeybees 7.3.2 Birds............ ...................... 119 .......119 7.3.2.1 Acutetoxicity ..................... 119 7.3.2.2Short-termtoxicity .............l2O 7.3.2.3 Studiesof reproduction 7.3.2.4 Interactionwith otherchemicals............... .......l2l ......121 7.3.2.5 Specialstudies ................... 122 7.3.2.6Behavioural studies

.....122 7.3.3 Mammals .....................122 7 . 3 . 3 . 1T o x i c i t y. . . . . . . . . . . . . . . . . ...................123 7.3.3.2Studiesof resistance 7.4 Effectsin thefield .........................1U 7.5 Appraisalof effectson organismsin the environment.............126 8.

EFFECTSON EXPERIMENTAL ANIMALS AND IN VITRO .......T27 8.i

8.2

8.3 8.4

8.5

............127 Acute toxicity of technical-gradeendrin 8.1.1 Oral administration............. .................... 127 8.1.2 Dermal administration ...... 127 8.1.3 Parenteral ........................ 127 administration 8.1.4 Toxicity of metabolitesandisomers .......l3l 8.1.4.1 Mammalianmetabolites ................................... l3 I 8.1.4.2Isomers .................132 8.1.5 Acute toxicity of formulatedmaterial .....I33 8.1.5.1Oral anddermaladministration ....................... 133 8.1.5.2Inhalation ............. 133 Short-term exposure ...................... 134 8.2.1 Oral administration............. .................... 134 8 . 2 . 1 . 1M o u s e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1. .3. 4 .. 8 . 2 . 1 . 2R a r . . . . . . . . . . . . . . . . ........134 8 . 2 . 1 . 3R a b b i t . . . . . . . . . . .........135 8 . 2 . 1 . 4D o g . . . . . . . . . . . . . . .........135 8.2.1.5Domesticanimals ....................... 136 8.2.2 Inhalation .... 137 8.2.3 Dermal administration ...... 137 Skin irritation ..........137 Reproduction, embryotoxicity,andteratogenicity ................... 137 8.4.1 Reproduction .....................137 8 . 4 . 1 . 1M o u s e . . . . . . . . . . . . . . . . . . . ......................I37 8 . 4 . 1 . 2R a t . . . . . . . . . . . . . . . . ........138 8.4.2 Embryotoxicityandrerarogenicity ..........138 8.4.2.1Mouse ................... 138 8 . 4 . 2 . 2R a t . . . . . . . . . . . . . . . . ........139 8.4.2.3Hamster................. ..................... 140 8.4.2.4 Perinatalbehavioural development.................. 141 8.4.3 Appraisalof reproductiveeffects ............142 Mutagenicityandrelatedend-points ...................142 8.5.1 Effectson microorganisms .............. ........142 8.5.2 Pointmutationsinmammaliancells ,,.,,.,144

..."."...".'."""IM 8.5.3 Dominantlethalmutations 8.5.4 Chromosomaland cytogeneticeffects ." " ". " " " " "'.'.'... 144 effects........... S.5.5 Host-mediated ".""......"....145 ....."...".....'."'145 8.5.6 Sisterchromatidexchange. .......'145 8.5.7 Effecs rn Drosophila melanogaster ....."'.i+0 8.5.8 Effectson DNA........ 8.5.9 Appraisalof mutagenicityandrelatedend-points...."". 146 8.6 Long+ermexposwe............ """-.-'147 ........'..147 .................. 8.7 Carcinogenicity .."""""'.'....'147 8.7.1 Oraladministration.............. ......................I47 8 . 7 . 1 . 1M o u s e . . . . . . . . . . . . . . . . . . . 8 . 7 . 1 . 2R a t . . . . . . . . . . . . . . . """'.' 148 150 ...'."'."...""". 8.7.1.3 Tumourpromotion 150 ............"'.."'.."""""'......'. of carcinogenicity 8.7.2 Appraisal ...'....151 8.8 Specialstudies '.......""..".151 8.8.1 Nervoussystem studies."'...".........""""'..15I 8.8.1.1 Electrophysiological studies 8.8.1.2 Histopathological """...'.152 systems......."...... 8.8.1.3 Neurotransmitter " " " "....". " " I 52 8.8.1.4 Appraisalof effecs on the nervoussystem...'..155 ..'... 155 system Cardiovascular 8.8.2 .....""..........""..156 8.8.3 Effectson liver enzymes 8.8.3.1Mouse ""..."'.'.."..'156 . . . . . . .1. '5 7 8 . 8 . 3 . 2R a t . . . . . . . . . . . . . . . 158 .......'."..'....... ............. 8.8.3.3Guinea-pig .'."'158 8.8.3.4 In-vitro srudies .'..'."""""'..... 159 8.8.4 Mscellaneoussrudies........ '..'.'.....'....' 159 8.8.5 Factorsthat influencetoxicity 159 ...................... 8.8.5.1Nutrition............... ..........160 8.8.5.2 Potentiation EFFECTSON HI.]MAN BEINGS

.,.......162

."".""."'..'162 Exposureof the generalpopulation.... '."'..'.."'...'.'.162 9.1.1 Acutetoxiciry 9.1.2 Poisoningincidents "'........162 .................. 165 exposure 9.2 Occupational 9.2.1 Factoryworkers......... """" 165 ...............................'.'.... relationships 9.2.2 Dose-response ". 167 ....". 168 9.2.3 Exposuresto mixtures 170 9.2.4 Appraisalof effectsof occupationalexposures.........'...

9.1

IO.

PREVIOUSEVALUATIONS BY INTERNATIONAL BODIES ... I7I

REF8R8NCES...................

......r13

ANNEX I Chemicalnamesof endrinandits metabolites......................21g ANNEX II Medicalrreatmenr of endrinpoisoning...... ......221 ANNEX III Management of major statusepilepticusin adulrs................223 RESUME RESITMEN

............226 .........234

WHO TASK GROUP ON ENVIRONMENTALHEALTH CRITERIA FOR ENDRIN Members Dr L.A. Albert, ConsultoresAmbientalesAsociados,Xalapa,Veracnrz, Mexico Dr V. Benes,Departmentof Toxicology and ReferenceLaboratory, lnstitute of Hygieneand Epidemiology,Prague,Czechoslovakia Dr S. Dobson,Instituteof TerrestrialEcology,Monks Wood ExperimentalStation,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 Instituteof OccupationalHealth, Ahmedabad.India Dr Yu.L Kundiev, ResearchInstituteof Labour Hygiene and OccupationalDi seases, Kiev, Ukraine (Vice-Chairnnn) Dr Y. Osman,Ministry of Health, Riyadh,SaudiArabia Dr H. Spencer,United StatesEnvironmentalProtectionAgency, WashingtonDC, USA (Chairman) Dr C. Winder,NationalInstituteof C)ccupational HealthandSafety,Forest Lodge, New SouthWales,Australia Secretariat Dr K.W. Jager,IntemationalProgrammeon ChemicalSafety,World Health Organization,Geneva,Switzerland(Secr etary) Ms B. Labarthe,IntemationalRegisterof PotentiallyToxic Chemicals,United NationsEnvironmentkogramme, Geneva, Switzerland Dr T.K. Ng, Office of OccupationalHealth,World Health Organization,Geneva,Switzerland

NOTE TO READERS OF THE CRITERIA MONOGRAPHS

Every effort has been made to present information in ttre Criteria monographs as accurately as possible without unduly delaying their publication. In the interestof all usersof theEnvironmental Health Criteria monographs,readersarekindly requestedto communicateany errors that may have occurred to the Director of the Intemational programme on Chemical Safety, World Health Organization, Geneva, Switzerland, in order that they may be included in corrigenda.

**t(

A detailed data profile and a legal file can be obtained from the Intemational Registerof Potentially Toxic Chemicals,palais desNarions, 1211Geneva10,Switzerland(Telephoneno. 798%ffi or 7985850).

:***

The proprietary information contained in this monograph cannot replace documentationfor regisftation pu{poses,becausethe latter has to be closely linked to the source, the manufacturing route, and the pwity/impurities of the substanceto beregistered.The datashouldbeused in accordancewith paragraphs82-84 andrecommendationsparagraph90 of the SecondFAO GovernmentCorsultation (1932).

t0

ENVIRONMENTALHEALTH CRITERIAFOR ENDRIN

A WHO Task Group on Environmental Health Criteria for Endrin and Isobenzanr"retat the World Health Organization,Geneva,from23 to27 July I 990.Dr K.W. Jager,IPCS,welcomedtheparticipantson behalfof Dr M. Mercier,Directorof IPCS,andthethreeIPCScooperatingorganizations (UNEP, ILO, WHO). The Group reviewedand revisedthe draft Criteria monographsandHealth andSafetyGuidesandmadean evaluationof the risks to human health and the environment f,rom exposureto endrin and isobenzan. The first drafts of thesemonographswere preparedin cooperation betweenDr E.A.H. van Heemstra-lrquin and Dr G.J. van Esch of the Netherlands.Dr van Esch preparedthe seconddrafts, incorporatingthe cofirmentsreceivedfollowing circulation of the first drafts to the IPCS contactpoints for Envilsrxlsnl4l Health Criteria monographs. Dr K.W. Jager of the IPCS Central Unit was responsiblefor the scientificcontentof the monographs,and Mrs E. Heseltine,St Ifon-surYEzdre,France,for the editing. The fact that ShellOil Co. madeavailableto IPCSandtheTaskGroup proprietary toxicological information on their products is gratefully acknowledged.This allowed the Task Group to basetheir evaluationon morecompletedata. The effort of all who helpedin thepreparationandfinalizationof the monographsis gratefully acknowledged.

Partialfinancialsupportfor thepublicationof thisCriteriamonograph was kindly provided by the United StatesDepartmentof Health and Human Services, through a contract from the National Institute of EnvironmentalHealth Sciences,ResearchTrianglePark,North Carolina, USA, a WHO CollaboratinsCentrefor EnvironmentalHealth Effects.

11

1. SUMMARYANDEVALUATION; CONCLUSIONS; RECOMMENDATIONS 1.1

Summaryand evaluation

1.r.1

Expsure Endrin is an organochlorineirsecticide which hasbeenusedsincethe 1950sagairst a wide rangeof agricultural pests,mostly on cotton but also on rice, sugar-cane,maize,andother crops.It is also usedasa rodenticide. It is availablecommerciallyasdusts,granules,pastes,andanemulsifiable concentrate. Endrin enters the air mainly by volatilization and aerial drift. In general,volatilizationtakesplaceafter applicationto soils andcropsand dependson many factors,suchasthe organic matter andmoisture content of the soil, humidity, air flow, and the surfaceareaof plants. The most important route of contaminationof surfacewater is run-off from soil. Contaminationfrom precipitation in the form of snow or rain is negligible. Local contamination of the environment may occw from industrialeffluentsandcarelessapplicationpractices. The major sourceof endrin in soil is from direct application to soil and crops.Endrin can be retained,transported,or degradedin soil, depending on a number of factors. The greatestretention occurs in soils with a high content of organic matter. The persistenceof endrin is highly dependent uponlocal conditions; its halflife in soil can range up to l2years. Volatilization and photodecomposition are the primary factors in the disappearanceof endrinfrom soil surfaces.Under theinfluence of sunlight (ultraviolet light), the isomer delta-ketoendrin is formed- In intense summersun,about507oof endrin wasisomerizedto this ketoendrinwithin 7 days. Microbial transformation(in fungi and bacteria) takes place, especiallyunder anaerobicconditiors, to give the sameproduct, Aquatic invertebratesand fish take up endrin rapidly from water, but exposed fish trarsfened to wrcontaminated water lose the pesticide rapidly. Bioconcentration factors of 14-18 000 have beenrecordedafter continuous exposure.Soil invertebratesmay also take up endrin readily.

13

Summaryand evaluation; conclusions; recommendations

The occasionalpresenceoflow levels ofendrin in air and in surface and drinking-water in agricultural areasis of little significance from the point of view of public health. The only exposurethat may be relevant is dietary intake. In general,however,thereportedintake levels arefarbelow the acceptabledaily intake of 0.fi)02 mglkg body weight esrablishedin 1970(FAO/WHO, 1971). 1.1.2

Uptake, metabolism, and excretion Unlike dieldrin, its stereoisomer,endrin is metabolizedrapidly by animals,andverylittle is accumulated infat incomparisonwithcompounds of similar chemicalstructure. Both uptakeandexcretionafteroral administrationarerapid in rats, and its biological half-life is 1-6 days, dependingon rhe doselevel. A steady state, at which the excretedamount equalsthe daily intake, is reachedafter 6 days.A sex differenceis observed,in that malesexcrete endrin andmetabolitesvia the bile much fasterthanfemales,resultingin less accumulationin male adiposetissue.Rats excretethis compound mainly in thefaecesasendrin, anti-12-hydroxyendrin,and a hydroxylated endrin derivativewithin the first 24h (70-7sEo);a third metabolite,12ketoendrin,accumulates in tissues.Rabbitsexcrete507oof themetabolites of endrin in urine, whereasinrats only 2Voareexcretedby this route; only unchangedendrin is found in the faecesofrabbits. Cows administeredendrin at0. I mg/kg of diet for 2 1 daysexcretedup to 65Voasmetabolitesinwine,ZoVoin faeces,partly asunchangedendrin, and3%oin milk, alsomainly as endrin.Thesecows had residuelevels of 0.003-0.006mg/litre in milk, 0.001--0.002mglkg in mear, and 0.020.I mg/kg in fat. Laying herx fed endrinshowedresiduelevels (dependingon thedoses given) of up to 0. I mg/kg in mear, I mglkg in fat, 0.1-O.2mg/kg in eggs (yolk), 0.4 mg/kg in kidney, and 0.5 mglkg in liver. Excepr in liver and kidney, theresiduesfound weremainly unchangedendrin.About 50% of the administeredendrin was excretedin faeces,mainly asmetabolites. Inhumanbeings,rats,rabbits,cows,andhens,themajorbiotransformed metabolite of endrin is anti-12-hydroxyendrin, rogether with its sulfare andglucuronideconjugates.Four othermetaboliteswerefound but in only minor quantities.Mainly unchangedendrinis found in body tissuesand 14

EHC 130:Endrin

milk. After this pesticidewas appliedto plants, unchangedendrin and two hydrophilic transformation products were identified.

1.1.3

Etfectson organismsln the environment The effect of endrin on soil bacteriaandfungi is minimal. Dose levels of 1G-l000mglkg of soilhadnoeffectondecompositionoforganicmatter, denitrification, or generation of methane. Endrin is very toxic to fish, aquaticinverteb'rates,andphytoplankton: the 96-h LC, values aremostly below 1.0 pgllitre. The lowest observedadverseeffect level in a life cycle test on the mysid shrimp, My sidopsisbahia,wasestablishedat 30 ng/litre. Thereported testson the acutetoxicity of endrin in aquaticorganisms were conducted in aquaria without sedimenl the presenceof sediment would be expectedto attenuatethe effect of endrin. Heavily contaminated sedimenthad little effect on speciesliving in open water, suggestingthat sediment-bound endrin has low bioavailability. Tests have not been conductedon aquatic animals living in sediment. The LD, for terrestrial mammals and birds is in the order of 1.G10.0mg/kg body weight. Mallard ducks fed up to 3.0 mg/kg body weight for 12 weeksshowedno effect on eggproduction, fertility, or hatchability. Certain species of aquatic invertebrates,fish, and small mammals havebeenreportedto be resistantto the toxicity ofendriq andexposureto several different organochlorine pesticides led to selection of strains resistantto endrin. Fish kills were observedin areasof agricultural run-off and industrial discharge; and declining populations of brown pelicans (in Louisiana, USA) and of sandwich tems (in the Netherlands)have been anribured to exposureto endrin in combination with other halogenatedchemicals.

1.1.4

Ettectson experimentalanlmals and in vitro Endrin is a highly toxic pesticide, the signs of intoxication being neruotoxic. The oral LD, of technical-gradeendrin for laboratory animals is in the rangeof 343 mg/kg body weight; the dermal LDro for rars is 520 mg*lg body weight. No substantialdifference in acuteoral or dermal toxicity was found betweentechnical-gradeandformulated (emulsifiable concentrateand wettable powder) products. 15

Summaryand evaluation; conclusions; recommendations

Short-term experimentsfor oral toxicity have beencarried out using mice, rats, rabbits, dogs, and domestic animals. In mice and rats, the maximumtolerateddosesfor6 weekswere5 and 15 mgAg diet (equivalent to 0.7 mg/kg body weight), respectively.Rarssurvived a 16-weekexposure to i mg/kg diet (equivalent to 0.05 mg/kg body weight); rabbits died after receiving repeateddosesof I mglkg body weight. In dogs, a doseof 1 mg/ kg of diet (approximatelyequivalentto 0.025 mglkg body weight),given over 2 years,was without effect. Thenewologicalbasisof theobservedsignsof intoxicationis inhibition of gamma-aminobut5nicacid (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, decreasedhexobarbital sleepingtime in mice. Dosesof 75-150 mglkg applieddermallyasa dry powderfor 2 h daily causedconvulsions anddeathin rabbits but did not result in skin irritation. Productionof systemictoxicity without irritation at the sire of contactis noteworthy. Long-termstudiesof toxicity andcarcinogenicityhavebeenperformed in mice and rats. No carcinogenic effect was found, but thesestudieshad shortcomings, including poor survival of the animals. The no-observedeffect level for toxicity in a two-year study in rats was I mg/kg of diet (equivalent to about 0.05 mg&g body weight). Tumour promoring effecrs were not demorstrated when endrin was tested in combination with subminimal quantitiesof chemicalsknown to be carcinogenicto animals. The Task Group concluded thar the data are insufficient to indicate thar endrin is a carcinogenic hazard to humans. Endrin was found to be nonmutagenicin severalstudies. In most studies,it wasnot teratogenicto mice, rats,or hamsters,even at dosesthat causedmatemalor fetotoxicity. The no-observed-adverseeffect level was 0.5 mg/kg body weight in mice and rarsand 0.75 mg/kg body weight in hamsters.Endrin did not induce reproducriveeffects in rats over three generatiors when given at a dose of 2 mg/kg of diet (about 0.1 mg/kg body weight).

16

EHC 13A:Endrin

A number of the metabolites of endrin have similar or higher acute toxicities than the parent compound, The uansformation product, deltaketoendrin, is lesstoxic thanendrin, but l2-ketoendrin is consideredto be the most toxic metabolite of endrin in mammals,with an oral LDro in rats of 0.8-1.1 mglkg body weight.

1.1.5

Effectson human belngs Severalepisodesof fatal andnon-fatalaccidentalandsuicidalpoisoning haveoccurred.Casesof acutenon-fatalintoxicationdueto accidentaloverexposurewere observedin workers in an endrin manufacturingplant. The oral dosethatcausesdeathhasbeenestimatedto be approximately10 mg/ kg body weight;thesingleoral dosethatcausesconwlsions wasestimated to be 0.25-1.0 mg/kg body weight. The primary site of action of endrin is the central nervoussystem. Exposureof humansto a toxic dosemay lead within a few hours to such signs and symptomsof intoxication as excitability and convulsions,and deathmay follow within 2-I2 h afterexposureif appropriatetreatmentis not administeredimmediately.Recoveryfrom non-fatalpoisoningis rapid and complete. Endrin does not accumulatein the human body to any significant degree.No long-termadverseeffectswerereportedin 232 occupationally exposedworkers(lengthof exposure,4-27 years)wrdermedicalsupervision (observationtime,4-29 years). The only effect observedwas indirect evidenceof a reversiblestimulationof drug metabolizingenzymes. Endrin wasdetectedin virtually noneof a largenumberof samplesof adiposetissue,blood, and breastmilk analysedin many countries.The Task Group attributedthe absenceof endrin in humansamplesto the low exposureof the general population to this pesticide and to its rapid metabolism. Endrin was detectedin blood (at up to 450 Fgfiitre) and in adipose tissue(at 89.5mg/kg) in casesof fatal accidentalpoisoning.No endrinwas found in workers under normal circumstances,The thresholdlevel of endrinin blood, below which no sign or symptomof intoxicationoccurs, hasbeenestimatedto be 50-100 pgllitre. The half-life of endrin in blood may be in the order of 24h.

t7

Summaryand evaluation; conclusions;recommendations

1.2

Conclusions Endrin is an insecticide with high acute toxicity. It may cause severe poisoning in cases of over-exposure caused by carelesshandling during its manufacture and use or by consumption of contaminated food. The general public is exposed to endrinmainly asits residues infood; however, the reported intake of endrin is generally far below the acceptable daily intake established by FAOAVHO. Such exposures should nor consrirure a health hazard to the general population. When good work practices, hygiene measures, and safety pre€autions are enforced, endrin is unlikely to present ahazard to exposed workers. It is clear that rurcontrolled discharges of endrin during its manufacture, formulation, and usecan result in acuteenvironmental 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 treen associated with the presence of high levels of residues of various organochlorines in the tissuesof adults andineggs. Endrinhas beenmeasured in someof these species; however, it is very difficult ro separarethe effects of the different organochlorines present.

1,3

Becommendations i. Endrin shouldnot be usedunlessit is indispensableandonly whenno lesstoxic alternativeis available. 2. For thehealthandwelfareof workersandthegeneralpopulation,the handlingandapplicationofendrinshouldbeenrrusred only to competently supervised, well-trainedoperatorswhowill follow adequate safetymeasures and apply endrin accordingto good agriculturalpractices. 3. The manufacture,formulation, agricultural use, and disposal of endrin should be managedcarefully to minimize contaminationof the environment,particularlysurfacewater, 4. Peopleexposedregularly to endrin shouldundergoperiodic health evaluations. 5. Epidemiologicalstudiesof exposedworker populationsshould be continued. 18

EHC 130:Endrin

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 l2-ketoendrin and deltaketoendrin.

19

2. IDENTITY, PHYSICALANDCHEMICAL PROPERTIES, ANALYTICAL METHODS 2.1

ldentity CAS chemical name:

(l aa,2B,2aB,3 a,6o',6aB,78,7au)3,4,5,6,9.9-hexachloroI a,2,2a,3,6, 6a,1,7a-x,talaydro-2,7:3,6-b]oxirene dimethanonaphth[2,3 (9Cr-CAS)

Former CAS chemical name:

-hexachloro-6,7-epoxy1,2,3,4,10,10 I,4,4a,5,6,7,8,8a-octahydro1,4endo,endo -5,8-dime&anonaphthalene

ruPAC chemical name:

lR,4Sy'aS,5S,6S,7R,8R,8aR)1,2,3,4,10,10-hexachloro1,4,4a,5,6,7,8.8a-octahydro-6,7epoxy-1,4:5,8-dimethanonaphthalene

Chemical structure:

Endrin is the endo,endostereoisomerof dieldrin Empirical formula: crrHsclp Relative molecular mass: 380.93 Commonname: Endrin CAS registry number: 72-20-8 RTECS registry number: I0i575000 Synonyms: Endrex,Experimental Insecticide 269, Hexadrin, Nendrin, NCI-COO 157, ENT17251,OMS 197,and Mendrin Trade name: Endrin 20

EHC 130:Endrln

Not lesstlvt92vo,Impruities include aldrin (0.03%), dieldrin (O.42Vo), isodrin (O.73Vo),endrin half-cage ketone (l.57Vo), endrin aldehyde (O.OSVo), and heptachloronorbomene (O.@Vo)@onosoet al., 1979).

Purity:

2.2

Physlcaland chemicalpropertles Table 1. Physicaland chemical propertiesof endrin

Physicalstate

Crystallinesolid

Colour

White to light-tan

Odour

Mild chemical

Melting-point

226-230'C (decomposesat above 245 "C)

Flash-point

None (dry powder is non-flammable,but commercial solutionscontraininflammable liquids wifr flash-poinlsas low as 27'C)

limits Explosion

Non-explosive

Specificgravity(density)

1.64g/ml at 20 "C

Vapourpressure

2.7 x 10-7mmHg at 25 'C (36 pPa at 25 "C)

Solubility in water

Practicallyinsoluble (0.23 mg/litre at 25'C)

Solubilityin organic solvents

Sparingly soluble in alcohol and petroleum hydrocarbons;moderately soluble in aliphatic hydrocarbons;and quite soluble in solvents such as acetone, benzene, carbon tehacfiloride, and xylene

Log P octanolAvater partitioncoefficient

5.34

Stability:

Technical-gradeendrin is stable in storageat ambient temperatwes. Endrin is stable in formulatiors with basic reagents,alkalineoxidizing agents,emulsifiers,

21

Identity,physical and chemicalproperties,analytical methods

wetting agents,and solvents. It isomerizesunder the influenceof ultravioletlight. It reactswithconcentrated mineral acids,acid catalysts,acidoxidizing agentsand 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 hexamethylenetetramineand form stable mixtures with endrin. When heatedto above 20OoC, endrin undergoesmolecular reaurangementsto form delta-ketoendrin,a compoundthat is lessactiveas an insectide (IARC, 1974;Donosoet al., 1979).

2.3

Gonverslon factors I ppm = 16 mg/m3at 20 "C i mg/m3= 0.063 ppm at 20 oC

2.4

Analyticalmethods Most of the analyticalproceduresusedsincetheearly 1960shavebeen basedon the following steps: (D extractionusing a suitablesolvent; (ii) clean-upby liquidfliquid partition followed by column chromatography; (iii) further separationfrom co-extractivesby gaschromatography (GC); and (i") quantificationwing an electron-capture, coulometric,or Hall electrolyticdetector General proceduresbasedon thesesteps are not specific for endrin; therefore, its identity must be confirmed in environmental samples.This can be achievedby chemical derivatization and massspectrometry(Chau & Cochrane, 1969, l97l; Belisle et al., 1972: Chau, 1974; Safe & Hutzinger, 1979). Roos et al. (1987) used size exclusionchromatographyto clean-up pesticidesafter extraction with ethyl acetatefrom fish oils, animal fat, cereals,vegetables, fruit, andliver. Therecoveriesof endrinwereg}-957o, at a limit of detectionof 0.02 mg/kg.This methodwasfound to be adequate for screeningand requires only 157oof the amount of solvents normally used. 22

EHC 130:Endrin

Giibeli & Clerc (1988) describeda relatively simple gas-liquid chromatographymethodfor the detectionand approximatequantification ofchlorinatedpesticidesinethanolicextractsofmedicinalplants(tinctures)' The methodwasbasedon extractionwith hexaneand capillary GCFNielectron-capturedetection.Thelimit ofdetectionforendrin was0.005 mglkg with a recoveryof 7'l .SVo. manypesticidesfrom extractsof crops Suzukiet al. (19'14)separated and soil into different groupsby column chromatographyprior to thintoobtainsystematicidentificationanddetermination. layerchromatography Silica gel wasusedfor the columnchromatographyandfor thethin-layer plates;glasscolumnspackedwith different absorbentswereusedfor GC detectionwith separation.Determinationwasdoneusingelectron-capture a 6Ni source. To improvetheseparationby heatof28 organochlorineinsecticides, including endrin,using gas-liquid chromatographywiithelectroncapture detection,Suzuki & Morimoto (1986) testedthree chemically bonded, fusedsilicacapillarycolumns.Thecolumnpreparedwith OV- 17performed best.The methodwasusedwith minimal clean-upand gavegoodresults samples,avoidingthedisadvantages intheanalysisofextractsofseveralsoil oflow resolutionofpeaksin packedcolumns,handlingofglasscapillary columnsand the high cost of GC-massspectrometrysystems. Kiang & Grob (1986) developed a screeningprocedure for the determinationof 49 pollutantsof high priority, includingendrin,in soil or sludge.Methylenechloride at two pH valueswas usedin the extraction procedure,which was followed by capillary GC. No clean-upprocedure wascarriedout. Separationandidentificationwereperformedwith a GCmassspectrometrysysteminvolving a 30-m fused silica column; a 60-m column was usedfor quantification.Recoveryof endrin from soil in the base-neutralextract was 92+ 14Vofrom 2.O4mglkg but only 70+ 87o from 20.4 mgftg. Japengaet al. (1987) describeda rapid clean-upprocedurefor the simultaneousdeterminationof groupsof micropollutantsin sediment.The sampleswerepretreatedwith acid,mixed with silica, and extractedon a Soxtrletcolumn with a mixture of benzeneandhexane.Humic substances and elementalsulfur were removed by passing the extract through a chromatographiccolumn containing basic alumina on which sodium sulfite andsodiumhydroxidewereabsorbed.After silicafractionation,the

23

Identity,physical and chemicalpropert'rcs,analytical methods

concentrations of polycyclic aromatic hydrocarbons, polychlorinated biphenyls,andctrlorinatedpesticidesweredeterminedby GC. Therecovery of endrin was reported to fluctuate between 93 and l03Vo. The efficiency of clean-up with sulfuric acid and confirmation with potassiumhydroxide-ethanolhydrolysis wasstudiedfor 22 organochlorine pesticidesandpolychlorinatedbiphenylsin watersamples(Hemandezet al., 1987);analysiswasbyGC/electron-capturedetection, andthepesticides were extractedby partition with lSVodiethyl ether in hexane.After cleanup with sulfuric acid, only 4.9Voof the endrin was recovered; however, with thepotassiumhydroxide-ethanoltreatment,9T-lOO7ow asrecovered, dependingon the endrin concentrationand the length of treatment, Method 8080 of the US Environmental Protection Agency (EPA) (Manual, SW-M6) was evaluatedin a single laboratorystudy by LopezAvila et al. (1988). Since the Florisil clean-upprocedurerecommended doesnotseparateorganochlorinepesticidesfrompolyctrlorinatedbiphenyls, GC analysis on a packed column may result in false identifications; therefore,silica gel was substitutedfor Florisil, a capillary glasscolumn was used instead of the packed column, and a procedure to remove elementalsulfur incorporated.Detectionlimits for liquid manicesranged from 0.02 to 0.09 pgAitre for organocNorinepesricides;for solid matrices, arangeof l-6 Fg/kgwasfound Therecoveryofendrininliquid wastewas up to I027o at a spikedconcentrationof 1.0 pg, but for a sandyloam soil it varied from47 to74%o. Donahue et al. (1988) compared rwo rechniquesfor quantifying environmental contaminants in human serum: peak area matching and linear regression.No statistically signifi,cant difference was seen in the resultsobtainedby thesetwo methodswhen theconcentrationof ctrlorinated pesticideswas> 0.5 pgllire. The sampling and determination of endrin in air were described in detailby NIOSH (1989). A methodfor determiningresiduesof themetaboliteanri-l2-hydroxyendrin,presentastheB-glucuronide,in urine wasdescribedby Baldwin & Hutson (1980). Following oxidation with sodium metaperiodateand hydrolysis with a mild base,the metaboliteis determinedby gas-liquid chromatographywith electron-capture detection.

24

EHC'130:Endrin

Polychlorinated biphenyls and 21 chlorinated pesticides, including endrin, were analysed in samples of water, soil, and sediment in six laboratoriesusing uniform calibration solutions, analytical methods, and specialsoftwareoperatingon minicomputersto control theoperationof the mass spectrometer. The results obtained for solid samples with four cornbinations of methods for extraction and clean-up were compared; althoughnocombinationwasoptimalfor all samples,shakerandsonicator extraction,bothwithFlorisil clean-up,gavethebestresults. Severalfactors that affected the quality of the results were identified, including errors in computation and transcription and inadequatereview of data (AlfordStevenset al., 1988). Seventeenlaboratoriesparticipated in an international comparisonof analysesfor 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., I 979) for the dererminationof endrin in pork fat (fortified to 0.019 mg/kg), themeanrecoveryin 11 laboraroriesw as84Vo, but the rangewas 5-l3lVo. Table2. Besultsfor endrinof an interJaboratory studyof the analysisof organochlorine compounds (Holden,1970) Type of sample

No. of laborator-Mean @ncen- Standard Coefficient Ranoe ies withresults tration (mg/litre deviation of variation for endrin or mg/kg)(%l

Solution 17 in hexanea

5.929b

Cod liver 14 oil

0.02

Chicken 16 egg

0.136

0.073

54

0.07-o.3"

Sprat

0.132

0.039

29

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14

1. 0 1

17.1

4.9-8.2 ND.-0.2G

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25

Identity, physicaland chemicalproperties,analytical methods

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Thier & Stijve (1986) reported a comparative study among 53 laboratoriesin Switzerlandon the analysisof avegetablefat spikedwith 13 organochlorine and five organophosphoruscompounds. Endrin was presentat a concentrationof 0.08 mg&g andwas identifiedby 77Voof 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 proceduresand the limits of detection refer to the specific investigations and are not absolutevalues. The percentagerecoveriesare an indication of the accuracyof the methods; the precision of individual method is of interestparticularly in regard to inter-laboratory comparisons, The many publications on specific procedures are reviewed in the Codex Alimentarius Commission public ation Recotnmendations fo r Metlnds of Annlysisof PesticideResidues,CAC/PR8-1986 (FAOflVHO, 1986a). That review lists 14 individual publications; ir also liss the following compendiaof methods,which may be consulted.

- Official M ethodsof Analysisof theAssociatbn of Official Analytical Chemists,14thEdition, 1984 PesticideAnalytical Manual, WashingtonDC, Food and Drug Administration -Manual on Analytical Methods for Pesticide Residues in Foods, Ottawa,Health ProtectionBranch,Health andWelfare Canada,1985 -Mbthodensammlung zur Riickstandsanalytikvon Pflanzenschutzmineln (Methods for Analysing Residuesof Plant ProrecrionAgents), Weinheim, Verlag ChemieGmbH, 1984 - Chemistry laboratory Guidebook,W ashingtonDC,US Deparrmenr of Agriculture Whatever procedure is adoptedshould be carried out following the requirementsof the Codex Alimentarius Commission publicatton Codex Guidelines on Good Laboratory Practice in Pesticide Residuc Analysis, CAC/PR7-1984(FAO VHO, 1984).

29

3. SOURCES OF HUMANAND ENVIRONMENTAL EXPOSURE 3.1

Naturaloccurrence Endrin doesnot occur naturally.

3.2

Man-made sources

3.2.1

Production levels and processes, uses Endrin is a foliar insecticidewhich acts againsta wide rangeof agricultural pestsat dosesof the active material of 0.2{).5 kg/ha. It has a broadspectrumof control andis particularly effective againstLepidoptera. It is usedmainly oncotton but also againstpestsof rice, sugarcane,maize, and other crops. It is also used as a rodenticide (IARC, 1974). An endrin emulsionof,2Voklled4Mo of Achatinafulica snails,an agriculturalpest, in India (Singtq 1988). A generalindication of thepossibleusesof endrincanbe derivedfrom the maximal residue limits recommended by FAOAMHO (1986b; see section10).

3.2.1.1

World production figures Endrin was developed by J. Hyman & Co. and licensed to be manufacturedby Shell Intemational Chemical Co. and Velsicol Chemical Co. in 1950 (Thompson, 19?6). It was made in the USA by Shell and Velsicol and in the Netherlandsby Shell. Its usehasbeenbannedin many countriesandseverelyrestrictedinothers@onosoet al., 1979;Gips, 1987; Pearce,1987).Shell discontinuedmanufactureof endrin in 1982:it is still manufacturedin Mexico. Whetstone(1964) estimatedthat 2.34.5 million kg of endrin were sold in the USA in 1962. Imports of endrin into Japan in 1970 were 72000 kg. The armual quantiries of endrin that were used in paddy rice production in Bali over the pericd 1963--'12varied from 171 to 10 700 kg (Machbub et al., 1988). After 1972, endrin was no longer used. 3A

EHC 130:Endrln

?.2.1.2 Manufacturingprocess Endrin is produced by condensingvinyl chloride with hexachlorocyclopentadiene,dehydrochlorinatingthe adduct,andsubsequentreaction with cyclopentadieneto form isodrin, which is epoxidized by peraceticor perbenzoic acid (Whetstone, 1964). The intermediate isodrin can be manufacturedvia 1,2,3,4,7,7-hexachloronorbomadiene (US EPA, 1985).

31

4. ENVIRONMENTAL AND TRANSPORT, OISTRIBUTION, TRANSFORMATION 4.1

Transportand distributionbetweenmedia

4.1.1

Air Endrin can enterthe air by volatilization, evaporation,andaerial drift during application, and as a vaporu from manufacturing and formulating plants.Most studiesshowedrapid volatilizationfollowing applicationto soils andcrops,the extent of vaporization dependingupon a large number of factors,including soil organicmatter,moistwe content,airhumidity, air flow, and surfaceareaof plants (Donosoet al., 1979).

4.1.2

Water Endrin can reach surfacewater by severalroutes, including effluents and wastedisposalfrom endrin manufacturingandformulating plants and careless aerial application, but by far the most important route of contamination is surfacerun-off from soil and crops. Run-off is affected by numerous,complex factors,suchasintensity of precipitation, irrigation practices,soil permeability,topographicrelief, organiccontentofthe soil, and the degree of vegetative cover. Soils of low permeability and low organic content allow copious run-off after heavy precipitation @onoso et al., 1979). Contamination of surface water by industrial effluents and careless practices and disposal (such a,swashing of drums and spray equipment in streams)results in regional effects. In 1961, studies were conducted in the Bayou Yokely basin in Louisiana,USA, where3300 acres(1335 ha) ofsugar-canewere treated with nearly 2000 lb (907 kg) of endrin between June and August. Of 18 water samplestaken between April and November, six contained endrin at levels of 0.001-O.36ltgftitre,with an averageof 0.1 pgllitre, In 1964,the areawastreatedwith 1200lb(544 kg) of endrin,andthepattern of residueswas the same.The meanresiduelevels in samplestaken in Septemberwere 0.44 Stgllitrengrab samplesand0.53 pgllitre in carbon adsorptionsamples;after three months, the averagelevels were 0.03 and 0.M pgnitr", respectively.Sedimentsamplescontained165 pgTkg;after threemonths,this level had decreasedto 70 ttgkg (Lauer et al., 1966). 32

EHC 130:Endrin

Another, lessimportant sourceof water contaminationis run-off from endrin-coatedseeds.Marstonet al. ( 1969)foud thatalthoughapproximately llVo of the initial amount was washed off by water under laboratory conditions, in field conditions the loss was smaller. The total amount detectedin the watershed6 daysafter aerial application of endrin-coated seedwas0. 12Voof the applieddose.The highestconcentrationfoundin the water was 0.O71tgllitre. A third possiblesourceof contaminationis fall-out by precipitationin the form of rain and snow, but the measruedlevels are negligible (see section5.I.3.2).

t,,

Soil

The major sowce of endrin in soil is from direct application to soil and crops. The amount of endrin that reachesthe soil dependson the type of crop and the method of application. The fate of endrin in soil determines the degreeto which the rest of the environment (water and afinosphere)is contaminated.hr soil, endrin can be retained, transported,or degraded, dependingon a large number of interrelatedfactors (Donoso et al., 1979). When endrinwas appliedto tall, densecropssuchas tobacco,no residue appearedin thesoil; whenit wasappliedto soil, the amountthatremained dependedon the retentiveability of the soil. Although endrin hasstrong absorptivepropertiesin soilssuchasclay andsandyloam,limited residues were found. Far greaterretention was found in soils with a high organic content,in which it wasadsorbedquickly andwasdifficult to remove.The degreeto which endrin was retained in the soil dependednot only on the soil type but on numerousother factors such as volatilization, leaching, wind erosion,surfacerun-off, and crop uptake (Harris et al., 1966).In general,thepersistence of endrinis highly dependentuponlocalconditions, and residuelevels can rangefrom tracesto milligrams per kilogram. Its half-life in soil canbe as long as 12years(Donosoer a1.,1979). The factors that affect the degreeto which endrin is retainedin soil (Donosoet al., 1979)can be generalizedas follows: (a) (b) (c)

Endrin appearsto be lesspersistentifit is appliedto the soil surfaceor to crops rather than being mixed into the soil. Volatilizationandphotodecompositionaretheprimaryroutes for the disappearanceof endrin from soil strfaces. Microbial degradationof endrin occurs anaerobically and is acceleratedby conditionssuchas flooding and soil deprh.

33

Environmentaltransport,Qistribution,and transformation

(d) (e)

4.'t.4

Soil cultivation andcrop rotation acceleratethe dissipation of endrin. When the percentageof organic matter is high, as in muck soils, the persistenceof eldrin is greater.In sandy soils, volatilization is high and persistence is low.

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 usedfor agriculture, Someof the sedimentcamefrom a basin near a pesticide manufacturing plant and was contaminatedwith many organochlorine hydrocarbons, including the pesticides hexachlorobenzene,aldrin, dieldrin, and endrin. The meanconcentration of endrin in the sedimentof the basin near the plant (expressedin mg/kg on a dry weight basis) was 0.48 (range, 0.01-2.6) n 1976 and 0.59 (< 0.01-3.6)in 1977.In crops,the concentrationof endrin rangedfrom none detectedto 0.06 mglkg of product; in carrots,however, levels up to 0.73 mg/kg were found (Wegmanet al., 1981).

4.2

Abioticdegradation When endrin was heatedto above200 "C, as can occur during gasliquid chromatographyar 230 oC, the molecule was isomerized to a ketone,delta-ketoendrin(1, Fig. l) andan aldehyde(3). A minor product oI the thermal reirrangement was an isomeric alcohol (4). Endrin is also transformed to delta-ketoendrin(1) under acid-catalysedconditions (Phillips et al., 1962). kradiation with ultravioletlight for 48 h alsoresultsin rearrangement to this ketone (37Vo)and,to a much lesserextent,to the aldehyde(97o) (Rosenet al., 1966;Plimmer, 1972;Mukerjee, 1985).Endrinunderwent a photolytic reaction in hexane and in cyclohexane after irradiation at 253.7and300nm,resultinginahalf-cageketone,pentachlorophotoproduct (2), in80Vo yield. This photolytic product has also been identified in the field and was found to be highly resistant to oxidation and reduction (Plimmer, 19721'Zabiket al., 1971;Mukerjee, 1985).When an acetone solutionof endrinwasirradiatedwith light from amercurylampin a quartz cell for 2Ah, rlueemetaboliteswere formed by the loss of one chlorine atom from the initially produced delta-ketoendrin;one of these was compound2 (Durejaet al., 1987). 34

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49

Environmentallevelsand human exposure

water(farant&Tatton, 1968),nor inatrnosphericair(Abbottetal., 1966); however, endrin hasnever beenusedextensively in the United Kingdom. Themeandaily intake of endrin by ffialation in thewestempart of the Netherlandswas calculated on the basis of an air concentrationof 4l pg/ m3(maximum, 300 pg/rrf) to be 0.S pglday or0.3 mgfear, on thebasisof air samplestaken in the period 1975-81 (Guicherit & Schulting, 1985). Table7. Concentrations of endrinin organismscollectedin a cotton-growing areain the Republicof Chadin 1969 Sample

No. of Concenfation (mS/kS) Comments samPles M"." R*s"

Fish,two species

0.02

Kingfishersand cormorants; liver

0.02

Birds, non-aquatic, various species Brain 12 Liver 12

0.51 0.88

LD-O.083 Cottonjrowing area, endrin and DDT used for pest control; limit LD-O.075 of detection,0.008 mg/kg

0.1H.77 0.13-1.42

Birds found dead soon after insecticide application;deaths of some birds atbibuted to endrin

From Everaartset al. (1971); LD, limit of detection

5.1.2

Soll, sediments, and sewage sludge

5.1.2.1 Soil In theUS National Soil Monitoring ProgranL 1486 soil samplesfrom 37 stateswere analysed:ur,l97l. Fourteensampleswere found to contain endrin, at a geometric mean level of < 0.001 (maximunr, 0.02-1.00) mg/ kg dry weight (Carey et al., 1978). The mean endrin concentration in 29 soil samplesin Kyushu Disrricr, Japan,was0. I 83 mg/kg (range,0.0 I 60.629mgTkg)dry mauer (Suzukiet al.,1973). 5.1.2.2

Sediments In 1964,levels in rhesedimenrof CypressCreek,Memphis, TN, USA, upstrqlm and downstream of a pesticide manufacturing plant, reached 12 80Omg/kg dry weight. In 1967, warerfrom the Creek containedlevels 50

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