UNEP/POPS/POPRC.1/4 Format for submitting pursuant to Article 8 of the Stockholm Convention the information specified in Annex E of the Convention Introductory information Name of the submitting Party/observer NGO Observers: Pesticide Action Network (PAN) International and the International POPs Elimination Network (IPEN) Contact details Meriel Watts, PhD Pesticide Action Network Aotearoa New Zealand PO Box 296,Ostend Waiheke Island, Auckland 1971, New Zealand ph/fax: 0064-372-2034 merielwatts@xtra.co.nz and Pamela Miller, M.En. Biologist and Executive Director Alaska Community Action on Toxics 505 W. Northern Lights Blvd., Suite 205 Anchorage, Alaska 99503 pkmiller@akaction.net Chemical name - Endosulfan CAS: 959-98-8 - alpha (α) Endosulfan 33213-65-9 - beta (β) Endosulfan 115-29-7 - technical Endosulfan 1031-07-8 - Endosulfan sulfate: Trade names and synonyms Agrisulfán, Afidan, Aikido, Akodan, Alodan, Axis, Benzoepin, Beosit, BIO 5462, Bromyx, Caiiman, Chlorbicyclen, Chlorthiepin, Crisulfan, Cyclodan, Cytophos, Devisulfan, Endel, Endocel, Endocide, Endocoral, Endocoton, Endofan, Endoflo, Endomight Super, Endopol, Endosan, Endosol, Endosulphan, Endotaf, Annex E information on ENDOSULFAN 1 UNEP/POPS/POPRC.1/4 Endoxilan, Enrofán, Ensure, ENT 23979, Flavylan 350E, FMC 5462, Galgofon, Galgptal, Global E, Goldenleaf Tobacco Spray, Hexasulfan, Hildan, HOE 2671, Insectophene, Isolan, Kop-thiodan, Lucasulfan, Malix, Misulfan, NIA 5462, Niagara 5462, Novasulfan, Palmarol, Parrysulfan, Phaser, Rasayansulfan, Red Sun, Rocky, SD-4314, Sharsulfan, Sialan, Sonii, Sulfan, Techn’ufan, Thifor, Thimul, Thiodan, Thiofanex, Thiofor, Thioflo, Thiomet, Thiomul, Thionate, Thionex, Thiosulfan, Thiosulfax, Thiokil, Thiotox, Tionel, Tionex, Tiovel, Tridane, Termizol pó, Veldosulfan, Vulcán, Zebra Ciagro. Date of submission - January 8, 2009 (a) Sources, including as appropriate (provide summary information and relevant references) (i) Production data: Quantity: 1. Cumulative global usage on crops was estimated in 2005 to be 338,000 tonnes.1 2. India has a reported production capacity of 9,900 tonnes 2 and exported 4,103.92 tonnes in 2007-08 to 31 countries.3 Hindustan Insecticides Ltd, owned by the Government of India produces 1,600 tonnes annually. 4 3. Germany produces 4,000 tonnes per year.5 4. China produces 2,400 tonnes per year.6 5. Israel produces an unspecified quantity of endosulfan.7 1 Li YF, Macdonald RW. 2005. Sources and pathways of selected organochlorine pesticides to the Arctic and the effect of pathway divergence on HCH trends in biota: a review. Sci Total Environ 342:87-106. 2 Performance of Chemical & Petrochemical Industry at a Glance (2001-2007). Monitoring and Evaluation Division, Department of Chemicals & Petrochemicals, Ministry of Chemicals & Fertilizers, Government of India, New Delhi. http://www.chemicals.nic.in/stat0107.pdf. 3 Export Import Data Bank. Export: Commodity-wise all countries. Commodity 38081018. Endosulfan technical. Government of India, Ministry of Commerce & Industry, Department of Commerce, http://commerce.nic.in/eidb/Default.asp. 4 Hindustan Insecticides Ltd Manufacturing Units. http://www.hil-india.com/manufacturingunits.htm. 5 Endosulfan. Draft Dossier prepared in support of a proposal of endosulfan to be considered as a candidate for inclusion in the CLRTAP protocol on persistent organic pollutants. German Federal Environment Agency – Umweltbundesamt, Berlin. 2007. 6 Li J, Zhang G, Guo L, Xu W, Li X, Lee CSL, Ding A, Wang T. 2007. Organochlorine pesticides in the atmosphere of Guangzhou and Hong Kong: Regional sources and long-range atmospheric transport. Atmos Environ 41:3889-903. 7 Makhteshim Agan. Thionex. http://www.maindustries.com/ProductsSolutions/CropProtection/tabid/61/Default.aspx. Annex E information on ENDOSULFAN 2 UNEP/POPS/POPRC.1/4 6. South Korea exports technical endosulfan.8 Location: 7. India - Hindustan Insecticides in Kerala;9 Coromandel Fertilisers in Mumbai;10 Excel Crop Care (in association with Australia’s Nufarm) in Bhavnagar, Gujarat.11 8. Germany - Bayer CropScience at Frankfurt.12 9. China - 3 manufacturers of technical endosulfan in Jiangsu province.13 10. Israel - Makhteshim Chemical Works Ltd, Beer-Sheva, Israel.14 (ii) Uses 11. Use of Endosulfan has been declining globally. It is now banned in at least 57 countries15 with former uses replaced by less hazardous products and methods. The Environmental Risk Management Authority of New Zealand (ERMANZ) said in its final decision to revoke registration of Endosulfan that “There is evidence that endosulfan use in New Zealand has been declining over the past 10 years. This has been market driven as well as resulting from the availability of some 8 Jia H, Li Y-F, Wang D, Cai D, Yang M, Ma J, Hu J. 2008. Endosulfan in China 1. Gridded usage inventories. Enviro Sci Poll Res Int [Epub September 4]. 9 Hindustan Insecticides Ltd Manufacturing Units. http://www.hil-india.com/manufacturingunits.htm. 10 Coromandel Fertilisers Ltd. http://www.cflindia.com/. 11 (a) Excel Crop Care. http://www.excelcropcare.com/ProductDetails.asp?name=1. (b) Excel Crop Care Investment research report with target. Dec 26, 2008. http://www.indianstocksnews.com/2008/12/excelcrop-care-investment-research.html. (c) Fundamental Research. Excel Industries Ltd. HDFC Securities. http://www.hdfcsec.com/Research/FResearch.aspx?Heading=FundamentalResearch&FP_Code=EXCELIN DUS&View=FRHistory.ascx. 12 Endosulfan. Draft Dossier prepared in support of a proposal of endosulfan to be considered as a candidate for inclusion in the CLRTAP protocol on persistent organic pollutants. German Federal Environment Agency – Umweltbundesamt, Berlin. 2007. 13 Jia H, Li Y-F, Wang D, Cai D, Yang M, Ma J, Hu J. 2008. Endosulfan in China 1. Gridded usage inventories. Enviro Sci Poll Res Int [Epub September 4]. 14 Makhteshim Agan Global Presence. http://www.maindustries.com/OurGroup/GlobalPresence/tabid/69/Default.aspx. 15 Austria, Bahrain, Belgium, Belize, Benin, Bulgaria, Burkina Faso, Cambodia, Cap-Vert, Colombia, Cote d’Ivoire, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Gambia, Germany, Greece, Guinea Bissau, Hungary, Indonesia, Ireland, Italy, Jordan, Kuwait, Latvia, Lithuania, Luxembourg, Malaysia, Mali, Malta, Mauritania, Netherlands, New Zealand, Niger, Nigeria, Norway, Oman, Poland, Portugal, Qatar, Romania, Saudi Arabia, Senegal, Singapore, Slovakia, Slovenia, Spain, Sri Lanka, St Lucia, Sweden, Syria, Tchad, the United Arab Emirates, United Kingdom. Annex E information on ENDOSULFAN 3 UNEP/POPS/POPRC.1/4 new insecticide chemistry.” … “The Committee notes that there are alternative products available for most of the current uses for endosulfan in New Zealand.” 16 (iii) Releases Discharges 12. Endosulfan is discharged directly to the environment when it is used deliberately on crops and other uses. That discharge is estimated to have been 338,000 tonnes by 2005 (based on cumulative global usage as estimated by Li & Macdonald 200517), and is estimated to be more than 16,000 tonnes per annum based on reported production figures (see Production Data, Quantity). 13. High residue levels of Endosulfan reported for the Vellar River (206-2035 ng/l) and Kolleru Lake (2396 ng/l) in India are stated to be “primarily the result of the close proximity of a pesticide manufacturing facility”, indicating discharge from the facility into the environment.18 Losses 14. Studies of Endosulfan application to cotton fields in Australia showed that about 70% of Endosulfan is lost from the cotton field through volatilisation, with only 8.5% remaining on the field one month after spraying; 2% is carried away in run-off, 1% remains in the soil, and the remainder is degraded by plants or microorganisms). Hence approximately 73% of Endosulfan applied, at least in hot/tropical environments, leaves the site of application and is transported in the wider environment.19 Emissions Other 16 ERMANZ. 2008. Environmental Risk Management Authority Decision. Application Code HRC07003. 10 December 2008. http://www.ermanz.govt.nz/search/registers.html?id=23290. 17 Li YF, Macdonald RW. 2005. Sources and pathways of selected organochlorine pesticides to the Arctic and the effect of pathway divergence on HCH trends in biota: a review. Sci Total Environ 342:87-106. 18 Sarkar SK, Bhattacharya BD, Bhattacharya A, Chatterjee, Alam A, Satpathy KK, Jonathan MP. 2008. Occurrence, distribution and possible sources of organochlorine pesticide residues in tropical coastal environment of India: An overview. Environ Int 34(7):1062-71. 19 Kennedy IR, Sanchez-Bayo F, Kimber SW, Hugo L, Ahmad N. 2001. Off-site movement of endosulfan from irrigated cotton in New South Wales. J Environ Qual 30:683-96. Annex E information on ENDOSULFAN 4 UNEP/POPS/POPRC.1/4 (b) Hazard assessment for endpoints of concern, including consideration of toxicological interactions involving multiple chemicals (provide summary information and relevant references) Toxicokinetics 15. Absorption through the gastrointestinal tract is very rapid and efficient with >90% absorbed in rats. Absorption through the skin is also rapid, with 73-89% in male rats at 24 hours and 20-46% in female rats at 168 hours.20 16. In humans, Endosulfan is absorbed across the skin, through the gastrointestinal tract, and through inhalation.21 17. Ingested Endosulfan is subject to significant first pass metabolism by the liver and biliary excretion. It is therefore expected to be more toxic by inhalation than oral exposure, and indeed, the limited number of inhalation toxicology studies that have been conducted found lower NOAELs than oral studies that evaluated similar endpoints.22 18. Endosulfan is metabolised in animals by microsomal enzymes to Endosulfan sulphate, Endosulfan diol, Endosulfan ether, Endosulfan hydroxyether, and Endosulfan lactone.23 19. It is excreted in urine and faeces, as well as being distributed to adipose, liver, kidney, heart, spleen, testes, epididymis, prostate, seminal vesicle, milk and muscle, with greater accumulation in adipose tissue of females than males.24 20 EU. 1999. Monograph prepared in the context of the inclusion of the following active substance in Annex I of the Council Directive 91/414/EEC. ENDOSULFAN. Volume I Report and Proposed Decision. Ministerio de Agricultura, Pesca y Alimentación, Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria (I.N.I.A.), Ctra. De La Coruña, km. 7, 28040 – Madrid, España. 21 ATSDR. 2000. Toxicological Profile for Endosulfan. Agency of Toxic Substances and Disease Registry, Atlanta, USA. http://www.atsdr.cdc.gov/toxprofiles/tp41.html. 22 OEHHA. 2008. Revised findings on the health effects of the active ingredient: endosulfan. Office of Environmental Health Hazard Assessment, California Environmental Protection Agency, June 4, 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/memo_findings060408.pdf. 23 EU. 1999. Monograph prepared in the context of the inclusion of the following active substance in Annex I of the Council Directive 91/414/EEC. ENDOSULFAN. Volume I Report and Proposed Decision. Ministerio de Agricultura, Pesca y Alimentación, Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria (I.N.I.A.), Ctra. De La Coruña, km. 7, 28040 – Madrid, España. 24 ATSDR. 2000. Toxicological Profile for Endosulfan. Agency of Toxic Substances and Disease Registry, Atlanta, USA. http://www.atsdr.cdc.gov/toxprofiles/tp41.html. Annex E information on ENDOSULFAN 5 UNEP/POPS/POPRC.1/4 20. In humans it is commonly found distributed to breast milk, adipose tissue, placental tissue, umbilical cord blood and follicular fluid.25 For more details refer section: Monitoring. 21. Residues have also been found in the liver, kidney and brain of humans.26 22. Residues in people not occupationally exposed are thought to result from intake of food chain residues.27 28 A positive correlation has been found between intake of vegetables containing residues of Endosulfan and the presence of Endosulfan-lactone in breast milk.29 Mode of action in mammals 23. Endosulfan has an affinity with the GABA (gamma-aminobutyric acid) receptors in the brain and acts as a non-competitive GABA antagonist. Binding of GABA to its receptors induces the uptake of chloride ions by neurons and blockage of this uptake by Endosulfan results in a state of uncontrolled excitation.30 24. In vitro assays indicate that Endosulfan can form DNA-adducts, and inhibit hepatocyte gap junction intercellular communication.31 25. In vitro assays also show that Endosulfan has an oestrogenic progestogenic action. 33 32 and an anti- 25 Cerrillo I, Granada A, Lopez-Espinosa MJ, Olmos B, Jimenez M, Cano A, Olea N, Fatima Olea-Serrano M. 2005. Endosulfan and its metabolites in fertile women, placenta, cord blood, and human milk. Environ Res 98(2):233-39. 26 ATSDR 2000, op. cit. 27 Sanghi R, Pillai MK, Jayalekshmi TR, Nair A. 2003. Organochlorine and organophosphorus pesticide residues in breast milk from Bhopal, Madhya Pradesh, India. Hum Exp Toxicol 22(2):73-6. 28 Carreno J, Rivas A, Granada A, Lopez-Espinosa MJ, Mariscal M, Olea N, Olea-Serrano F. 2007. Exposure of young men to organochlorine pesticides in Southern Spain. Environ Res 103:55-61. 29 Campoy C, Jimenz M, Olea-Serrano MF, Moreno-Frias M, Canabate F, Olea N, Bayes R, Molina-Font JA. 2001. Analysis of organochlorine pesticides in human milk: preliminary results. Early Hum Devel 65(s2):S183-90. 30 UNEP/FAO. 2007. Inclusion of the Chemical Endosulfan in Annex III of the Rotterdam Convention. United Nations Environment Programme and Food and Agriculture Organisation UNEP/FAO/RC/COP.4/9. http://www.pic.int/COPS/COP4/i9)/English/K0763331%20COP-4-9.pdf. 31 SRP. 2008. Findings of the Scientific Review Panel on Toxic Air Contaminants on the Proposed Identification of Endosulfan as a Toxic Air Contaminant. Scientific Review Panel on Toxic Air Contaminants, Department of Pesticide Regulation, California Environmental Protection Agency, Sacramento. May 16, 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/srp_finding_end_final.pdf. 32 Soto AM, Chung KL, Sonnenschein C. 1994. The pesticides endosulfan, toxaphene, and dieldrin have estrogenic effects on human estrogen-sensitive cells. Environ Health Perspect 102(4):380-83. 33 Chatterjee S, Kumar V, Majumder CB, Roy P. 2008. Screening of some anti-progestin endocrine disruptors using a recombinant yeast-based in vitro bioassay. Toxicol in Vitro 22(3):788-98. Annex E information on ENDOSULFAN 6 UNEP/POPS/POPRC.1/4 Acute effects 26. Endosulfan is of high acute toxicity in experimental animal studies with an acute oral LD50 rat of 10-22.7 mg/kg in females, and 48-160 mg/kg in males.34 27. It is even more toxic by inhalation, with LC50 values of 0.0126 mg/L (2.1 mg/kg) in females and 0.0345 mg/L (5.8 mg/kg) in males.35 28. In rats, Endosulfan is acutely toxic in small oral doses of 3.0 mg/kg, causing stilted gait, straddled hind-limbs, irregular respirations, panting and decreased motor activity. This study resulted in a NOAEL of 1.5 mg/kg/day, which the US EPA selected as the critical endpoint for evaluation of dietary risk for Endosulfan.36 It is even more toxic to pregnant rabbits causing hyperactivity after a single oral 1.8 mg/kg dose. The NOAEL for this study was 0.7 mg/kg/day, which the US state of California selected as the critical endpoint for evaluation of dietary risk in its assessment of Endosulfan.37 29. Acute toxicity effects observed in animal studies include hyperexcitability, tremors, convulsions, seizures, irregular respiration, altered heart rate, brain oedema, salivation, dilated pupils, poor muscle tone, head swaying, vomiting, diarrhoea, emphysema, cyanosis, respiratory paralysis, haemorrhage of heart muscle, lung and kidney; death.38 30. Acute effects reported in humans as a consequence of occupational inhalation exposure are primarily neurotoxic and include malaise, nausea, vomiting, dizziness, confusion, and/or weakness, and convulsions.39 31. Endosulfan is very toxic to some amphibian species. A recent study (Relyea 2008) found that leopard frog tadpoles (Rana pipines) exposed to 6.4 ppb aqueous Endosulfan experienced 84% mortality. A combination of 5 insecticides 34 EU. 1999. Monograph prepared in the context of the inclusion of the following active substance in Annex I of the Council Directive 91/414/EEC. ENDOSULFAN. Volume I Report and Proposed Decision. Ministerio de Agricultura, Pesca y Alimentación, Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria (I.N.I.A.), Ctra. De La Coruña, km. 7, 28040 – Madrid, España. 35 CDPR. 2008. Endosulfan Risk Characterization Document, Volume I: Health Risk Assessment. Department of Pesticide Regulation, California Environmental Protection Agency, Sacramento. August 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/hlth_rsk_asmt1.pdf. 36 US EPA. 2007. Endosulfan. Acute and Chronic (Food and Drinking Water) Dietary Exposure Assessment to update the 2002 Registration Eligibility Decision. March 14, 2007. United States Environmental Protection Agency. Available in the public docket at www.regulations.gov under docket ID No. EPA-HQ-OPP-2002-0262-0061. 37 CDPR. 2008. Endosulfan Risk Characterization Document, Volume I: Health Risk Assessment. Department of Pesticide Regulation, California Environmental Protection Agency, Sacramento. August 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/finaleval/endosulfan.htm. 38 ATSDR. 2000. Toxicological Profile for Endosulfan. Agency of Toxic Substances and Disease Registry, Atlanta, USA. http://www.atsdr.cdc.gov/toxprofiles/tp41.html. 39 ATSDR 2000, op. cit. Annex E information on ENDOSULFAN 7 UNEP/POPS/POPRC.1/4 including Endosulfan was even more toxic, causing 99% mortality. In contrast grey tree frog tadpoles (Hyla versicolor) were unaffected by exposure to this level of Endosulfan alone or in combination with other insecticides, and survival to metamorphosis was statistically identical to controls. Relyea also cites unpublished work finding LC50s as low as 1 ppb for undisclosed tadpole species, a study finding that Litoria Citropa tadpoles exposed to 0.8 ppb experienced 11– 34% mortality, and other studies reporting significant mortality in salamander and tadpole species exposed to Endosulfan in the range of tens to hundreds of ppb. 40 32. Endosulfan is highly toxic to bees, with an acute oral toxicity LD50 of 2 μg ai/bee, and an acute contact toxicity LD50 of 0.82 μg ai/bee (both based on formulated product).41 Sublethal effects of Endosulfan on bees include reduced olfactory learning.42 33. Endosulfan is toxic to a wide range of beneficial insects. It significantly reduced the emergence and the parasitism of the parasitic wasp Trichogramma pretiosum,43 which kills the eggs of various moth pests such as heliothis, corn borer, cabbage moth, loopers, and yellow peach moth. It is toxic to Orius insidiosus (Minute pirate bug / insidious flower bug), which predates thrips, mites, aphids and small caterpillars; and to the parasitic wasp Aphidius colemani, which parasitizes aphids 44 —both important in glasshouse IPM programmes. Orius insidiosus also predates Helicoverpa zea, cotton bollworm, as does Geocoris punctipes. Endosulfan is toxic to both of these predators, but more so to females of the latter species, and it reduces fecundity and consumption of bollworm eggs by both predators.45 It is also toxic to the predacious mite Phytoseiulus persimilis, which predates upon spider mites and is very important in IPM programmes. Endosulfan reduces the number of females laying eggs and the number of eggs that hatch.46 Endosulfan is highly toxic to the eggs and larvae of Chrysoperla externa, a lacewing that predates mites and is a valuable biological control 40 Relyea R. 2008. A cocktail of contaminants: how mixtures of pesticides at low concentrations affect aquatic communities. Oecologica [Epub November 11]. 41 UNEP/FAO. 2006. Endosulfan. Documentation received from the European Commission to support its notification of final regulatory action on endosulfan. United Nations Environment Programme and Food and Agriculture Organisation. UNEP/FAO/RC/CRC.3/10/Add.1. http://www.pic.int/incs/crc3/j10add1)/English/K0654655%20CRC3-10-ADD-1%20final.pdf. 42 Decourtye A, Devillers J, Genecque E, Le Menach K, Budzinski H, Cluzeau S, Pham-Delegue MH. 2005. Comparative sublethal toxicity of nine pesticides on olfactory learning performances of the honeybee Apis meillifera. Arch Environ Contam Toxicol 48(2):242-50. 43 Bastos CS, de Almeida RP, Suinaga FA. 2006. Selectivity of pesticides used on cotton (Gossypium hirsutum) to Trichogramma pretiosum reared on two laboratory-reared hosts. Pest Manag Sci 62:91–8. 44 Bostanian NJ, Akalach M. 2004. The contact toxicity of indoxacarb and five other insecticides to Orius insidiosus (Hemiptera: Anthocoridae) and Aphidius colemani (Hymenoptera: Braconidae), beneficials used in the greenhouse industry. Pest Manag Sci 60(12):1231-6. 45 Elzen GW. 2001. Lethal and sublethal effects of insecticide residues on Orius insidiorus (Hemiptera: Anthocoridae) and Geocoris punctipes (Hemiptera: Lygaeidae). J Econ Entomol 94(1):55-9. 46 Bostanian NJ, Akalach M. 2006. The effect of indoxacarb and five other insecticides on Phytoseiulus persimilis (Acari: Phytoseiidae), Amblyseius fallacis (Acari: Phytoseiidae) and nymphs of Orius insidiosus (Hemiptera: Anthocoridae). Pest Manag Sci 62:334–9. Annex E information on ENDOSULFAN 8 UNEP/POPS/POPRC.1/4 species. 47 It also reduces prey consumption and web building of the spider Araneus pratensis, an important predator of agricultural pests such as midges, and an indicator of ecosystem disturbance (Benamú et al. 2007).48 34. Endosulfan significantly reduced the development of the ‘entomopathogenic’ fungus, Verticillium lecanii (Zimm.)—a fungus used in some IPM programmes to kill insect pests such as aphids, thrips and whitefly.49 35. Endosulfan treatment of cotton fields in India resulted in a 60.5% decrease in the population of the beneficial bacteria actinomycetes 10 days after treatment. 50 Actinomycetes play a vital role in replenishing the supply of nutrients in the soil: they help with the decomposition of organic matter and the formation of humus, particularly by breaking down cellulose and chitin; and help non-leguminous plants fix nitrogen. Endosulfan is also toxic to the major groups of beneficial small soil invertebrates, mites and springtails, causing a persistent decline in populations. These invertebrates are key to maintaining soil fertility and mixing the organic and mineral components of soil.51 36. Coral organisms are highly sensitive to Endosulfan at around detection limits, with effects noted including bleaching, reduced larval set, metamorphosis and photosynthetic efficiency. Contamination of coral reefs with run-off from agricultural areas could have a profound effect—even at levels at the limits of detection—on the replenishment of populations of coral organisms, and hence survival of the reefs.52 Systemic effects 37. The primary systemic targets are the liver and kidney, but Endosulfan also causes haematological and respiratory effects as a result of generalised effects on the central nervous system. Observed effects on rats include inflammation of lungs; congestion and degeneration of kidney tubules, renal necrosis, and renal haemorrhage; congestion and necrosis of the liver; blood in small intestines; decreased haemoglobin and red blood cell count in protein deficient rats; 47 Schneider MI, Pineda P, Smagghe G. 2006. Side effects of conventional and non-conventional insecticides on eggs and larvae of Chrysoperla externa (Hagen) (Neuroptera: Chrysopidae) in Argentine. Commun Agric Appl Biol Sci 71(2 Pt B):425-7. 48 Benamú MA, Schneider MI, Pineda S, Sanchez NE, Gonzalez A. 2007. Sublethal effects of two neurotoxican insecticides on Araneus pratensis (Araneae: Araneidae). Commun Agric Appl Biol Sci 72(3):557-9. 49 Alizadeh A, Samih MA, Izadi H. 2007. Compatibility of Verticillium lecani (Zimm.) with several pesticides. Commun Agric Appl Biol Sci 72(4):1011-5. 50 Vig K, Singh DK, Agarwal HC, Dhawan AK, Dureja P. 2008. Soil microorganisms in cotton fields sequentially treated with insecticides. Ecotoxicol Environ Saf 69(2):263-76. 51 Joy VC, Chakravorty PP. 1991. Impact of insecticide on nontarget microarthropod fauna in agricultural soil. Ecotoxicol Environ Saf 22(1):8-16). 52 Markey KL, Baird AH, Humphrey C, Negri AP. 2007. Insecticides and a fungicide affect multiple coral life stages. Mar Ecol Prog Ser 330:127–37. Annex E information on ENDOSULFAN 9 UNEP/POPS/POPRC.1/4 calcification of heart and coronary and mesenteric arteries, aneurisms, cardiotoxicity through oedema and swelling of myocardial cells, heart and circulatory failure; reduced body weight gain, reduced appetite; and hyperglycaemia more marked in older animals.53 38. “At a concentration of 0.001 pg/ml (1 ppb) Endosulfan was found to damage human red cell membranes as demonstrated by fluorescence of 30-50% of red cells on staining with MC-540. This was supported by the finding of crenation and threading of red blood cells under SEM. At a concentration of 1 pg/ml (1 ppm) the cells were markedly damaged.” … “This is accompanied with increased permeability of these membranes as shown by estimation of plasma haemoglobin in supernatants after incubation with Endosulfan”.54 Neurological and behavioural effects 39. Occupational inhalation of Endosulfan, in an Israeli chemical factory, led to long-term brain damage with psychiatric manifestations. The man suffered longterm cognitive and emotional deterioration, severe memory impairment, and inability to perform small tasks, with impaired visual-motor coordination. The acute phase included malaise, repeated convulsions and impaired consciousness, and after recovery from these the person became disoriented and agitated.55 40. An agricultural pilot exposed to Endosulfan showed persistent “nonspecific epileptic foci in the cerebral frontal lobes”.56 41. From 1992–2005, Endosulfan was identified as a potential contributor to 58 cases of pesticide related illness in the state of California, USA. Almost all cases involved either pesticide applicators or farmworkers exposed occupationally. Skin irritation and rashes were the most common symptoms (43 cases), though systemic effects and signs of neurotoxicity (nausea, numbness, headache, etc.) were also sometimes noted (15 cases), as were respiratory effects (15 cases).57 Elsewhere in the US, two cases are noteworthy. In one case, a mixer spilled Endosulfan onto his clothes and did not wash or change his clothing. He may also have been exposed to acephate and maleic hydrazide. The second was 53 ATSDR. 2000. Toxicological Profile for Endosulfan. Agency of Toxic Substances and Disease Registry, Atlanta, USA. http://www.atsdr.cdc.gov/toxprofiles/tp41.html. 54 Daniel CS, Agarwal S, Agarwal SS. 1986. Human red blood cell membrane damage by endosulfan. Toxicol Letts 32(1-2):113-8. 55 Alexsandrowicz DR. 1979. Endosulfan poisoning and chronic brain syndrome. Arch Toxicol 43:65-8. 56 ATSDR. 2000. Toxicological Profile for Endosulfan. Agency of Toxic Substances and Disease Registry, Atlanta, USA. http://www.atsdr.cdc.gov/toxprofiles/tp41.html. 57 CDPR. 2008. Endosulfan Risk Characterization Document, Volume II: Exposure Assessment, HS-1647. Department of Pesticide Regulations, California Environmental Protection Agency, May 2008. http://www.cdpr.ca.gov/docs/whs/pdf/hs1647.pdf. Annex E information on ENDOSULFAN 10 UNEP/POPS/POPRC.1/4 similar, but involved only Endosulfan. The first case was fatal; the second resulted in “permanent neurological impairment”.58 42. A case-control study, by the National Institute of Occupational Health (NIOH), of 619 school children in the Kasargod District of Kerala, India, that had been chronically exposed to Endosulfan through spraying of neighbouring cashew nut plantations, found a “significantly higher prevalence of neurobehavioural disorders” in the study group compared with the control group of 416 children. The finding included significantly higher “scholastic backwardness” and reduced IQ, and a higher prevalence of arrogant and aggressive behaviour and restlessness. The authors concluded that “in the study groups the children are having a number of functional abnormalities of the nervous system which though not severe enough to prevent them from attending school, may interfere with their optimal intellectual development and total personality”. There was also a non-statistically significant increase in prevalence of epilepsy in girls. 59 43. An epidemiological study in California (USA), by Roberts et al. (2007), linked maternal non-occupational exposure to Endosulfan and dicofol to autism in children amongst women living within 500m of its application during the first trimester of pregnancy, suggesting exposure by inhalation of drift. The rate of autism was 6 times higher than expected.60 44. Endosulfan caused behavioural effects in rats, including aggression and increased time to learn tasks, even after exposure had ceased; and impaired learning and memory processes, extreme sensitivity to noise and light, and muscle spasms.61 45. Developmental exposure to Endosulfan may increase the risk of Parkinson’s disease through its effects on neurotransmitters and amino acids in the brain. It changes the brain levels of the neurotransmitters dopamine, noradrenalin and serotonin.62 Mice exposed to endosulfan from postnatal days 5 to 19 exhibited only insignificant changes in dopamine, acetylcholinesterase and alpha-synuclein levels; however when re-exposed as adults they showed significantly depleted dopamine, increased levels of alpha-synuclein and increased 58 Brandt VA, Moon S, Ehlers J, Methner MM, Struttmann T. 2001. Exposure to endosulfan in farmers: two case studies. Am J Ind Med 39(6):643-9. 59 NIOH. 2003. Final Report of the Investigation of Unusual Illnesses Allegedly Produced by Endosulfan Exposure in Padre Village of Kasargod District (N Kerala). National Institute of Occupational Health, Indian Council for Medical Research, Ahmedabad. 60 Roberts EM, English PB, Grether KJ, Windham GC, Somberg L, Wolff C. 2007. Maternal residence near agricultural pesticide applications and autism spectrum disorders among children in the California Central Valley. Environ Health Perspect 115(10):1482-9. 61 ATSDR. 2000. Toxicological Profile for Endosulfan. Agency of Toxic Substances and Disease Registry, Atlanta, USA. http://www.atsdr.cdc.gov/toxprofiles/tp41.html. 62 ATSDR 2000, op. cit. Annex E information on ENDOSULFAN 11 UNEP/POPS/POPRC.1/4 acetylcholinesterase activity in the brain.63 Endosulfan, at low concentrations (10 nmol/l to 10 umol/l) also inhibits proteasome activity and degradation of alphasynuclein.64 The loss of dopamine and the accumulation of alpha-synuclein are both associated with Parkinson’s disease. 46. Cabaleiro et al. (2008) 65 recently reported a developmental neurotoxicity (DNT) study in which Endosulfan was administered to pregnant Sprague-Dawley rats at 0, 0.61, and 6.12 mg Endosulfan/kg/day orally via gavage from the beginning of gestation until weaning. Changes in neurochemistry in pups were noted at doses that were not maternally toxic. At the highest dose tested (HDT), the body weight of dams was statistically significantly depressed at the end of gestation. Adverse effects were not noted in dams at the lowest dose tested (LDT), but were observed in their offspring. Male offspring were sacrificed at post-natal days (PND) 15, 30, and 60, and biogenic amine and amino acid levels in the prefrontal cortex were determined. At the LDT, aspartate, glutamate, and serotonin levels differed statistically significantly from controls at PND 30; GABA levels differed significantly at PND 60; the ratio of homovanilic acid to dopamine differed significantly at PND 15; the ratio of 3,4-dihydroxyphenylacetic acid to dopamine differed significantly at PND 15 and 60; and taurine levels differed significantly at PND 15 and 30. At the HDT, aspartate and glutamate levels differed significantly from controls at PND 15 and 30; glutamine levels differed significantly at PND 15; taurine levels differed significantly at PND 15, 30, and 60; the ratio of 3,4-dihydroxyphenylacetic acid to dopamine differed significantly at PND 15 and 60; serotonin levels differed significantly at PND 30 and 60; and the ratio of 5-hydroxyindole acetic acid to serotonin differed significantly at PND 60. Pup weight gain was statistically significantly decreased at PND 21 at the LDT (and at PND 15, 21, and 30 at the HDT). 47. Gilmore (2006)66 reported a developmental neurotoxicity (DNT) study to the US EPA in support of continued Endosulfan registration in the US. In this study, Endosulfan was administered to dams beginning on the 6 th day of pregnancy and continuing until weaning (post-natal day 21). This study did not find signs of DNT in pups or of neurotoxicity in dams, even at the highest dose tested, 29.8 mg/kg/day. However other adverse effects were noted, including decreased weight gain (pups and dams) and delayed preputial separation (pups). 63 Jia Z, Misra HP. 2007. Developmental exposure to pesticides zineb and/or endosulfan renders the nigrostriatal dopamine system more susceptible to these environmental chemicals later in life. Neurotoxicology 28(4):727-35. 64 Wang XF, Li S, Chou AP, Bronstein JM. 2006. Inhibitory effects of pesticides on proteasome activity: implication in Parkinson's disease. Neurobiol Dis 23(1):198-205. 65 Cabaleiro T, Caride A, Romero A, Lafuente A. 2008. Effects of in utero and lactational exposure to endosulfan in prefrontal cortex of male rats. Toxicol Lett 176(1):58-67. 66 Gilmore RG, Sheets LP, Hoss HE. 2006. A Developmental Neurotoxicity Study with Technical Grade Endosulfan in Wistar Rats. Bayer CropScience LP, Toxicology, Stilwell KS: Report No. 201563; 9/26/06. See also: US EPA. 2007. PC079402: Endosulfan—Developmental Neurotoxicity Feeding Study in Rats with Endosulfan [MRID £ 46968301], Docket ID No. EPA-HQ-OPP-2002-0262-58, March, 2007. Both can be found in public docket http://www.regulations.gov under document ID no EPA-HQ-OPP-20020262-0058.1. Annex E information on ENDOSULFAN 12 UNEP/POPS/POPRC.1/4 Interpretation of this study’s results has been difficult, and there is disagreement among experts about what the No Observable Adverse Effects Levels (NOAEL) are. The authors identified 3.74 mg/kg/day as the NOAEL for both dams and pups based on effects observed at the next highest dose. For dams these effects were “Statistically significant decreases in body weight, weight gain and food consumption during gestation and statistically significant decreases in body weight during lactation”; and for pups “Statistically significant decreases in pre(both sexes) and post-weaning (males only) body weight and similar decreases in body weight gain, a delay in balanopreputial separation and significant decrease in PND 21 terminal body weight (perfused females)”. Reviewers at the US EPA disagreed with the authors’ conclusions about the pup NOAEL, finding that pup weights were also reduced at 3.74 mg/kg/day. US EPA therefore considers 3.74 mg/kg/day to be the Lowest Observable Adverse Effects Level (LOAEL) for pups, and estimates the pup NOAEL to be 1.75 mg/kg/day by applying a 3-fold uncertainty factor to the LOAEL. 67 In contrast, the California Department of Pesticide Regulation (USA) considers 3.74 mg/kg/day to be the LOAEL for both dams and pups. 68 The usefulness of this study is further undermined by the fact that dosing did not begin until the sixth day of gestation. In humans, early pregnancy is a critical period for neural development, and Roberts et al. (2007; see above) found that Endosulfan exposure during the first trimester was correlated with increased autism incidence. Since dosing in the Gilmore study did not begin until about 1/3 through gestation, this window of increased susceptibility was missed. Finally, LD50 values for Endosulfan in females range from 10-22.7 mg/kg, 69 and convulsions have been observed in female Wistar rats fed a single 3.0 mg/kg dose. 70 In contrast, in the Gilmore study, which was also carried out in Wistar rats, no convulsions or other signs of neurotoxicity were observed, even in females fed doses as high as 29.8 mg/kg/day for 5 weeks. The large discrepancy between the results of this study vis-à-vis others casts doubts on its integrity. Reproductive and developmental effects 48. The NIOH case-control study of 619 school children in the Kasargod District US EPA. 2007. Endosulfan. The Health Effects Division’s Addendum and Update to the 2002 Risk Assessment. November 13, 2007. Available in the public docket at http://www.regulations.gov under Docket ID No. EPA-HQ-OPP-2002-0262-0064. 68 CDPR. 2008. Endosulfan Risk Characterization Document, Volume II: Exposure Assessment, HS-1647. Department of Pesticide Regulations, California Environmental Protection Agency, May 2008. http://www.cdpr.ca.gov/docs/whs/pdf/hs1647.pdf. 69 EU. 1999. Monograph prepared in the context of the inclusion of the following active substance in Annex I of the Council Directive 91/414/EEC. ENDOSULFAN. Volume I Report and Proposed Decision. Ministerio de Agricultura, Pesca y Alimentación, Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria (I.N.I.A.), Ctra. De La Coruña, km. 7, 28040 – Madrid, España. 70 EPA. 2007. Endosulfan. Hazard Characterization and Endpoint Selection Reflecting Receipt of a Developmental Neurotoxicity Study and Subchronic Neurotoxicity Study. United States Environmental Protection Agency, April 2, 2007. Available in the public docket at http://www.regulations.gov under Docket ID No. EPA-HQ-OPP-2002-0262-0065. 67 Annex E information on ENDOSULFAN 13 UNEP/POPS/POPRC.1/4 of Kerala, India, that had been chronically exposed to Endosulfan through spraying of neighbouring cashew nut plantations, found a “significantly higher prevalence of congenital malformations in female subjects and abnormalities related to the male reproductive system” in the study group compared with the control group of 416 children. “The prominent abnormalities were congenital heart diseases and skeletal abnormalities.” … “The abnormalities of testes like Cryptorchidism and hydrocele were reported exclusively amongst the study subjects.” The study found statistically significant lower sexual maturity rating scores for males for pubic hair, penis and testes, and higher physiological goitre occurring at onset of puberty. It also found significantly higher prevalence of subnormal or delayed mental development.71 72 49. Pregnant rats were exposed to Endosulfan (1 or 2 mg/kg/day) from day 12 of gestation through parturition. Exposure to Endosulfan during foetal gonadal differentiation altered the process of spermatogenesis by affecting testicular lactate dehydrogenase and sorbitol dehydrogenase. Reduction in spermatid count in testis and sperm count in cauda epididymis was observed. Testis, epididymis and seminal vesicle showed significant decrease in weights in both the treated groups while no effect on prostate weight was recorded. “Hence it can be suggested that endosulfan interferes in the process of spermatogenesis”. The overall toxicity was dose dependent. The dose levels were not maternally toxic, and no mortality, clinical or behavioural effects were observed.73 50. In a study of 21 women attending an in vitro fertilisation programme in Canada, a correlation was found between levels of Endosulfan in serum and lack of fertilisation. The mean level of endosulfan in serum from women who became pregnant was 160 pg/ml, whilst that of women who did not achieve fertilisation was 810 pg/ml.74 51. Dose levels of 4 mg/kg/day completely inhibited implantation in female mice, as well as significantly decreasing dioestrus and increasing oestrus.75 52. Endosulfan at concentrations ranging from 0.5 to 10 uM disrupted the human retinoid signalling pathway in reporter cell lines, and Lemaire et al. (2005) 71 NIOH. 2003. Final Report of the Investigation of Unusual Illnesses Allegedly Produced by Endosulfan Exposure in Padre Village of Kasargod District (N Kerala). National Institute of Occupational Health, Indian Council for Medical Research, Ahmedabad. 72 Saiyed H, Dewan A, Bhatnagar V, Shenoy U, Shenoy R, Rajmohan H, Patel K, Kashyap R, Kulkarni P, Rajan B, Lakkad B. 2003. Effect of endosulfan on male reproductive development. Environ Health Perspect 111(16):1958-62. 73 Sinha N, Adhikari N, Saxena DK. 2001. Effect of endosulfan during gonadal differentiation on spermatogenesis in rats. Environ Toxicol Pharmacol 10:29-32. 74 Younglai EV, Foster WG, Hughes EG, Trim K, Jarrell JF. 2002. Levels of environmental contaminants in human follicular fluid, serum, and seminal plasma of couples undergoing in vitro fertilization. Arch Environ Contam Toxicol 43(1):121-26. 75 Hiremath MB, Kaliwal BB. 2002. The anti-implantation action of endosulfan in albino mice: possible mechanisms. J Basic Clin Physiol Pharmacol 13(4):329-40. Annex E information on ENDOSULFAN 14 UNEP/POPS/POPRC.1/4 proposed this as the explanation for observed teratogenic effects in humans as a result of long-term exposure.76 53. Endosulfan, at a dose level of 1 mg/kg body weight administered to pregnant rats by oral intubation, “caused significant teratogenic effects in the developing fetuses. There was no maternal mortality, however, reduced maternal weight gain and number of live fetuses and increased fetal resorptions were recorded. The fetal body weights and crown to rump lengths were significantly decreased and the per cent gross, visceral and skeletal anomalies were significantly increased in the fetuses of dams of all the treated groups. The internal hydrocephalus, cerebellar hypoplasia, microphthalmia, contracted and notched kidneys, multilobulated liver, dilated renal pelvis, incomplete ossification of skull bones, rib anomalies and sacral and caudal vertebrae agenesis were the important fetal malformations.” 77 54. Dalsenter et al. (1999)78 treated pregnant Wistar rats from gestation day 15 through day 21 of lactation with endosulfan at 0, 1.5, and 3 mg/kg/day and examined male offspring for reproductive effects. Age of testis descent and preputial separation were not affected at either dose, but at both doses sperm production was reduced and histology revealed abnormalities at puberty (day 65). At the highest dose only, sperm production was still reduced at day 140. In a follow-up study (Dalsenter 2003),79 female Wistar rats were treated at 0, 0.5, and 1.5 mg/kg/day from 21 days prior to mating through lactation. Age of testis descent and preputial separation in male offspring were evaluated along with a number of other reproductive endpoints including sex organ weights, sperm parameters, and testosterone levels. The authors reported that “with the exception of a significant increase in the relative epididymis weight seen in the group treated with the lowest dose, we have not found any statistically significant adverse effect in the reproductive endpoints investigated at adulthood.” However, the authors assessed statistical significance only at the P < 0.01 level, rather than the more common P < 0.05 level. We observe that the age of preputial separation increased with dose, and this increase does appear to reach statistical significance at the P < 0.05 level for the 1.5 mg/kg/day dose group.80 76 Lemaire G, Balaguer P, Michel S, Rahmani R. 2005. Activation of retinoic acid receptor-dependent transcription by organochlorine pesticides. Toxicol Appld Pharmacol 202:38-49. 77 Singh ND, Sharma AK, Dwivedi P, Patil RD, Kumar M. 2006. Citrinin and endosulfan induced teratogenic effects in Wistar rats. J Appl Toxicol 27(6):589-601. 78 Dalsenter PR, Dallegrave E, Mello JR, Langeloh A, Oliveira RT, Faqi AS. 1999. Reproductive effects of endosulfan on male offspring of rats exposed during pregnancy and lactation. Hum Exp Toxicol 18(9):5839. 79 Dalsenter PR, de Araújo SL, de Assis HC, Andrade AJ, Dallegrave E. 2003. Pre and postnatal exposure to endosulfan in Wistar rats. Hum Exp Toxicol 22(4):171-5. 80 Using the Student t-test and assuming unequal population standard deviations, the one- and two-tailed pvalues are thus 0.022 and 0.043, respectively. Annex E information on ENDOSULFAN 15 UNEP/POPS/POPRC.1/4 55. Reproductive endpoints were also evaluated in the Gilmore (2006) 81 DNT study discussed above. Despite its shortcomings noted above, the study did find that preputial separation was delayed at 10.8 and 29.8 mg/kg/day. Sperm parameters were not affected, but the California Office of Environmental Health Hazard Assessment (USA) has noted since treatment was stopped at weaning and did not continue through puberty, this study cannot be used to rule out the possibility of adverse effects on male reproduction from endosulfan exposure. 82 Immune effects 56. The ATSDR derived a NOAEL of 0.45 mg/kg/day for immunological effects of Endosulfan, on the basis of a dietary study83 in which male Wistar rats received technical-grade Endosulfan at dietary levels of 0, 5, 10, or 20 ppm, equivalent to 0, 0.45, 0.9, and 1.8 mg/kg/day, and were immunized with tetanus toxin. Rats in the 10 ppm dose group had significantly decreased serum IgG levels at weeks 12, 18, and 22. These rats also had significantly decreased antibody titer to tetanus toxin at weeks 8, 12, 18, and 22. Leukocyte and macrophage migration were also inhibited at weeks 8, 12, 18, and 22. The magnitude of the differences between the 10 ppm rats and the controls increased at each later time point. These rats also had an increased albumin-to-globulin ratio at week 22. Rats in the 20 ppm dose group exhibited similar changes, but to a greater degree. In addition, at weeks 2, 18, and 22, these rats showed an increased albumin-toglobulin ratio, and at 22 weeks, these rats showed a decrease in relative spleen weight. The NOAEL value of 0.45 mg/kg/day was calculated from the 5 ppm group.84 57. “Endosulfan can induce apoptosis in a human T-cell leukemic cell line which may have direct relevance to loss of T cells and thymocytes in vivo.” … “Endosulfan lowered cell viability and inhibited cell growth in a dose- and timedependent manner. DAPI staining was used to enumerate apoptotic cells and we observed that endosulfan at 10–200 AM induced a significant percentage of cells to undergo apoptotic cell death. At 48 h, more than 90% cells were apoptotic with 50 μM of endosulfan.” 85 81 Gilmore RG, Sheets LP, Hoss HE. 2006. A Developmental Neurotoxicity Study with Technical Grade Endosulfan in Wistar Rats. Bayer CropScience LP, Toxicology, Stilwell KS: Report No. 201563; 9/26/06. Can be found in public docket http://www.regulations.gov under document ID no EPA-HQ-OPP-20020262-0058.1. 82 OEHHA. 2008. Revised findings on the health effects of the active ingredient: endosulfan. Office of Environmental Health Hazard Assessment, California Environmental Protection Agency, June 4, 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/memo_findings060408.pdf. 83 Banerjee BD, Hussain QZ. 1986. Effect of sub-chronic endosulfan exposure on humoral and cellmediated immune responses in albino rats. Arch Toxicol 59:279-84. 84 Abadin HG, Chou C-HSJ, Llados FT. 2007. Health effects classification and its role in the derivation of minimal risk levels: Immunological effects. Reg Toxicol Pharmacol 47:249–56. 85 Kannan K, Holcombe RF, Jain SK, Alvarez-Hernandez X, Chervenak R, Wolf RE, Glass J. 2000. Evidence for the induction of apoptosis by endosulfan in a human T-cell leukemic line. Mol Cell Biochem 205:53-66. Annex E information on ENDOSULFAN 16 UNEP/POPS/POPRC.1/4 58. Endosulfan was immunosuppressive and immunotoxic in sheep leukocytes. At a concentration of 10-1 M it caused significant suppression of the metabolic activity of phagocytic cells and decreased spontaneous migration of leukocytes, and at 10-3 M it significantly decreased lymphocytic activation.86 59. In broiler chicks, Endosulfan at 2 ppm (dietary) significantly reduced total leucocytes, T-lymphocytes, B-lymphocytes, macrophages, and caused atrophy and haemorrhage of the thymus gland.87 60. At concentrations of 10-11 to 10-8 M, Endosulfan caused rapid, dose-related release of β–hexosaminidase (a marker for the granules that contain preformed allergic mediators) from human mast cells, and enhanced IgE-mediated release.88 Genotoxicity and mutagenicity 61. The ATSDR concluded “In summary, genotoxicity studies of endosulfan have provided evidence that this compound is mutagenic and clastogenic, and that it induces effects on cell cycle kinetics in two different mammalian species.” 89 62. Both OEHHA 90 and the Scientific Review Panel for California’s Toxic Air Contaminants Program (USA)91 concluded in 2008 that Endosulfan is likely to be genotoxic. 63. Endosulfan and its metabolites (diol, ether, hydroxyether, lactone and sulphate) were genotoxic in Chinese hamster ovary cells and human lymphocytes using the comet assay and mutagenic in Salmonella using the Ames test. There were statistically significant concentration dependent (0.25-10 86 Pistl J, Kovalkovicova N, Holovska V, Legath J, Mikula I. 2003. Determination of the immunotoxic potential of pesticides on functional activity of sheep leukocytes in vitro. Toxicology 188(1):73-81. 87 Garg UK, Pal AK, Jha GJ, Jadhao SB. 2004. Haemato-biochemical and immuno-pathophysiological effects of chronic toxicity with synthetic pyrethroid, organophosphate and chlorinated pesticides in broiler chicks. Int Immunopharmacol 4(13):1709-22. 88 Narita S, Goldblum RM, Watson CS, Brooks EG, Estes DM, Curran EM, Midoro-Horiuti T. 2007. Environmental estrogens induce mast cell degranulation and enhance IgE-mediated release of allergic mediators. Environ Health Perspect 115(1):48-52. 89 ATSDR. 2000. Toxicological Profile for Endosulfan. Agency of Toxic Substances and Disease Registry, Atlanta, USA. http://www.atsdr.cdc.gov/toxprofiles/tp41.html. p 135. 90 OEHHA. 2008. Revised findings on the health effects of the active ingredient: endosulfan. Office of Environmental Health Hazard Assessment, California Environmental Protection Agency, Sacramento. June 4, 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/memo_findings060408.pdf. 91 SRP. 2008. Findings of the Scientific Review Panel on Toxic Air Contaminants on the Proposed Identification of Endosulfan as a Toxic Air Contaminant. Scientific Review Panel on Toxic Air Contaminants, Department of Pesticide Regulation, California Environmental Protection Agency, Sacramento. May 16, 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/srp_finding_end_final.pdf. Annex E information on ENDOSULFAN 17 UNEP/POPS/POPRC.1/4 uM) increases in DNA damage in both the ovary cells and the lymphocytes. It was mutagenic in some strains of Salmonella at concentrations of 1-20 ug/plate.92 64. Endosulfan caused significant DNA damage as determined by increases in tail length in the comet assay, in human lymphocytes in vitro, at concentrations from 0.7 to 1 mg/ml.93 65. Endosulfan was genotoxic in human HepG2 cells. DNA strand breaks were significantly induced by alpha-Endosulfan at concentrations from 2×10-4 M to 1×10-3 M, and by beta-Endosulfan at 1×10-3 M, as detected by the single-cell gel electrophoresis assay.94 66. Endosulfan was genotoxic in the fresh water teleost fish Mystus vittatus at nonlethal concentrations 1/10 of the LC50. Using the comet assay, it caused significant single-strand DNA breaks in gill, kidney and erythrocytes, in a concentration dependent manner at all concentrations (0.5, 1, 2, 4, and 8 ug/l).95 67. Endosulfan caused significant dose-dependent increases in erythrocytic micronuclei and erythrocytic nuclear abnormalities in the blood of gilthead sea bream Sparus aurata L., using micronuclei assays, at concentrations 0.5 and 1 ug/l.96 68. Endosulfan was genotoxic in embryos of the Pacific oyster, Crassostrea gigas, causing DNA strand breaks using the comet assay, in a dose-dependent manner that became statistically significant at the highest dose used, 150 nM.97 69. Endosulfan was genotoxic in the root tip cells of the wetland macrophyte Bidens laevis L (bur marigold, beggars tick) at environmentally relevant concentrations. It interacted with the mitotic spindle at concentrations of 5 ug/l.98 92 Bajpayee M, Pandey AK, Zaidi S, Musarrat J, Parmar D, Mathur N, Serth PK, Dhawan A. 2006. DNA damage and mutagenicity induced by endosulfan and its metabolites. Environ Mol Mutagen 47(9):682-92. 93 Jamil K, Shaik AP, Mahboob M, Krishna D. 2004. Effect of organophosphorus and organochlorine pesticides (monocrotophos, chlorpyriphos, dimethoate, and endosulfan) on human lymphocytes in-vitro. Drug Chem Toxicol 27(2):133-44. 94 Lu Y, Morimoto K, Takeshita T, Takeuchi T, Saito T. 2000. Genotoxic effects of alpha-endosulfan and beta-endosulfan on human HepG2 cells. Environ Health Perspect 108(6):559-61. 95 Sharma S, Nagpure NS, Kumar R, Pandey S, Srivastava SK, Singh PJ, Mathur PK. 2007. Studies on the genotoxicity of endosulfan in different tissues of fresh water fish Mystus vittatus using the Comet assay. Arch Environ Contam Toxicol 53(4):617-23. 96 Neuparth T, Bickham JW, Theodorakis CW, Costa FO, Costa MH. 2006. Endosulfan-induced genotoxicity detected in the Gilthead Seabream, Sparus aurata L., by means of flow cytometry and micronuclei assays. Bull Environ Contam Toxicol 76(2):242-8. 97 Wessel N, Rousseau S, Caisey X, Quiniou F, Akcha F. 2007. Investigating the relationship between embryotoxic and genotoxic effects of benzo[a]pyrene, 17a-ethinylestradiol and endosulfan on Crassostrea gigas embryos. Aquat Toxicol 85:133-42. 98 Perez DJ, Menone ML, Camadro EL, Moreno VJ. 2007. Genotoxicity evaluation of the insecticide endosulfan in the wetland macrophyte Bidens laevis L. Environ Pol 153(3):695-8. Annex E information on ENDOSULFAN 18 UNEP/POPS/POPRC.1/4 70. Endosulfan caused DNA strand breaks in a comet assay on microalgae Karenia mikimotoi at concentrations of 1 ug/l.99 Cancer 71. Endosulfan, as the formulated product Thiodan, “induced malignant neoplasms at all sites in male and female [Osborne-Mendel] rats and in the endocrine organs of male rats. Rats of both sexes developed lymphosarcomas, and female rats had neoplasms of the reproductive system. Endosulfan is carcinogenic for the liver of female mice.” 100 72. Alpha-Endosulfan and beta-Endosulfan “enhanced development of CGTpositive foci in rat liver indicating that it is a potential liver tumour promoter in a similar manner to structurally-related chlorinated cyclodienes”.101 73. Endosulfan is described as a potential carcinogen as a result of its ability to inhibit apoptosis, the generation of reactive oxygen species resulting in oxidative stress, and increased DNA strand breaks.102 74. Through its oestrogenic effects (see below) it has the potential to contribute to cancers of oestrogen-sensitive tissue such as breast tissue. 75. The Scientific Review Panel for California’s Toxic Air Contaminants Program (USA) concluded that although “[e]ndosulfan has not consistently induced tumors in rats and mice… due to its genotoxicity and tumor promoting ability, endosulfan has the potential to be carcinogenic with further studies required.” 103 Endocrine effects 76. The NIOH study of the children in Kerala exposed to Endosulfan previously referred to found endocrine disruption had occurred. It found statistically 99 Akcha F, Arzul G, Rousseau S, Bardouil M. 2008. Comet assay in phytoplankton as biomarker of genotoxic effects of environmental pollution. Mar Environ Res 66(1):59-61. 100 Reuber MD. 1981. The role of toxicity in the carcinogenicity of endosulfan. Sci Total Environ 20(1):2347. 101 Fransson-Steen R, Flodstrom S, Warngard L. 1992. The insecticide endosulfan and its two stereoisomers promote the growth of altered hepatic foci in rats. Carcinogenesis 13(12):2299-303. 102 Antherieu S, Ledirac N, Luzy AP, Lenormand P, Caron JC, Rahmani R. 2007. Endosulfan decreases cell growth and apoptosis in human HaCaT keratinocytes: Partial ROS-dependent ERK1/2 mechanism. J Cell Physiol 213(1):177-86. 103 SRP. 2008. Findings of the Scientific Review Panel on Toxic Air Contaminants on the Proposed Identification of Endosulfan as a Toxic Air Contaminant. Scientific Review Panel on Toxic Air Contaminants, Department of Pesticide Regulation, California Environmental Protection Agency, Sacramento. May 16, 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/srp_finding_end_final.pdf. Annex E information on ENDOSULFAN 19 UNEP/POPS/POPRC.1/4 significant higher prevalence of menstrual disorders particularly longer periods and irregular or excessive flow, as well as statistically significantly higher skin fold thickness in female pre-pubertal and pubertal children, and significantly lower skin fold thickness in males less than 10 years of age. The study found that the levels of luteinizing hormone, progesterone and oestradiol were higher in the exposed children and the levels of testosterone were lower, when comparing for sex and age.104 77. An in vivo study on rats found Endosulfan modulated oestrogen-sensitive genes at the mRNA and protein levels. It caused statistically significant alterations in levels of hormone receptors and complement factor-3 mRNAs in the uteri of ovariectomized rats dosed on three consecutive days with 0.006 mg/kg/day Endosulfan, a non-uterotrophic dose, which mimicked the actions of estradiol. This dose level is 100 times smaller than the NOEL.105 78. “Endosulfan significantly inhibited testicular androgen biosynthesis in adult rats, when fed at 7.5 and 10 mg/kg body weight dose levels, consecutively for 15 and 30 days. No appreciable alterations were apparent in body weights, testicular wet weights, and cytosolic and microsomal protein contents of testis in treated rats. Profound decrease in the levels of plasma gonadotrophins (FSH and LH) along with plasma testosterone and testicular testosterone were observed at both the doses of endosulfan, particularly after the longer exposure of 30 days. Activities of steroidogenic enzymes studied (3 beta- and 17 beta-hydroxysteroid dehydrogenases) were considerably lowered on longer exposure of endosulfan. A significant decrease in the contents/activities of microsomal cytochrome P-450 and related mixed function oxidases (MFOs) in testis of treated rats was also observed, along with a marked inhibition in the activity of cytosolic conjugation enzyme, glutathione-S-transferase at both doses studied. These biochemical changes were reversed when the endosulfan treatment was withdrawn.” However the testicular testosterone remained depressed.106 79. Technical grade Endosulfan and the alpha and beta isomers were found to be oestrogenic at concentrations of 10-25 uM, causing proliferation of human breast cancer oestrogen sensitive MCF7 cells in an E-screen assay.107 104 NIOH. 2003. Final Report of the Investigation of Unusual Illnesses Allegedly Produced by Endosulfan Exposure in Padre Village of Kasargod District (N Kerala). National Institute of Occupational Health, Indian Council for Medical Research, Ahmedabad. p37-38. 105 Varayoud J, Monje L, Bernhardt T, Munoz-de-Toro M, Luque EH, Ramos JG. 2008. Endosulfan modulates estrogen-dependent genes like a non-uterotrophic dose of 17B-estradiol. Repro Toxicol 26(2):138-45. 106 Singh SK, Pandey RS. 1990. Effect of sub-chronic endosulfan exposures on plasma gonadotrophins, testosterone, testicular testosterone and enzymes of androgen biosynthesis in rat. Indian J Exp Biol 28(10):953-6. 107 Soto AM, Chung KL, Sonnenschein C. 1994. The pesticides endosulfan, toxaphene, and dieldrin have estrogenic effects on human estrogen-sensitive cells. Environ Health Perspect 102(4):380-83. Annex E information on ENDOSULFAN 20 UNEP/POPS/POPRC.1/4 80. Alpha-Endosulfan (100 nM) caused concentration dependent oestrogen receptor mediated cell proliferation in BG-1 ovarian cells, as well as upregulation of the ERE-dependent progesterone receptors.108 81. Endosulfan elicited rapid extracellular-regulated kinase activation in pituitary tumour cells, which leads to cell proliferation, in a manner similar to the other oestrogenic substances tested. It showed a bimodal response: it was active at 10-14 M and at 10-8 M, but not at 10-10 M concentrations.109 82. Alpha-Endosulfan was anti-progestogenic in a recombinant yeast based in vitro bioassay, causing significant reduction in progesterone-induced transactivation at 1 uM concentration.110 83. Endosulfan at 10 uM concentrations significantly induced aromatase activity in human choriocarcinoma JEG-3 cells after 24 hr exposure.111 Interactions with other chemicals 84. Like the related organochlorine pesticides Lindane, Aldrin, Dieldrin, and Chlordane, Endosulfan is a GABA antagonist. Therefore, there exists the possibility of cumulative or additive effects resulting from co-exposure to Endosulfan and these pesticides. 85. In rats, simultaneous exposure to Endosulfan and methyl parathion can cause “behavioral alternations” not observed when these pesticides are administered individually. Co-exposed rats performed worse on a water-maze and displayed impaired learning compared to singly-exposed and control animals. These effects were observed in the absence of signs of systemic toxicity.112 86. It has been shown that chickens may be adversely affected by simultaneous exposure to arsenic and Endosulfan more than the exposure to either chemical in isolation.113 108 Wong PS, Matsumura F. 2006. Serum free BG-1 cell proliferation assay: a sensitive method for determining organochlorine pesticide estrogen receptor activation at the nanomolar range. Toxicol In Vitro 20(3):382-94. 109 Bulayeva NN, Watson CS. 2004. Xenoestrogen-induced ERK-1 and ERK-2 activation via multiple membrane-initiated signalling pathways. Environ Health Perspect 112(15):1481-7. 110 Chatterjee S, Kumar V, Majumder CB, Roy P. 2008. Screening of some anti-progestin endocrine disruptors using a recombinant yeast-based in vitro bioassay. Toxicol in Vitro 22(3):788-98. 111 Laville N, Balguerf P, Brion F, Hinfray N, Casellas C, Porcher JM, Ait-Aissa S. 2006. Modulation of aromatase and mRNA by various selected pesticides in the human choriocarcinoma JEG-3 cell line. Toxicology 228(1):98-108. 112 Castillo CG, Montante M, Dufour L, Martínez ML, Jiménez-Capdeville ME. 2002. Behavioral effects of exposure to endosulfan and methyl parathion in adult rats. Neurotoxicol Teratol 24(6):797–804. 113 (a) Aggarwal M, Naraharisetti SB, Sarkar SN, Rao GS, Degen GH, Malik JK. 2008. Effects of subchronic coexposure to arsenic and endosulfan on the erythrocytes of broiler chickens: A biochemical Annex E information on ENDOSULFAN 21 UNEP/POPS/POPRC.1/4 87. Endosulfan and zineb in combination exhibited significantly higher toxicity to human cells than either by itself.114 (c) Environmental fate (provide summary information and relevant references) Chemical/physical properties Persistence 88. The US State of California recently finalized its Risk Characterization Document (RCD) for endosulfan and concluded that: “Both α- and β-endosulfan can be oxidized to endosulfan sulfate via biotic metabolism. Endosulfan sulfate is of comparable toxicity as its parents and more persistent with half-life of 1002148 days, two or more times longer than its parents. Estimated half-lives for αand β-endosulfan in different soils and other environmental conditions ranged 19124 and 42-265 days respectively, and those for the combined toxic residues (αand β-endosulfan plus endosulfan sulfate) ranged from 9 months to 6 years. They all can, when in water, hydrolyze abiotically or biotically to endosulfan diol. Endosulfan diol is more hydrophilic and less toxic. Hydrolysis is favored in neutral to alkaline media. At 250C estimated half-lives of α- and β- endosulfan were 11 and 19 days at pH 7, and 4 and 6 days, respectively, at pH 9. However, at pH 5, they were more than 200 days for both α- and β-endosulfan.” 115 89. US EPA’s revised Ecological Risk Assessment of Endosulfan from 2007 identifies 1336 days as the aerobic soil half-life for total Endosulfan (alpha + beta + sulfate).116 90. Volatilized Endosulfan is not subject to photolysis or abiotic hydrolysis, and the atmospheric half-life of alpha-Endosulfan was estimated to be 1.4 years.117 study. Arch Environ Contam Toxicol [Epub April 29]. (b) Aggarwal M, Naraharisetti SB, Dandapat S, Degen GH, Malik JK. 2008. Perturbations in immune responses induced by concurrent subchronic exposure to arsenic and endosulfan. Toxicology 251(1-3):51-60. 114 Jia Z, Misra HP. 2007. Exposure to mixtures of endosulfan and zineb induces apoptotic and necrotic cell death in SH-SY5Y neuroblastoma cells, in vitro. J Appl Toxicol 27(5):434-6. 115 CDPR. 2008. Endosulfan Risk Characterization Document: Executive Summary. Department of Pesticide Regulation, California Environmental Protection Agency, Sacramento. May 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/tacpdfs/endosulfan/exec_sum.pdf. 116 US EPA. 2007. Addendum to the Ecological Risk Assessment of Endosulfan. October, 31 st, 2008. Available in the public docket at http://www.regulations.gov under docket ID No. EPA-HQ-OPP-20080262-0063. http://www.cdpr.ca.gov/docs/emon/pubs/tac/finaleval/endosulfan.htm. 117 CDPR 2008, op cit. Annex E information on ENDOSULFAN 22 UNEP/POPS/POPRC.1/4 91. The overall persistence and long-range transport potential of the Endosulfan substance family are similar to those of acknowledged POPs, such as aldrin, DDT, and heptachlor. Results also show that the overall persistence and longrange transport potential of the entire substance family, i.e. including the transformation products, are significantly higher than those of the parent compounds alone.118 92. The half-life of Endosulfan in water at pH 5, which is relevant in the Arctic, is >1 year at 220C, persistence increasing with decreasing temperature and therefore likely to be significantly more persistent at < 5 0C.119 MacDonald et al. (2000) note that rates of degradation of pesticides such as endosulfan satisfy the conditions to be called “persistent” because rates of degradation of these compounds in water decrease dramatically as temperature drops to the water temperatures observed in the Arctic.120 How are chemical/physical properties and persistence linked to environmental transport, transfer within and between environmental compartments, degradation and transformation to other chemicals? 93. Studies of Endosulfan application to cotton fields in Australia showed that about 70% of Endosulfan is lost from the cotton field through volatilisation, with only 8.5% remaining on the field one month after spraying; 2% is carried away in run-off, 1% remains in the soil, and the remainder is degraded by plants or microorganisms). Hence approximately 73% of Endosulfan applied, at least in hot/tropical environments, leaves the site of application and is transported in the wider environment.121 94. In a controlled laboratory setting with a constant airflow of 1 m/s at 21-22 oC and 50% relative humidity, 25-30% of Endosulfan applied to soil had volatilized and dissipated within 24 hours. Sixty-four percent dissipated from foliage under the same conditions. Endosulfan sulfate was found to be less volatile, and 118 Becker L, Schenker U, Scheringer M. 2008. Overall Persistence and Long-Range Transport Potential of Endosulfan and its Transformation Products. Submission by Switzerland to the Persistent Organic Pollutants Review Committee, 13 October 2008, Geneva. http://www.sust-chem.ethz.ch/downloads. 119 Mackay N, Arnold D. 2005. Evaluation and Interpretation of Environmental Data on Endosulfan in Arctic Regions. Draft Report for Bayer CropScience. Report Number CEA.107, p 38. 120 Macdonald RW, Barrie LA, Bidleman TF, Diamond ML, Gregor DJ, Semkin RG, Strachan WMJ, Li YF, Wania F, Alaee M, Alexeeva LB, Backus SM, Bailey R, Bewers JM, Gobeil C, Halsall CJ, Harner T, Hoff JT, Jantunen LMM, Lockhart WL, Mackay D, Muir DCG, Pudykiewicz J, Reimer KJ, Smith JN, Stern GA, Schroeder WH, Wagemann R, Yunker MB. 2000. Contaminants in the Canadian Arctic: 5 years of progress in understanding sources, occurrence, and pathways. Sci Total Environ 254(2-3):93-234. 121 Kennedy IR, Sanchez-Bayo F, Kimber SW, Hugo L, Ahmad N. 2001. Off-site movement of endosulfan from irrigated cotton in New South Wales. J Environ Qual 30:683-96. Annex E information on ENDOSULFAN 23 UNEP/POPS/POPRC.1/4 dissipation of Endosulfan from a water surface was slower than from soil or foliage.122 95. Dissipation half-lives for alpha- and beta-Endosulfan were measured at 40 oC in a field study and found to be 12 and 36 hours, respectively. At 29 oC they were 24 and 60 h, respectively.123 96. Endosulfan is subject to regional and long-range atmospheric transport and deposition in colder regions. Endosulfan was found in the air and soil in neotropical montane forests in Costa Rica, as a result of regional transport. Endosulfan was ubiquitous in the air across the country with very high concentrations at some lowland sites (e.g. 2.3 ng/m3), and lesser concentrations in the mountain air. However the reverse was true for residues in the soil with higher residue levels (e.g. 3.175 ng/kg) in the mountain soils. The authors of this study (Daly et al. 2007) explained a process whereby Endosulfan used in lowland agriculture is carried by easterly winds to the downwind mountains; forced atmospheric uplift causes the formation of orographic clouds and subsequent rainfall. The drop in temperature with elevation greatly increases the scavenging by the rain of Endosulfan from the air (only slightly scavenged at the higher temperatures in the lowlands), leading to greater deposition in rainfall and a build up of residues in the soil because of lower evaporation. The authors suggested that the high soil residues in the mountain forest may be a factor in the observed decline in amphibia in the mountains.124 97. LeNoir (1999) observed Endosulfan transport from California’s San Joaquin Valley (USA) to the adjacent Sierra Nevada Mountains during the summer of 1996. One air sample per month (May-September) was collected from each of 3 sites. The western-most site was closest to the agricultural activity in the Valley and at elevation of 200 m. Mean alpha, beta, and sulfate concentrations were 2.3, 4.6, and 0.5 ng/m3, respectively. At the middle site, located at 533 m elevation and 18 km northeast of the first, mean concentrations were 1.09, 0.16, and 0.03 ng/m3. At the western-most site, elevation 1,920 and even further from agricultural activity, mean concentrations were 0.95, and 0.03 ng/m 3, respectively. The two western sites were located within Sequoia National Park (USA). Surface water samples were also collected at several altitudes within the park. For samples collected at elevations from 118 to 2,042 m, alpha-Endosulfan concentrations ranged from 16.96–24.8 ng/m3, and beta from 87.35–140.5 ng/m3. The two samples from above 3000 m had levels of 0.34 and 0.9 ng/m 3 for alpha- and 1.0 and 0.41 ng/m3 for beta-Endosulfan. Temporally, peak Endosulfan concentrations in air and water “correlated roughly with peak application periods 122 CDPR. 2008. Endosulfan Risk Characterization Document, Volume III: Environmental Fate. Department of Pesticide Regulations, California Environmental Protection Agency, May 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/finaleval/endosulfan.htm. 123 CDPR 2008, op cit. 124 Daly G, Lei YD, Teixeira C, Muir DCG, Castillo LE, Wania F. 2007. Accumulation of current-use pesticides in neotropical montane forests. Environ Sci Total 41:118-23. Annex E information on ENDOSULFAN 24 UNEP/POPS/POPRC.1/4 in the [San Joaquin Valley, USA] in summer”, and demonstrate that Endosulfan is transported from the warmer valley and deposited in the cooler, higher altitude Sierra Nevada Mountains (USA).125 98. The US National Parks Service has concluded that “endosulfan contamination by air transport is actually occurring in ENP [Everglades National Park, Florida].” As evidence, the Service cites studies showing Endosulfan in rainwater in the region—levels are highest during the growing season, but it is present year-round—and studies finding Endosulfan in tissue of animals collected far from areas of Endosulfan use. They also note that in the Chesapeake Bay (on the US east coast), a study has found that “from the total annual endosulfan applied to a site, 14% of alpha endosulfan and 90% of beta endosulfan were deposited by rain back into the watershed”.126 99. The Global Air Passive Sampling (GAPS) study carried out over 4 consecutive 3-month periods in 2005 found residues of alpha-Endosulfan in the air at every one of the more than 50 sites tested—from Alert in the Canadian Arctic through Europe, Africa, Asia and Central America, to Chile and Australia in the south (see Table 1)—including in a number of urban areas. The annual geometric mean concentration was higher for Endosulfan (82 pg.m -3) than any other persistent organic pollutant. “Exceptionally high concentrations (pg.m -3) of [sum] Endosulfan were observed at agricultural sites in Bahia Blanca, Argentina (~19,000) during period 1, Delhi, India during periods 3 (~11,000) and 4 (~4,000) and at a rural site in Accra, Ghana (~5,200) during period 2.” … “Endo1, the dominant congener, accounted for 82% of total, with 16% associated with endo2 and 2% associated with Endo SO4.” … “Concentrations range from less than 100 pg.m-3 at background sites to several thousand pg.m -3. The occurrence of endosulfan in remote and polar sites demonstrates its ability to travel long distances in the environment.”127 Table 1: Residues found in GAPS study Country Location Site type Argentina India Korea Ghana France Brazil Bahia Blanca Delhi Seoul Accra Paris Indaiatuba Agricultural Agricultural Urban Rural Urban Background pg.m-3 18,739 10,898 5,407 5,198 4,520 2,822 Sampling period 1 2 3 2 2 2 125 LeNoir JS, McConnell LL, Fellers GM, Cahill TM, Seiber JN. 1999. Summertime transport of current use pesticides from California’s Central Valley to the Sierra Nevada Mountain range, USA. Environ Toxicol Chem 18(12):2715–22. 126 NPS. 2008. Comments on Petition to Revoke All Tolerances for Endosulfan. U.S. National Parks Service. October 29, 2008. Available in the public docket at http://www.regulations.gov under Document ID No. EPA-HQ-OPP-2008-0615-0041.1. 127 Pozo K, Harner T, Lee SC, Wania F, Muir DCG, Jones KC. 2008. Seasonally resolved concentrations of persistent organic pollutants in the global atmosphere from the first year of the GAPS study. Environ Sci Technol [Epub December 10]. Annex E information on ENDOSULFAN 25 UNEP/POPS/POPRC.1/4 Canary Islands Turkey Spain Canada Canada USA Norway USA Telde Ismir Barcelona Whistler Alert Barrow Ny-Alesund St Lawerence Is Background Urban Urban Background Polar Polar Polar Polar 2,441 1,823 1,738 129 63 55 37 7 1 3 1 1 1 4 1 3,4 100. An earlier pilot study carried out over 2002-2004 found higher levels at Whistler Mountain in Canada (321 pg.m-3). According to the study’s authors, “India is currently the world’s largest consumer of endosulfan which may partly explain the elevated concentrations at Whistler Mountain during period 4 when advective trans-Pacific flow was greater”.128 101. A study by Tuduri et al. (2006) concluded that Endosulfan is “one of the most abundant and ubiquitous organochlorine pesticides in the North American atmosphere today.”129 102. “Long-range atmospheric transportation was evidenced by widely distributed endosulfan in a pristine environment, the Arctic region, where endosulfan air concentrations ranged 4.2-4.7 pg/m3 during 1993-1997 (Patton, et al., 1989; Halsall, et al., 1998; Hung, et al., 2002). In the eastern Arctic, endosulfan concentrations in air were reported between 1–10 pg/m3 (De Wit, et al., 2002; Konoplev, et al., 2002).”130 103. Residues of organochlorine pesticides were collected at the Canadian high Arctic site of Alert, Nunavut over a 5-year period 1992-1997. “Several compounds showed a general decline over the 5 years of study, including cisand trans-chlordane and R- and γ-HCH. Endosulfan I, on the other hand, 128 Harner T, Pozo K, Gouin T, Macdonald A-M, Hung H, Cainey J, Peters A. 2006. Global pilot study for persistent organic pollutants (POPs) using PUF disk passive air samplers. Environ Poll 144:445-52. 129 Tuduri L, Harner T, Blanchard P, Li Y-F, Poissant L, Waite DT, Murphy C, Belzer W. 2006. A review of currently used pesticides (CUPS) in Canadian air and precipitation: Part 1: lindane and endosulfans. Atmos Environ 40:1563-78. 130 CDPR. 2008. Endosulfan Risk Characterization Document, Volume III: Environmental Fate. Department of Pesticide Regulations, California Environmental Protection Agency, May 2008. http://www.cdpr.ca.gov/docs/emon/pubs/tac/finaleval/endosulfan.htm. Citing: (a) Patton GW, Hinckley DA, Walla MD, Bidleman TF. 1989. Airborne organochlorines in the Canadian High Arctic. Tellus 41B:243-255. (b) Halsall CJ, Bailey R, Stern GA, Barrie LA, Fellin P, Muir DCG, Rosenberg B, Rovinsky FY, Kononov EY, Pastukhov B. 1998. Multi-year observations of organohalogen pesticides in the Arctic atmosphere. Environ Poll 102:51-62. (c) Hung H, Halsall CJ, Blanchard P, Li H, Fellin P, Stern G, Rosenberg B. 2002. Temporal trends of organochlorine pesticides in the Canadian Arctic atmosphere. Environ Sci Technol 36:862-868. (d) De Wit CA, Fisk AT, Hobbs KE, Muir DCG. 2002. Levels, trends and effects of Persistent Organic Pollutants (POPs) in the Arctic environment. 2nd AMAP International Symposium on Environmental Pollution in the Arctic, Rovaniemi 1-3 October 2002. (e) Konoplev A, Fellin P, Li H, Blanchard P, Hung H, Samsonov D, Stern G. 2002. Monitoring of POPs in Arctic ambient air: Initial results from Anderma (Russia) and preliminary assessment. 2nd AMAP International Symposium on Environmental Pollution in the Arctic, Rovaniemi 1-3 October 2002. Annex E information on ENDOSULFAN 26 UNEP/POPS/POPRC.1/4 appeared to be increasing”.131 104. “Endosulfan was found as a widely distributed currently-used pesticide in the polar atmosphere.” Endosulfan was first measured in Arctic air in 1986-87132 and with a general increasing trend measured over the long term from 1993-2005 at Alert in the Canadian Arctic.133 In a 2002 paper by Hung, concentrations of Endosulfan in air measured in the Canadian Arctic are exceeded only by HCH and HCB.134 “Arctic marine fog was sampled in the Bering and Chukchi Seas, and for the first time, several currently-used pesticides (chlorpyrifos, trifluralin, metolachlor, chlorothalanil, terbufos, and endosulfan) were detected at concentrations several times higher than in adjacent waters or ice.” 135 105. According to the Canadian Arctic Contaminants Assessment Report: “Unlike most other organochlorine pesticides, concentrations of endosulfan in Arctic air have not declined over the last 7 years.”136 106. In 2005 Braune et al. had also stated that “Chlorobenzenes and endosulfan were among the few OCs [organochlorines] to show increases during this period (1997-2005) while ∑HCH remained relatively constant in most species.” 137 Researchers reported 0.4-8.8 pg/l alpha-Endosulfan and 0.1-7.8 beta-Endosulfan on the scientific expedition from the Chukchi Sea across the Polar Cap. Unlike other organochlorine contaminants, levels of the Endosulfans were higher in the Chukchi Sea than in the northern Canada Basin. Alpha-Endosulfan is routinely found in air at the Alert, Tagish, and Dunay monitoring stations, with annual means of 2-5 pg m3.138 131 Hung H, Halsall CJ, Blanchard P, Li HH, Fellin P, Stern G, Rosenberg B. 2002. Temporal trends of organochlorine pesticides in the Canadian Arctic atmosphere. Environ Sci Technol 36(5):862-8. 132 German Federal Environmental Agency, 2007. Endosulfan Draft Dossier prepared in support of a proposal of endosulfan to be considered as a candidate for inclusion in the CLRTAP Protocol on POPs. 133 Hung H. 2008. Hayley Hung, Environment Canada, Personal communication with Pamela Miller, October 7, 2008. 134 Hung H, Halsall CJ, Blanchard P, Li HH, Fellin P, Stern G, Rosenberg B. 2002. Temporal trends of organochlorine pesticides in the Canadian Arctic atmosphere. Environ Sci Technol 35(5):862-8. 135 Chernyak SM, Rice CP, McConnell LL. 1996. Evidence of currently used pesticides in air, ice, fog, seawater, and surface microlayer in the Bering and Chukchi Seas. Mar Poll Bull 32(5):410-19. 136 NCP. 2006. Canadian Arctic Contaminants Assessment Report II, Sources, Occurrence, Trends, and Pathways in the Physical Environment. Northern Contaminants Programme, Indian and Northern Affairs Canada, Ottawa. http://www.ainc-inac.gc.ca/nth/ct/ncp/pubs/phy/phy-eng.pdf. 137 Braune BM, Outridge PM, Fisk AT, Muir DCG, Helm PA, Hobbs K, Hoekstra PF, Kuzyk ZA, Kwan M, Letcher RJ, Lockhart WL, Norstrom RJ, Stern GA, Stirling I. 2005. Persistent organic pollutants and mercury in marine biota of the Canadian Arctic: an overview of spatial and temporal trends. Sci Total Environ 351-352: 4-56. 138 Macdonald RW, Barrie LA, Bidleman TF, Diamond ML, Gregor DJ, Semkin RG, Strachan WMJ, Li YF, Wania F, Alaee M, Alexeeva LB, Backus SM, Bailey R, Bewers JM, Gobeil C, Halsall CJ, Harner T, Hoff JT, Jantunen LMM, Lockhart WL, Mackay D, Muir DCG, Pudykiewicz J, Reimer KJ, Smith JN, Stern GA, Schroeder WH, Wagemann R, Yunker MB. 2000. Contaminants in the Canadian Arctic: 5 years of progress in understanding sources, occurrence, and pathways. Sci Total Environ 254(2-3):93-234. Annex E information on ENDOSULFAN 27 UNEP/POPS/POPRC.1/4 107. In 2008 Jantunen reported levels of alpha-Endosulfan as follows: Lake Superior, August 2005, air average 20+17 pg/m3 (range 4.8-53), water average 12+5 (range 6-20); North Shore of Labrador, Hudson Bay and Churchill Manitoba, August 2007, air average 3.4+1.2 pg/m3 (range 1.05-5); Canadian Archipelago, Summer 1999, air average 6.5+3.7 pg/m3 (range 1.4-12.5), water average 12+11 pg/L (range 2.2-19).139 108. Endosulfan, like other POPs, has a marked tendency to deposit out of the air (cold condensation) in remote environments at high latitudes and at high elevations. This is caused by low temperatures and efficient scavenging from the atmosphere, by snow, of both particle-bound and gas-phase pesticides.140 141 109. Evidence that Endosulfan arriving in the Arctic, Antarctic, and high mountains by long-range atmospheric transport then deposits out is provided by findings of residues of Endosulfan in the snow, ice, water, soil and biota of these regions—and these findings are summarised in Section (e) Exposure in local areas – as a result of long-range environmental transport. 110. Endosulfan is more easily deposited onto water than it is onto ice, and it is expected that as the ice in the Arctic—presumably also the Antarctic—diminishes with increasing global temperatures, the deposition of Endosulfan in polar waters will increase and hence become more available to plants and animals in the marine food-web.142 Bio-concentration or bio-accumulation factor, based on measured values (unless monitoring data are judged to meet this need) 111. Kelly & Gobas (2003) 143 and Kelly et al. (2007) 144 proposed that biomagnification of Endosulfan (particularly the beta isomer) is greater in terrestrial food chain than the marine food chain, because it has a high log which is of greater importance than the Kow in air-breathing animals. A high causes slow respiratory elimination. the the K oa Koa 139 Jantunen L. 2008. Liisa Jantunen, Environment Canada. Personal Communication with Pamela Miller, September 29, 2008. 140 Hageman KJ, Simonich SL, Campbell DH, Wilson GR, Landers DH. 2006. Atmospheric deposition of current-use and historic-use pesticides in snow at national parks in the western United States. Environ Sci Technol 40:3174-80. 141 Daly G, Lei YD, Teixeira C, Muir DCG, Castillo LE, Wania F. 2007. Accumulation of current-use pesticides in neotropical montane forests. Environ Sci Total 41:118-23. 142 NCP. 2003. Canadian Arctic Contaminants Assessment Report II: Highlights. Northern Contaminants Programme, Indian and Northern Affairs Canada, Ottawa. http://www.aincinac.gc.ca/nth/ct/ncp/pubs/hig/hil-eng.asp. 143 Kelly BC, Gobas FAPC. 2003. An arctic terrestrial food-chain bioaccumulation model for persistent organic pollutants. Environ Sci Technol 37(13):2966-74. 144 Kelly BC, Ikonomou MG, Blair JD, Morin AE, Gobas FAPC. 2007. Food web-specific biomagnification of persistent organic pollutants. Science 317:236-9. Annex E information on ENDOSULFAN 28 UNEP/POPS/POPRC.1/4 log Koa alpha-Endosulfan = 10.29 log Koa beta-Endosulfan = 10.29 log Koa Endosulfan sulphate = 5.18 112. Armitage & Gobas et al. (2008)145 concluded that chemicals with a log Kow between 1.75 and 12, and a log Koa > 5.25 have the potential to bioaccumulate in air-breathing organisms. 113. Kelly & Gobas (2003) 146 established predicted biomagnification factors (BMFs) for beta-Endosulfan in male wolves at various ages, showing significantly higher biomagnification than found in the aquatic food chain even at 1.5 years, and increasing considerably with age—refer Table 2. Table 2: BMFs for beta-Endosulfan in male wolves 1.5 years 2.25 years 13.1 years BMF 5.3 17.9 39.8 114. Kelly et al. (2007)147 summarised residues of Endosulfan found in the Arctic food web in Hudson’s Bay, 1999-2002, to illustrate bioaccumulation especially of beta-Endosulfan in beluga, a small arctic whale that feeds mainly on fish (units are ug/kg lipid equivalent, geometric means)—refer Table 3. Table 3: Endosulfan residues in Arctic food web (ug/kg lipid equivalent, geometric means) species alpha-Endosulfan beta-Endosulfan Endosulfan sulphate lichen 0.03 sediment 0.16 0.33 0.16 cod (B. saida) 2.91 salmon 0.41 0.85 0.18 beluga (m) 12.56 0.86 beluga (f) 4.87 0.58 ringed seals (f) 3.02 0.19 ringed seals (m) 0.30 2.26 0.32 eider ducks 2.32 scotors 0.87 115. Kelly et al. (2007) then showed that, although the less hydrophobic compounds (Kow <5) such as alpha-, beta-, and gamma-HCH (Kow = 103.8), tetrachlorobenzenes (Kow = 104.1) and Endosulfans (Kow = 103.7) did not biomagnify in the piscivorous food web, they have a high degree of biomagnification in the lichen-caribou-wolf food chain and in air breathing organisms of the marine mammalian food web.148 145 Armitage JM, Gobas FAPC. 2008. A terrestrial food-chain bioaccumulation model for POPs. Environ Sci Technol 41:409-25. 146 Kelly BC, Gobas FAPC. 2003. An arctic terrestrial food-chain bioaccumulation model for persistent organic pollutants. Environ Sci Technol 37(13):2966-74. 147 Kelly BC, Ikonomou MG, Blair JD, Morin AE, Gobas FAPC. 2007. Food web-specific biomagnification of persistent organic pollutants. Science 317:236-9. 148 Kelly BC, Ikonomou MG, Blair JD, Morin AE, Gobas FAPC. 2007. Food web-specific biomagnification of persistent organic pollutants. Science 317:236-9. Annex E information on ENDOSULFAN 29 UNEP/POPS/POPRC.1/4 Table 4: Beta-Endosulfan: biomagnification factors (BMF ) species BMF reptile 4.9 amphibian 11 seabird 10 terrestrial herbivore 2.5 terrestrial carnivore 28 marine mammal 22 human 23 116. Mackay & Arnold (2005) reported measured bioaccumulation factor (BAF) values for a number of Arctic species ranged from 3.4 x 10 3 to 2.6 x 107. It is postulated that low temperatures of the Arctic may increase bioaccumulation by reducing metabolism potential. The authors state (p 124) that “Such an influence could account for differences between bioconcentration profiles observed under laboratory conditions (BCF: 200-3700), typically measured at 20-250C, and ambient Arctic conditions”.149 117. Mackay & Arnold (2005, p89) stated that “Although endosulfan is not expected to biomagnify because of its relatively short half-life in biota, there are apparent increases in α-endosulfan from prey to predator within each food web particularly from fish to seals.” They also noted, on p 29, “As with the southern Beaufort Sea food web, there is a significant increase in α-endosulfan concentration with trophic level (r2 = 0.44, p = 0.34).” The BMFs for ringed seal to cod were > 1 for all locations, except the White Sea, and as high as 22.7 for Barrow, Alaska. Overall mean BMFs for alpha-endosulfan were 10.2 for fish to marine mammals, and cross the threshold of concern, with a high degree of uncertainty.150 118. Mackay & Arnold (2005)151 concluded that the trophic magnification factor for alpha-Endosulfan, if marine mammals are included in the food web, is >1 in the Southern Beaufort Sea and Amundsen Gulf food webs. This value is higher than for chlordane, lindane and similar to alpha-HCH and DDE. 119. US EPA (2007d) calculated a BMF of 7 for male beluga and 3 for female beluga.152 120. Menone et al. (2000)153 found residues of Endosulfan sulfate in the liver, gonads, fat and muscle of fish from a coastal lagoon in Argentina, at levels 149 Mackay N, Arnold D. 2005. Evaluation and Interpretation of Environmental Data on Endosulfan in Arctic Regions. Draft Report for Bayer CropScience Report Number CEA.107. 150 Mackay N, Arnold D. 2005. Evaluation and Interpretation of Environmental Data on Endosulfan in Arctic Regions. Draft Report for Bayer CropScience Report Number CEA.107. 151 Mackay & Arnold 2005, op cit. 152 US EPA. 2007. Appendix 1 to Addendum. Environmental Fate and Ecological Risk Assessment of Endosulfan. Office of Prevention, Pesticides, and Toxic Substances. http://www.regulations.gov. Annex E information on ENDOSULFAN 30 UNEP/POPS/POPRC.1/4 ranging up to 0.018 ug/kg of tissue. They calculated a BMF of 4.02, higher than that for DDT. 121. Lanfranchi et al. (2006) found Endosulfan biomagnified in striped weakfish also in Argentina, with higher concentrations of beta-Endosulfan in adult liver tissue than in juvenile liver tissue. The BMFs for adult males were 3.6 for betaEndosulfan, 2.3 for alpha-Endosulfan and 0.9 for Endosulfan sulfate.154 122. Bioconcentration of Endosulfan may be occurring in freshwater fish in Ghana: Endosulfan levels in fish (up to 0.42 ug/kg) were, on average, 10 times those found in water samples, although the mean level in the sediments was about 14 times the levels measured in fish.155 123. Bioaccumulation has been found in plants: a BCF of 30.9 was found for Endosulfan sulfate in bulrushes from a lake in Argentina, which appear to have sequestered it from the sediment. This BCF was significantly higher than those for other POPs such as DDT (1.1), Chlordane (2.1), Dieldrin (2.1), and Heptachlor (3.8), with the exception of HCH (61.1).156 124. An analysis of airborne pollutants in the western national parks of the USA, carried out from 2002 to 2007, found evidence of the bioaccumulation of Endosulfan in vegetation, the degree of accumulation increasing with forest productivity and proximity to sources of Endosulfan. The mean level of total Endosulfan in two-year-old needles of White Fir (7573 ug/kg lipid) was 3 times higher than the levels in one-year-old needles (2448 ug/kg). The degree of bioaccumulation varies between species with firs accumulating substantially higher concentrations than pines. The coniferous forests of the western United States and Alaska are estimated to be removing between 1,280 and 7,210 kg of Endosulfan from the air annually, amounting to about 2% of the USA’s annual usage. There was no estimation of how much other vegetation types might also be accumulating, but there were significantly higher levels of Endosulfan in some lichen species than in the conifers (nearly 6 times higher).157 153 Menone ML, Aizpun de Moreno JE, Moreno VJ, Lanfranchi AL, Metcalfe TL, Metcalfe CD. 2000. PCBs and organochlorines in tissues of silverside (Odontesthes bonariensis) from a coastal lagoon in Argentina. Arch Environ Contam Toxicol 38:202-8. 154 Lanfranchi AL, Menone ML, Miglioranza KSB, Janiot LJ, Aizpun JE, Moreno VJ. 2006. Striped weakfish (Cynoscoon guatucupa): a biomonitor of organochlorine pesticides in estuarine and near-coastal zones. Mar Poll Bull 52:74-80. 155 Darko G, Akoto O, Oppong C. 2008. Persistent organochlorine pesticide residues in fish, sediments and water from Lake Bosomtwi, Ghana. Chemosphere 72:21-4. 156 Miglioranza KS, de Moreno JE, Moreno VJ. 2004. Organochlorine pesticides sequestered in the aquatic macrophyte Schoenoplectus californicus (C.A. Meyer) Sojak from a shallow lake in Argentina. Water Res 38(7):1765-72. 157 Landers DH, Simonich SL, Jaffe DA, Geiser LH, Campbell DH, Schwindt AR, Schreck CB, Kent ML, Hafner WD, Taylor HE, Hageman KJ, Usenko S, Ackerman LK, Schrlau JE, Rose NL, Blett TF, Erway MM. 2008. The Fate, Transport, and Ecological Impacts of Airborne Contaminants in Western National Parks (USA). EPA/600/R-07/138. U.S. Environmental Protection Agency, Office of Research and Development, NHEERL, Western Ecology Division, Corvallis, Oregon. Annex E information on ENDOSULFAN 31 UNEP/POPS/POPRC.1/4 125. Leeks grown on an organic farm in Argentina, and not treated with Endosulfan, were found to contain residues of Endosulfan. 158 Samples were taken at 15, 59, and 210 days of growth. The residues in the roots were believed to have bioaccumulated from the soil, with the highest bioaccumulation factor being for Endosulfan sulphate in the early stages of growth. Residues in the soil were thought to have resulted from atmospheric deposition and/or surface run-off from neighbouring farms. The Root Bioaccumulation Factors were calculated as pesticide concentration in plant dry mass divided by pesticide concentration in soil dry mass, as follows: Table 5: Root Bioaccumulation Factors for leek 15 days 59 days 210 days alpha-Endosulfan 9.1 0.9 2.8 beta-Endosulfan 3.9 1.2 2.8 Endosulfan sulfate 20.1 8.8 11.6 These were calculated on the basis of the following residue levels: Table 6: residues of endosulfan in leek (ng/g dry weight) soil rhizosphere rhizosphere 59 days 210 days alpha-Endosulfan 0.08 0.01 0.04 beta-Endosulfan 0.04 0.2 0.2 Endosulfan sulfate 16.0 7.1 11.9 root 15 days 0.7 1.4 321.9 root 59 days 0.1 0.4 141.0 root 210 days <DL 1.0 185.4 (d) Monitoring data (provide summary information and relevant references) Human breast milk 126. Alpha-Endosulfan was found in breastmilk fat of 80% of women sampled in rural Indonesia, with concentrations ranging from <0.01 to 0.02 mg/kg milk fat.159 127. In a study of breast milk from healthy women in two areas of Southern Spain, one in an area of intensive agriculture, the other urban, 80% of urban and 61.1% of rural samples contained alpha-Endosulfan. The maximum level of 0.87 ng/ml alpha and 26.89 ng/ml beta was found in the rural women. The frequency of detection was lower for colostrum and it was mainly the beta isomer found – in 158 Gonzalez M, Miglioranza KS, Aizpun De Moreno JE, Moreno VJ. 2003. Organochlorine pesticide residues in leek (Allium porrum) crops grown on untreated soils from an agricultural environment. J Agric Food Chem 51(17):5024-9. 159 Burke ER, Holden AJ, Shaw IC. 2003. A method to determine residue levels of persistent organochlorine pesticides in human milk from Indonesian women. Chemosphere 50(4):529-35. Annex E information on ENDOSULFAN 32 UNEP/POPS/POPRC.1/4 28.5% of urban samples and 25% of rural samples, with the maximum level of 24.8 ng/ml found in urban women.160 128. In a study of 60 breast milk samples from 20 Egyptian governates, the mean level of alpha-Endosulfan was 4.84 ppb.161 129. Residues of Endosulfan were found in 60% of pregnant women in a survey in Delhi, India, with maximum levels of 6.9 ug/ml in maternal blood and 5.9 ug/ml in cord blood, with the mean values (3.7 and 2.27) indicating a 60% transfer from mothers to newborns.162 130. A mean level of 363 ug/l (range 0-763 ug/l) of Endosulfan in breast milk in Bhopal, India, in women who were not occupationally exposed to it, resulted in infants consuming 8.6 times more Endosulfan than the WHO Acceptable Daily Intake (ADI).163 Human placenta, cord blood and follicular tissue 131. A study of Danish and Finish women found mean levels of Endosulfan of 7.41 ng/g lipid (Danish) and 7.3 ng/g (Finnish) in breast milk, and 2.28 ng/g (Danish) and 2.52 ng/g (Finnish) in placental tissue. “Despite a lower burden, transplacental exposure of the developing foetus may still be more critical with regard to physical development and cognitive functioning of the child than postnatal exposure via breast milk.”164 132. A study of 130 women in Denmark found alpha-Endosulfan in 100% of samples of breast milk, with a maximum level of 22.66 ng/g lipid (mean 6.66-6.95 ng/g).165 160 Campoy C, Jimenz M, Olea-Serrano MF, Moreno-Frias M, Canabate F, Olea N, Bayes R, Molina-Font JA. 2001. Analysis of organochlorine pesticides in human milk: preliminary results. Early Hum Devel 65(s2):S183-90. 161 Saleh M, Kamel A, Ragab A, El-Baroty G, El-Sebae AK. 1996. Regional distribution of organochlorine insecticide residues in human milk from Egypt. J Environ Sci Health B 31(2):241-55. 162 Pathak R, Suke SG, Ahmed RS, Tripathi AK, Guleria K, Sharma CS, Makhijani SD, Mishra M, Banerjee BD. 2008. Endosulfan and other organochlorine pesticide residues in maternal and cord blood in North Indian population. Bull Environ Contam Toxicol 81(2):216-9. 163 Sanghi R, Pillai MK, Jayalekshmi TR, Nair A. 2003. Organochlorine and organophosphorus pesticide residues in breast milk from Bhopal, Madhya Pradesh, India. Hum Exp Toxicol 22(2):73-6. 164 Shen H, Main KM, Virtanen HE, Damgaard IN, Haavisto A-M, Kaleva M, Boisen KA, Schmidt IM, Chellakooty M, Skakkebaek NE, Toppari J, Schramm K-W. 2007. From mother to child: investigation of prenatal and postnatal exposure to persistent bioaccumulating toxicants using breast milk and placenta biomonitoring. Chemosphere 67:S256-62. 165 Damgaard IN, Skakkebaek NE, Toppari J, Virtanen HE, Shen H, Schramm KW, Petersen JH, Jensen TK, Main KM, Nordic Cryptorchidism Study Group. 2006. Persistent pesticides in human breast milk and cryptorchidism. Environ Health Perspect. 114(7):1133-8. Annex E information on ENDOSULFAN 33 UNEP/POPS/POPRC.1/4 133. In a study of 72 pregnant women giving birth by caesarean section in southern Spain, alpha-Endosulfan was found in 61% of samples of maternal serum and cord blood. The levels found were: maternal adipose, alphaEndosulfan (max 334.18 ng/g fat, mean 75.46 ng/g); maternal serum, betaEndosulfan (max 201.57 ng/g, mean 76.38 ng/g); cord blood, beta-Endosulfan (max 299.48 ng/g, mean 66.05 ng/g).166 134. A study of 32 urban pregnant women in Japan found Endosulfan (alpha + beta) in 90% of maternal serum and 70% of umbilical cord tissue but not in cord serum. The maximum levels found in maternal serum were 1,100 pg/g lipid (mean = 380 pg/g), and in umbilical cord tissue 9,400 pg/g lipid (mean = 2,090 pg/g).167 135. In a study of 149 women in southern Spain, a range of Endosulfan isomers and metabolites were found in various human tissues. In breast milk Endosulfan ether was found in 100% of samples and at the highest level (57.58 ng/m). Alpha-Endosulfan, beta-Endosulfan and Endosulfan sulfate were all found in adipose tissue (max = 944.1 ng/g fat alpha), placental tissue (max = 150 ng/g beta), umbilical cord blood (max = 60.25 ng/ml alpha), and breast milk (max= 26.89 ng/ml beta). Mean residue levels were 6.11 ng/ml (alpha-Endosulfan + beta-Endosulfan) in umbilical cord blood, and 7.74 in placental tissue.168 136. In a study of 21 females attending an in vitro fertilisation programme in Canada, Endosulfan sulfate was found in the follicular fluid of one subject.169 Human adipose tissue 137. A study of 200 postmenopausal women in Southern Spain found Endosulfan in the serum of 96% of women and in adipose tissue of 78%. “Endosulfans I and II and their metabolites followed DDTs in the frequency of their presence in adipose tissue and serum samples but were found at lower concentrations. Among endosulfan metabolites, endosulfan-ether was the most predominant compound in both adipose tissue (68%) and serum (86%) samples.” The maximum levels of total Endosulfan found were 417.59 ng/g lipid in adipose 166 Jimenz Torres M, Campoy Folgoso C, Canabate Reche F, Rivas Velasco R, Cerrillo Garcia I, Mariscal Arcas M, Olea-Serrano F. 2006. Organochlorine pesticides in serum and adipose tissue of pregnant women in Southern Spain giving birth by cesarean section. Sci Total Environ 372(1):32-8. 167 Fukata H, Omori M, Osada H, Todaka E, Mori C. 2005. Necessity to measure PCBs and organochlorine pesticide concentrations in human umbilical cords for fetal exposure assessment. Environ Health Perspect 113:297-303. 168 Cerrillo I, Granada A, Lopez-Espinosa MJ, Olmos B, Jimenez M, Cano A, Olea N, Fatima Olea-Serrano M. 2005. Endosulfan and its metabolites in fertile women, placenta, cord blood, and human milk. Environ Res 98(2):233-39. 169 Younglai EV, Foster WG, Hughes EG, Trim K, Jarrell JF. 2002. Levels of environmental contaminants in human follicular fluid, serum, and seminal plasma of couples undergoing in vitro fertilization. Arch Environ Contam Toxicol 43(1):121-26. Annex E information on ENDOSULFAN 34 UNEP/POPS/POPRC.1/4 tissue (mean 21.37 ng/g), and 210.99 ng/ml in serum (mean 8.85 ng/ml). 170 Human blood 138. In a study of 220 young males in southern Spain, “residues of endosulfans were detected in all serum samples. Detectable concentrations of endosulfan I and II and metabolites endosulfan-diol, and -sulfate were found in the samples. Endosulfan-diol was the most frequently detected metabolite (92%) followed by alpha endosulfan (80%). Among endosulfans, endosulfan-diol showed the highest concentration (15.39+14.87 ng/mL).” The highest concentration of total Endosulfan was 145.55 ng/ml, the median was 18.66 ng/ml.171 139. In a study of organochlorine pesticides in the serum of 160 students from Coimbra, Portugal over the period 1997-2001, Endosulfan sulfate, p,p’-DDE, o,p’DDT, and p,p’-DDD were the most frequently identified residues (87.5%). “Endosulfan sulfate presented the highest mean level, 42.6 ug/l, with concentrations ranging from undetected to 1295.5 ug/l.”172 140. In a study of cacao farmers in southwestern Nigeria, 29% had residues of Endosulfan in their serum, with a mean level of 0.033 mg/kg.173 (e) Exposure in local areas (provide summary information and relevant references) - general Air Regionally transported 141. In Canada Endosulfan has been measured in the air in both agricultural areas and in so-called receptor sites demonstrating regional atmospheric transport, including in the Great Lakes Basin, the City of Toronto, the Fraser Valley in British Columbia, Prince Edward Island, Quebec, Ontario and Saskatchewan. 100% of air samples collected at 5 sites across Canada in the 170 Botella B, Crespo J, Rivas A, Cerrillo I, Olea-Serrano MF, Olea N. 2004. Exposure of women to organochlorine pesticides in Southern Spain. Environ Res 96(1):34-40. 171 Carreno J, Rivas A, Granada A, Lopez-Espinosa MJ, Mariscal M, Olea N, Olea-Serrano F. 2007. Exposure of young men to organochlorine pesticides in Southern Spain. Environ Res 103:55-61. 172 Lino CM, da Silveira IN. 2006. Evaluation of organochlorine pesticides in serum from students in Coimbra, Portugal: 1997-2001. Environ Res 102:339-51. 173 Sosan MB, Akingbohungbe AE, Ojo IAO, Durosinmi MA. 2008. Insecticide residues in the blood serum and domestic water source of cacao farmers in Southwestern Nigeria. Chemosphere 72(5):781-4. Annex E information on ENDOSULFAN 35 UNEP/POPS/POPRC.1/4 summer of 2003 contained Endosulfan, at high levels of 5.71 ng/m 3 alphaEndosulfan.174 142. Alpha-Endosulfan was present in 100% of air samples taken on the campus of the University of Maryland beside the Choptank River, Chesapeake Bay over a 7-month period Apr-Nov, with a maximum concentration of 0.68 ng/m 3. The Endosulfan was thought to come from sources outside the Choptank River watershed area.175 143. Regional transport of Endosulfan has been identified in China and over the Yellow Sea. The beta isomer was found, at levels up to 0.025 ng/m 3, in all 9 dayand night-time samples taken at the Ocean University of China, which is in an urban setting in Qingdao on the Yellow Sea coast. 176 High concentrations of Endosulfan have also been reported in Guangzhou and Hong Kong and are thought to originate in agricultural areas of East China where it is used in cotton fields, and to have been carried from there by the winter monsoon. Levels of alpha-Endosulfan at a suburban site in Guangzhou were as high as 2.5 ng/m 3 and in urban Hong Kong 0.84 ng/m 3.177 The air around Lake Taihu contained residues of alpha-Endosulfan up to 0.888 ng/m3,178 with an estimated deposition rate of 25 ng/m2/day in summer179 indicating that it is rapidly moving out of the air and into the Lake. 144. In Chile alpha-Endosulfan was found in a concentration gradient that decreased from 0.099 ng/m3 in the north to 0.035 ng/m3 in the south.180 Transported to Mountains 145. Endosulfan has been found in the air around a number of mountains. Temperate mountains in particular experience effective upslope air movement 174 Yao Y, Tuduri L, Harner T, Blanchard P, Waite D, Poissant L, Murphy C, Belzer W, Aulagnier F, Li YF, Sverko E. 2006. Spatial and temporal distribution of pesticide air concentrations in Canadian agricultural regions. Atmos Environ 40:4339-51. 175 Kuang Z, McConnell LL, Torrents A, Meritt D, Tobash S. 2003. Atmospheric deposition of pesticides to an agricultural watershed of the Chesapeake Bay. J Environ Qual 32(5):1611-22. 176 Lammel G, Ghim Y-S, Grados A, Gao H, Huhnerfuss H, Lohmann R. 2007. Levels of persistent organic pollutants in air in China and over the Yellow Sea. Atmos Environ 41:452-64. 177 Li J, Zhang G, Guo L, Xu W, Li X, Lee CSL, Ding A, Wang T. 2007. Organochlorine pesticides in the atmosphere of Guangzhou and Hong Kong: Regional sources and long-range atmospheric transport. Atmos Environ 41:3889-903. 178 Qiu X, Zhu T, Li J, Pan H, Li Q, Miao G, Gong J. 2004. Organochlorine pesticides in the air around the Taihu Lake, China. Environ Sci Technol 38(5):1368-74. 179 Qiu X, Zhu T, Wang F, Hu J. 2008. Air-water gas exchange of organochlorine pesticides in Taihu Lake, China. Environ Sci Technol 42:1928-32. 180 Pozo K, Harner T, Shoeib M, Urrutia R, Barra R, Parra O, Focardi S. 2004. Passive-sampler derived air concentrations of persistent organic pollutants on a north-south transect in Chile. Environ Sci Technol 38(24):6529-37. Annex E information on ENDOSULFAN 36 UNEP/POPS/POPRC.1/4 which brings with it residues originating from regional applications, residue levels increasing with elevation.181 146. It has been found as a ubiquitous air contaminant in the mountains of the Canadian Rockies and the California Sierra Nevada,182 and the USA’s western national parks.183 147. It has also been measured in air in the European Central Pyrenees (0.006 ng/m3 alpha-) and the High Tatras (0.042 ng/m3 alpha-); 184 and in mean concentrations of 27.6 pg/m3, higher than any other organochlorine pesticide, in the air in the Mt Everest region.185 148. Concentrations of alpha-Endosulfan measured in the atmosphere of the Central Himalaya “were similar to those found in North American mountains. Concentration gradients with altitude displayed large differences between summer (May to October) and winter (November to April). In summer concentrations of all the chemicals increased with elevation up to a maximum at 5000 m a.s.l [above sea level] and then declined above that elevation. Winter time concentration of all chemicals declined with altitude, except for HCB which had similar elevational trends year-round. This indicates that during the summer monsoon lower tropospheric air contaminated with pesticides is being driven by thermal and mechanical forcing from the Indian subcontinent into the central Himalaya.”186 149. Concentrations of 27.6 pg/m3 of alpha-Endosulfan were measured in the Rongbuk Valley, and 71.1 pg/m3 at Dingri, both in the Mt Everest region in 2002. Backward trajectory analysis was used to identify the origin of the endosulfan and other pesticides measured. “The trajectory for sample E [1 of 3 from Rongbuk Valley] started from an area to the west of Afghanistan and reached the Mt. Everest region driven by westerly winds. Compared to sample E, air masses 181 Daly G, Lei YD, Teixeira C, Muir DCG, Castillo LE, Wania F. 2007. Accumulation of current-use pesticides in neotropical montane forests. Environ Sci Technol 41:118-23. 182 Daly GL, Lei YD, Teixeira C, Muir DCG, Wania F. 2007. Pesticides in western Canadian mountain air and soil. Environ Sci Technol 41:6020-5. 183 Landers DH, Simonich SL, Jaffe DA, Geiser LH, Campbell DH, Schwindt AR, Schreck CB, Kent ML, Hafner WD, Taylor HE, Hageman KJ, Usenko S, Ackerman LK, Schrlau JE, Rose NL, Blett TF, Erway MM. 2008. The Fate, Transport, and Ecological Impacts of Airborne Contaminants in Western National Parks (USA). EPA/600/R-07/138. U.S. Environmental Protection Agency, Office of Research and Development, NHEERL, Western Ecology Division, Corvallis, Oregon. http://www.epa.gov/nheerl/wacap/WACAP_Table_of_Contents_Abbrev_Acknow.pdf. 184 van Drooge BL, Grimalt JO, Camarero L, Catalan J, Stuchlik E, Torres Garcia CJ. 2004. Atmospheric semivolatile organochlorine compounds in European high-mountain areas (central Pyrenees and high Tatras). Environ Sci Technol 38(13):3525-32. 185 Li J, Zhu T, Wang F, Qiu XH, Lin WL. 2006. Observation of organochlorine pesticides in the air of the Mt. Everest region. Ecotoxicol Environ Saf 63(1):33-41. 186 Loewen MD, Sharma S, Fuchs C, Wang F, Wania F, Muir DCG, Tomy GT. 2007. Seasonal and altitudinal trends of chlorinated pesticides in the central Himalayan atmosphere. In: Book of Abstract, Persistent Organic Pollutants in Mountainous Areas, An International Symposium Nov. 26–27, 2007, Salzburg, Austria. Annex E information on ENDOSULFAN 37 UNEP/POPS/POPRC.1/4 associated with other samples had higher OCP [organochlorine pesticide] concentrations and traveled shorter distances, and many originated from areas close to OCP source regions, e.g., India and north Pakistan. Driven by the Asian monsoon, the air masses for samples A and B started at the Nepal–Indian border, initially moved westward, and then climbed Himalaya eastward to Dingri. Air masses for samples C, D, and F collected at Rongbuk Valley were driven mostly by westerly winds and passed through three different paths: India–Nepal, Afghanistan–Pakistan– India–Nepal, and western Tibetan plateau.”187 Short-range drift and ambient air contamination 150. In a passive air sampling study at 18 locations in urban, rural and wetland sites along the coastal length of India, Endosulfan was “regularly detected”. Total Endosulfan ranged from 0.45 to 1122 pg/m 3, with highest level at Porto Nova. “Except for South America (29-14600 pg/m3) the level is comparable to Europe (21-1760 pg/m3) and higher than the rest of the world. The range detected is also consistent with the GAPS study (40-1090 pg/m3).” 188 151. Endosulfan was the most prevalent organochlorine pesticide measured in rural air in South Korea (max 12 ng/m3 alpha- + beta-),189 and in urban Seoul (alpha- + beta-: mean 329, max 1086 pg/m3; sulfate: mean 60.5, max 316 pg/m3).190 152. Beta-Endosulfan (av 20, max 30 pg/m3) and Endosulfan sulfate (av 369, max 1271 pg/m3) were measured in air samples taken in Izmir, Turkey.191 153. In France, endosulfan was measured in 79% of indoor air samples in the Paris area (median 0.3, max 13.5 ng/m3),192 and in 100% of air samples taken in urban Strasbourg during July (max alpha 102, and beta 85 pg/m3).193 187 Li J, Zhu T, Wang F, Qiu XH, Lin WL. 2006. Observation of organochlorine pesticides in the air of the Mt. Everest region. Ecotoxicol Environ Saf 63(1):33-41. 188 Zhang G, Chakraborty P, Li J, Sampathkumar P, Balasubramanian T, Kathiresan K, Takahashi K, Subramanian A, Tanabe S, Jones KC. 2008. Passive atmospheric sampling of organochlorine pesticides, polychlorinated biphenyls, and polybrominated diphenyl ethers in urban, rural, and wetland sites along the coastal length of India. Environ Sci Technol 42:8218-23. 189 Yeo H-G, Choi M, Chun M-Y, Sunwoo Y. 2003. Concentration distribution of polychlorinated biphenyls and organochlorine pesticides and their relationship with temperature in rural air in Korea. Atmos Environ 37(27):3831-9. 190 Yeo H-G, Choi M, Sunwoo Y. 2004. Seasonal variations in atmospheric concentrations of organochlorine pesticides in urban and rural areas of Korea. Atmos Environ 38(28):4779-88. 191 Sofuoglu A, Cetin E, Bozacioglu SS, Sener GD, Odabasi M. 2004. Short-term variation in ambient concentrations and gas/particle partitioning of organochlorine pesticides in Izmir, Turkey. Atmos Environ 38(27):4483-93. 192 Bouvier G, Blanchard O, Momas I, Seta N. 2006. Pesticide exposure of non-occupationally exposed subjects compared to some occupational exposure: a French pilot study. Sci Total Environ 366(1):74-91. 193 Scheyer A, Graeff C, Morville S, Mirabel P, Millet M. 2005. Analysis of some organochlorine pesticides in an urban atmosphere (Strasbourg, east of France). Chemosphere 58(11):1517-24. Annex E information on ENDOSULFAN 38 UNEP/POPS/POPRC.1/4 154. Ambient air concentrations of endosulfan were found in farming areas of Prince Edward Island in Canada, where it is used in potato cultivation. AlphaEndosulfan was detected in the air at 48% of farms (mean 6.3, max 14.8 ng/m3) and beta-Endosulfan at 41% (mean 2.2, max 7.2 ng/m 3).194 155. Endosulfan was found in 66 out of 75 rural air samples taken in California (USA), on the roofs of community buildings such as schools in both rural and urban communities. The mean concentration in urban areas was 3.8 ng/m 3, and in rural areas was 180 ng/m3.195 156. In the United States, the California Department of Pesticide Regulation (CDPR) monitored the air adjacent to a 2.4 ha apple orchard treated with Endosulfan at 1.7 kg/ha. Monitoring stations were set up 6.4–16.5 m from the boundaries of the orchard, and monitoring began when the application began and continued for 3 days. For the first 24-hour period, time weighed average concentrations ranged from 75–1,630 ng/m3 (sum, alpha and beta), and for the entire 3-day sampling period, average concentrations were 37–952 ng/m3. CDPR also conducted an ambient air monitoring studying in 1996, setting up monitoring stations atop 5 buildings in Fresno County. Approximately 20 samples were collected from each site from late July through August, and average alpha and beta concentrations ranged from 2-54 ng/m3 and 6-8 ng/m3, respectively. About 6,400 kg of Endosulfan were reportedly used that August in the county, which has an area of 15,444 km2.196 157. Pesticide Action Network North America (PANNA) has also conducted air monitoring studies in the vicinity of Endosulfan applications. In 2006 and 2007 PANNA placed an air monitoring station at a private home next to an elementary school in northern Florida, U.S. The station was 20 m from the edge of a Chinese cabbage field treated with Endosulfan. Eight samples were collected from December 6–14, 2006, and all contained alpha- and 7 contained betaEndosulfan. The average and maximum total Endosulfan concentrations were 278 and 626 ng/m3, respectively. 197 Thirty-nine samples were collected from October 1–December 6, 2007, and 87% contained alpha-Endosulfan, 69% contained beta-Endosulfan, 38% contained Endosulfan sulfate. The average and maximum total Endosulfan concentrations were 248 ng/m 3 and 1,376 ng/m3.198 194 White LM, Ernst WR, Julien G, Garron C, Leger M. 2006. Ambient air concentrations of pesticides used in potato cultivation in Prince Edward Island, Canada. Pest Manag Sci 62(2):126-36. 195 Lee S, McLaughlin R, Harnly M, Gunier R, Kreutzer R. 2002. Community exposures to airbourne agricultural pesticides in California: Ranking of inhalation risks. Environ Health Perspect 110(2):1175-84. 196 CDPR. 2008. Endosulfan Risk Characterization Document, Volume II: Exposure Assessment, HS-1647. Department of Pesticide Regulation, California Environmental Protection Agency, May 2008. http://www.cdpr.ca.gov/docs/whs/pdf/hs1647.pdf. 197 PANNA. 2007. Air Monitoring in Hastings, Florida December 6–14, 2006: Technical Report. Pesticide Action Network North America, April 2007, Docket ID No. EPA-HQ- OPP-2002-0262-92. http://www.panna.org/drift/catcher/results/hastings. 198 PANNA. 2008. Air Monitoring in Hastings, Florida October 1–December 6, 2007: Technical Report. Pesticide Action Network North America, September 2008. http://www.panna.org/drift/catcher/results/hastings07. Annex E information on ENDOSULFAN 39 UNEP/POPS/POPRC.1/4 Rainfall 158. For 20 years, between 1980 and 2000 Endosulfan was monitored in rainfall in Nova Scotia, New Brunswick and Newfoundland, on a monthly basis. The highest concentrations found were 2 ng/l alpha-Endosulfan at Jackson, Nova Scotia and Gros Morne, Newfoundland; and 10 ng/l beta-Endosulfan at Kejimkujik, Nova Scotia. Frequency of detection varied between 0 and 6.9% for the alpha isomer, and between 12.4 and 16.9% for the beta isomer.199 159. Samples taken at seven US and Canadian sites around the Great Lakes between 1997 and 2003 showed residues of Endosulfan peaked in summer corresponding to maximum usage in nearby agricultural areas, with highest average concentration being 1,400 pg/l alpha and 600 pg/l beta-Endosulfan at Point Petre near Lake Ontario.200 160. Endosulfan has also been measured in rainfall in urban areas: between 2000 and 2003, Endosulfan was measured in rain in the urban areas of Cuiaba, Brazil at 107 ng/l,201 in Chicago at 700 pg/l alpha- + 680 pg/l beta-.202 In 2000, the beta isomer was found in 28%, and alpha isomer in 13%, of rainfall samples, taken on the campus of the University of Maryland beside the Choptank River, Chesapeake Bay over a 7-month period Apr-Nov, with a maximum concentration of 81 ng/l (beta-).203 161. Endosulfan was measured in 85% of rainwater samples taken in urban Strasbourg and rural Erstein in France, in 2002-03, the highest concentration being 3667 ng/l (alpha- + beta-) in Strasbourg.204 162. Endosulfan was measured in 100% of samples of rainwater collected in Hisar, India in 2002, at levels of total Endosulfan as high as 3.020 ppb.205 Surface waters and sediment 199 Brun GL, MacDonald RM, Verge J, Aube J. 2008. Long-term atmospheric deposition of current-use and banned pesticides in Atlantic Canada; 1980-2000. Chemosphere 71:314-27. 200 Sun P, Backus S, Blanchard P, Hites RA. 2006. Temporal and spatial trends of organochlorine pesticides in Great Lakes precipitation. Environ Sci Technol 40:2135-41. 201 Laabs V, Amelung W, Pinto AA, Wantzen M, da Silva CJ, Zech W. 2002. Pesticides in surface water, sediment, and rainfall of the northeastern Pantanal Basin, Brazil. J Environ Qual 31:1636-48. 202 Sun P, Backus S, Blanchard P, Hites RA. 2006. Temporal and spatial trends of organochlorine pesticides in Great Lakes precipitation. Environ Sci Technol 40:2135-41. 203 Kuang Z, McConnell LL, Torrents A, Meritt D, Tobash S. 2003. Atmospheric deposition of pesticides to an agricultural watershed of the Chesapeake Bay. J Environ Qual 32(5):1611-22. 204 Scheyer A, Morville S, Mirabel P, Millet M. 2007. Pesticides analysed in rainwater in Alsace region (Eastern France): Comparison between urban and rural sites. Atmos Environ 41(34):7241-52. 205 Kumari B, Madan VK, Kathpal TS. 2007. Pesticide residues in rain water from Hisar, India. Environ Monit Assess 133:467-71. Annex E information on ENDOSULFAN 40 UNEP/POPS/POPRC.1/4 163. Published reports of Endosulfan contamination of surface water between 1982 and 2003 contain 606 detections in Canada, USA, Sweden, Australia, South Africa, and Argentina, 206 a far from complete record with many more reports since then. The U.S. EPA207 reported 667 detections between 1980 and 1999 for beta-Endosulfan in the USA alone. 164. The contamination of surface waters has frequently occurred at levels above those reported to cause adverse effects on aquatic life.208 The US EPA209 reports toxicity to estuarine/marine amphipods of Endosulfan in sediment at concentrations as low as 1.5 ug/kg of pore water (water filling spaces between grains of sediment). Other estimations for hazardous concentrations for aquatic organisms include 0.2-11 ug/l for fish;210 and a mean level of 0.02 ug/l for effects on 5% of aquatic organisms. 211 All of the figures reported below exceed this level. 165. Endosulfan reaches surface waters as a result of direct deposition and runoff from agricultural use. Reports of Endosulfan concentrations in run-off include 100 ug/l in southern USA, 45 ug/l in Australia, 66.5 ug/l in India,212 12,082 ug/kg of suspended particles in South Africa, 213 and up to 1,530 ug/l in ditch water during application on adjacent fields in British Columbia, Canada.214 166. Kennedy et al. (2001) found “significant contamination of all runoff water throughout the entire cotton-growing season in New South Wales”, Australia, with residue levels in the runoff reaching 10 ug/l seven days after aerial application, and typically being 2-10 ug/l. Major storms soon after application can cause runoff of 10% of the Endosulfan applied.215 167. Concentrations of Endosulfan in Australian rivers during the cotton growing season were reported by Raupach et al. (2001) to be in the range of 0.02 to 0.2 ug/l, significantly exceeding the 0.01 ug/l guideline for ecosystem protection set 206 Schulz R. 2004. Field studies on exposure, effects, and risk mitigation of aquatic nonpoint-source insecticide pollution: a review. J Environ Qual 33(2):419-48. 207 US EPA. 2007. Addendum to the Ecological Risk Assessment for Endosulfan. Memorandum to Special Review and Reregistration Branch. Oct 31. EPA-HQ-OPP-2002-0262-0063. http://www.regulations.gov. 208 Schulz 2004, op cit. 209 US EPA 2007, op cit. 210 Kennedy IR, Sanchez-Bayo F, Kimber SW, Hugo L, Ahmad N. 2001. Off-site movement of endosulfan from irrigated cotton in New South Wales. J Environ Qual 30:683-96. 211 Bollmohr S, Day JA, Schulz R. 2007. Temporal variability in particle-associated pesticide exposure in a temporarily open estuary, Western Cape, South Africa. Chemosphere 68:479-88. 212 Menone ML, Pesce SF, Dı ́az MP, Moreno VJ, Wunderlin DA. 2008. Endosulfan induces oxidative stress and changes in detoxication enzymes in the aquatic macrophyte Myriophyllum quitense. Phytochemistry 69(5):1150-7. 213 Shulz R. 2001. Comparison of spray drift- and runoff-related input of azinphos-methyl and endosulfan from fruit orchards into the Lourens River, South Africa. Chemosphere 45(2001):543-51. 214 Schulz R. 2004. Field studies on exposure, effects, and risk mitigation of aquatic nonpoint-source insecticide pollution: a review. J Environ Qual 33(2):419-48. 215 Kennedy IR, Sanchez-Bayo F, Kimber SW, Hugo L, Ahmad N. 2001. Off-site movement of endosulfan from irrigated cotton in New South Wales. J Environ Qual 30:683-96. Annex E information on ENDOSULFAN 41 UNEP/POPS/POPRC.1/4 by the Australia and New Zealand Conservation Council in 1992—due to nearly continuous low level input from spray drift and vapour transport representing “a steady drizzle”, and occasional higher input from run-off.216 168. In the USA, the National Sediment Quality Survey found endosulfan stream sediments in 30 out of 76 watersheds it tested for residues; 217 year-round detections of endosulfan in freshwater canals draining from agricultural areas in South Florida into the Everglades and Florida Bay, indicating chronic exposure to aquatic species;218 0.45 ug/kg (sulphate) in Florida surface waters and 120 ug/kg (sulfate) in sediment;219 571 ug/kg in the sediment of tailwater ponds collecting runoff from lettuce fields in California and 17.7 ug/kg in a nearby creek; 220 frequent detections in the water of 30 lakes in Canada and northeastern USA; 221 and in the sediment of mountain lakes in the Rocky Mountain and Glacier National Parks in Western USA at up to 1.2 ug/kg (sulphate).222 According to a recent review by the US National Parks Service, the State of Florida has monitored surface water in the Florida Everglades since the 1980s, and the mean and 90th percentile Endosulfan concentrations measured in the area are 0.09 mg/l and 0.25 mg/l, respectively. Others have found concentrations in the region as high as 1.34 mg/l. The contamination is presumed to come from the adjacent Homestead Agriculture Area, and levels are as much as three orders of magnitude higher in the dry season that the rainy season (0.18–1.35 mg/l versus 0.005–0.001 mg/l).223 169. Endosulfan has agricultural region of detections exceeded was reported to be been found in 47% of surface water samples tested in an Western Cape, South Africa. Thirty seven percent of the 0.1 ug/l, and reached levels of 3.6 ug/l. The main source washout from the agricultural soils after irrigation and 216 Raupach MR, Briggs PR, Ford PW, Leys JF, Muschal M, Cooper B, Edge VE. 2001. Endosulfan transport: I. Integrative assessment of airborne and waterborne pathways. J Environ Qual 30:714-28. 217 US EPA. 2002. Reregistration Eligibility Decision for Endosulfan. EPA 738-R-02-013. Pollution, Pesticides and Toxic Substances (7508C), United States Environmental Protection Agency. http://www.epa.gov/oppsrrd1/REDs/endosulfan_red.pdf. 218 DeLorenzo ME, Taylor LA, Lund SA, Pennington PL, Strozier ED, Fulton MH. 2002. Toxicity and bioconcentration potential of the agricultural pesticide endosulfan in phytoplankton and zooplankton. Arch Environ Contam Toxicol 42:173-81. 219 Pfeuffer RJ, Rand GM. 2004. South Florida ambient pesticide monitoring program. Ecotoxicology 13(3):195-205. 220 Weston DP, You J, Lydy MJ. 2004. Distribution and toxicity of sediment-associated pesticides in agriculture-dominated water bodies of California’s Central Valley. Environ Sci Technol 38:2752-9. 221 Muir DC, Teixeira C, Wania F. 2004. Empirical and modeling evidence of regional atmospheric transport of current-use pesticides. Environ Toxicol Chem 23(10):2421-32. 222 Mast MA, Foreman WT, Skaates SV. 2007. Current-use pesticides and organochlorine compounds in precipitation and lake sediment from two high-elevation national parks in the western United States. Arch Environ Contam Toxicol 52:294-305. 223 NPS. 2008. Comments on Petition to Revoke All Tolerances for Endosulfan. U.S. National Parks Service. October 29, 2008. Available in the public docket at http://www.regulations.gov under Document ID No. EPA-HQ-OPP-2008-0615-0041.1. Annex E information on ENDOSULFAN 42 UNEP/POPS/POPRC.1/4 rainfall.224 A pervious study in Western Cape, reported by Dalvie et al. (2003), found endosulfan in 26 out of 27 Elgin dams at levels up to 626 ug/l; Bollmohr et al. (2007) report 12.7 ug/l particle-associated endosulfan.225 170. Levels of 1.85 ug/l of Endosulfan were found in water samples from the Selangor River in Malaysia in 2003.226 171. In China Endosulfan has been measured in the sediment of Lake Taihu at 50.5 ug/kg (sulfate); 227 water at 445.9 ng/l (beta-) and sediment at 0.18 ng/l (beta-) of the Tonghui River;228 and water (215.9 ng/l beta-), pore water (1042 ng/l beta-) and sediment (8.84 ng/l sulfate) in the Minjiang River estuary. 229 172. In India, endosulfan has been measured in a number of surface water bodies, including water from the Yamuna River at Delhi, India (114 ng/l total Endosulfan);230 streams, ponds and canals of the northern Indo-Gangetic alluvial plains (0.13 ug/l total Endosulfan);231 water of the Gomti River, a tributary of the Ganges (0.09 ug/l sulfate);232 water (98.6 ng/l) and sediment (89.6 to 238 ug/g) in prawn ponds near Kolleru lake;233 and in the water of the Vellar River (206-2035 ng/l) and Kolleru Lake (2396 ng/l) possibly as the result of discharges from a nearby Endosulfan manufacturing facility.234 173. Endosulfan has been found in surface waters and sediments in a number of other countries, including Taiwan (10.5 ug/l sulfate in Wu-Shi River estuary 224 Dalvie MA, Cairncross E, Solomon A, London L. 2003. Contamination of rural surface and ground water by endosulfan in farming areas of the Western Cape, South Africa. Environ Health 2(1):1-15. 225 Bollmohr S, Day JA, Schulz R. 2007. Temporal variability in particle-associated pesticide exposure in a temporarily open estuary, Western Cape, South Africa. Chemosphere 68:479-88. 226 Leong KH, Tan LL, Mustafa AM. 2007. Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003. Chemosphere 66(6):1153-59. 227 Huang S, Qiao M, Wang H, Wang Z. 2006. Organchlorinated pesticides in surface sediments of Meiliang Bay in Taihu Lake, China. J Environ Sci Health A Tox Hazard Subst Environ Eng 41(2):223-34. 228 Zhang Z, Huang J, Yu G, Hong H. 2004. Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China. Environ Pollut 130(2):249-61. 229 Zhang ZL, Hong HS, Zhou JL, Huang J, Yu G. 2003. Fate and assessment of persistent organic pollutants in water and sediment from Minjiang River Estuary, Southeast China. Chemosphere 52(9):142330. 230 Aleem A, Malik A. 2005. Genotoxicity of the Yamuna River water at Okhla (Delhi), India. Ecotox Environ Saf 61(3):404-12. 231 Singh KP, Malik A, Sinha S. 2007. Persistent organochlorine pesticide residues in soil and surface water of northern Indo-Gangetic alluvial plains. Environ Monit Assess 125:147–55. 232 Malik A, Ojha P, Kunwar P, Singh KP. 2009. Levels and distribution of persistent organochlorine pesticide residues in water and sediments of Gomti River (India)—a tributary of the Ganges River. Environ Monit Assess 148(1-4):421-35. 233 Amaraneni SR. 2006. Distribution of pesticides, PAHs and heavy metals in prawn ponds near Kolleru lake wetland, India. Environ Int 32(3):294-302. 234 Sarkar SK, Bhattacharya BD, Bhattacharya A, Chatterjee M, Alam A, Satpathy KK, Jonathan MP. 2008. Occurrence, distribution and possible sources of organochlorine pesticide residues in tropical coastal environment of India: An overview. Environ Int 34(7):1062-71. Annex E information on ENDOSULFAN 43 UNEP/POPS/POPRC.1/4 sediment);235 Turkey (42.6 ng/ml water and 107.8 ng/g sediment beta-Endosulfan in Uluabat Lake);236 Ghana (62.3 + 7.3 alpha-, 31.4 + beta-, 30.8 + 12.3 sulfate ng/l water sampled from the environs of Akumadan); 237 Mexico (0.814 ug/kg sulfate in sediment from a coastal wetland); 238 and Argentina (319 ug/kg max alpha- + beta- in suspended particles of a stream in a soybean growing area).239 Groundwater: 174. In Haryana, India, all samples of water from tube wells in agricultural areas were contaminated with Endosulfan, with 83% of samples exceeding 0.1 ug/l, and maximum levels of 0.405 ug/l.240 175. In Hyderabad City, India, all the samples of domestic well water contained Endosulfan, at levels up to 11.23 ug/l, assumed to derive from agricultural use near the city.241 176. In the Thiruvallur area of Tamil Nadu, India, where Endosulfan is used on rice, total Endosulfan in open well and bore wells ranged from 1.1 to 19.2 ug/l.242 177. Endosulfan has recently been measured in 38% of groundwater samples in Portugal, with 12% of them exceeding the European Union’s limit of 0.1 ug/l.243 178. In South Africa, Dalvie et al. (2003) found Endosulfan in 32% of groundwater samples taken in farming areas in the Western Cape at levels up to 0.89 ug/l.244 235 Doong R-A, Peng C-K, Sun Y-C, Li P-L. 2002. Composition and distribution of organochlorine pesticide residues in surface sediments from the Wu-Shi River estuary, Taiwan. Mar Poll Bull 45(112):246-53. 236 Barlas N, Cok I, Akbulut N. 2006. The contamination levels of organochlorine pesticides in water and sediment samples in Uluabat Lake, Turkey. Environ Monit Assess 118:383-91. 237 Ntow WJ. 2001. Organochlorine pesticides in water, sediments, crops and human fluids in a farming community in Ghana. Arc Environ Contam Toxicol 40(4):557-63. 238 Hernandez-Romero AH, Tovilla-Hernandez C, Malo EA, Bello-Mendoza R. 2004. Water quality and presence of pesticides in a tropical coastal wetland in southern Mexico. Mar Pollut Bull 48(11-12):113041. 239 Jergentz S, Mugni H, Bonetto C, Schulz R. 2005. Assessment of insecticide contamination in runoff and stream water of small agricultural streams in the main soybean area of Argentina. Chemosphere 61:817–26. 240 Kumari B, Madan VK, Kathpal TS. 2008. Status of insecticide contamination of soil and water in Haryana, India. Environ Monit Assess 136(1-3):239-44. 241 Shukla G, Kumar A, Bhanti M, Joseph PE, Taneja A. 2006. Organochlorine pesticide contamination of ground water in the city of Hyderabad. Environ Int 32(2):244-47. 242 Jayashree R, Vasudevan N. 2007. Organochlorine pesticide residues in ground water of Thiruvallur district, India. Environ Monit Assess 128(1-3):209-15. 243 Goncalves CM, Silva JC, Alpendurada MF. 2007. Evaluation of the pesticide contamination of groundwater sampled over two years from a vulnerable zone in Portugal. J Agric Food Chem 55(15):622735. 244 Dalvie MA, Cairncross E, Solomon A, London L. 2003. Contamination of rural surface and ground water by endosulfan in farming areas of the Western Cape, South Africa. Environ Health 2(1):1-15. Annex E information on ENDOSULFAN 44 UNEP/POPS/POPRC.1/4 Marine sediments and seawater 179. Endosulfan has been found in marine sediment and seawater in a number of countries. Concentrations of Endosulfan sulphate of 0.4 ug/l were found in sediment taken from the mouth of the Hugli estuary in the vicinity of the Sundarban mangrove environment in eastern India.245 180. Endosulfan sulphate was measured at 0.025 ug/l in sediment on the Black Sea coast of Turkey in 2001-2003.246 181. It has also been measured inland coastal waters of Malaysia (0.4 ug/l) and the Philippines, and the sediment in the Straits of Malacca;247 in the sediment of Alexandria Harbour, Egypt; 248 in a coastal lagoon in Spain; 249 in the water of harbours in South Africa;250 in the coastal waters of Honduras and Jamaica, the sediment of Kingston Harbour; 251 and in coastal lagoons of the subtropical Mexican Pacific.252 Soil 182. Very high levels of contamination have been found in Ethiopia, with total Endosulfan reaching levels of 56,000 ug/kg in the soil of a state farm where organochlorine insecticides have been used for about three decades. The Upper Awash Agro Industry Enterprises grows cotton, fruits, vegetables, allium flowers 245 Bhattacharya B, Sarkar SK, Mukherjee N. 2003. Organochlorine pesticide residues in sediments of a tropical mangrove estuary, India: implications for monitoring. Environ Int 29(5):587-92. 246 Ozkoc HB, Bakan G, Ariman S. 2007. Distribution and bioaccumulation of organochlorine pesticides along the Black Sea coast. Environ Geochem Health 29:59-68. 247 GEF SEA SP. 2002. Regionally Based Assessment of Persistent Toxic Substances – South East Asia and South Pacific Regional Report. Global Environment Facility, United Nations Environmental Programme, Geneva. http://www.chem.unep.ch/Pts/. 248 Barakat AO, Kim M, Qian Y, Wade TL. 2002. Organochlorine pesticides and PCB residues in sediments of Alexandria Harbour, Egypt. Mar Poll Bull 44(12):1421-34. 249 GEF M. 2002. Regionally Based Assessment of Persistent Toxic Substances – Mediterranean Regional Report. Global Environment Facility, United Nations Environmental Programme, Geneva. http://www.chem.unep.ch/Pts/. 250 Fatoki OS, Awofolu OR. 2004. Levels of organochlorine pesticide residues in marine-, surface-, groundand drinking waters from the Eastern Cape Province of South Africa. J Environ Sci Health B 39(1):101-14. 251 GEF CAC. 2002. Regionally Based Assessment of Persistent Toxic Substances – Central America and the Caribbean Regional Report. Global Environment Facility, United Nations Environmental Programme, Geneva. http://www.chem.unep.ch/Pts/. 252 GEF M. 2002. Regionally Based Assessment of Persistent Toxic Substances – Mediterranean Regional Report. Global Environment Facility, United Nations Environmental Programme, Geneva. http://www.chem.unep.ch/Pts/. Annex E information on ENDOSULFAN 45 UNEP/POPS/POPRC.1/4 and cereals, and their annual Endosulfan use is 29,000 litres, estimated to be about 10 tonnes active ingredient.253 183. In Australian cotton fields where Endosulfan was applied 3 times throughout the cotton-growing season, residues from the previous season’s spraying were found in the soil at the beginning of the next season (at 10 to 80 ug/kg), indicating a continual build up in the soil.254 184. Similarly, in Tamil Nadu, India, 100 to 1,000 ug/kg residual Endosulfan sulphate was found at the beginning of the rice season, with this level increasing to 22,000 ug/kg during the season—still present at 5,500 ug/kg at 210 days after application,255 again indicating accumulating residual levels. 185. Although at much lower levels, Endosulfan contamination of the soil in cotton fields of the Punjab has been shown to increase with time, by a factor of 5 over the course of 3 years: in 1995 the residue after application was 7.3 ug/kg reducing to 2.4 ug/kg after 22 days. But in 1998 in the same field the levels were 35.6 ug/kg reducing to 22 ug/kg after 22 days, despite the insecticide being applied at the same rate (Vig et al. 2008).256 186. All samples of soil taken in cotton-wheat, paddy-wheat and sugarcane fields in Haryana, India, were contaminated with Endosulfan at levels ranging up to 39 ug/kg.257 187. Endosulfan has also been found in the soils of the northern Indo-Gangetic plains; 258 Hong Kong, 259 and the Taihu Lake Region of China; 260 Ghana, 261 253 Westbom R, Hussen A, Megersa N, Retta N, Mathiasson L, Bjorklund E. 2008. Assessment of organochlorine pesticide pollution in Upper Awash Ethiopian state farm soils using selective pressurised liquid extraction. Chemosphere 72(8):1181-7. 254 Kennedy IR, Sanchez-Bayo F, Kimber SW, Hugo L, Ahmad N. 2001. Off-site movement of endosulfan from irrigated cotton in New South Wales. J Environ Qual 30:683-96. 255 Jayashree R, Vasudevan N. 2007. Persistence and distribution of endosulfan under field conditions. Environ Monit Assess 131(1-3):475-87. 256 Vig K, Singh DK, Agarwal HC, Dhawan AK, Dureja P. 2008. Soil microorganisms in cotton fields sequentially treated with insecticides. Ecotoxicol Environ Saf 69(2):263-76. 257 Kumari B, Madan VK, Kathpal TS. 2008. Status of insecticide contamination of soil and water in Haryana, India. Environ Monit Assess 136(1-3):239-44. 258 Singh KP, Malik A, Sinha S. 2007. Persistent organochlorine pesticide residues in soil and surface water of northern Indo-Gangetic alluvial plains. Environ Monit Assess 125:147–55. 259 Zhang HB, Luo YM, Zhao QG, Wong MH, Zhang GL. 2006. Residues of organochlorine pesticides in Hong Kong soils. Chemosphere 63(4):633-41. 260 Wang F, Jiang X, Bian YR, Yao FX, Gao HJ, Yu GF, Munch JC, Schroll R. 2007. Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China. J Environ Sci (China) 19(5):584-90. 261 Ntow WJ. 2001. Organochlorine pesticides in water, sediments, crops and human fluids in a farming community in Ghana. Arc Environ Contam Toxicol 40(4):557-63. Annex E information on ENDOSULFAN 46 UNEP/POPS/POPRC.1/4 Senegal and Kenya;262 Portugal,263 Czech Republic,264 and rice fields in Spain;265 Colombia (at 350 ug/kg), Honduras, Nicaragua, and Panama,266 and in the soils of environmental reserves in Brazil.267 Animals Aquatic Species 188. In a study of organochlorine residues in bivalves from the lagoons of Ghana, the following levels were measured during the dry season, with generally lower levels in the wet season (except for mussels): in cockles, 21 (5-30) ng/g dry weight alpha-, plus 51 (2-78) ng/gm beta-; in oysters, 31(10-93) ng/gm alpha-, plus 20 (16-83) ng/g beta-; in mussels 18 (2-66) ng/g alpha-, plus 29 (21-66) ng/g beta-.268 189. In India, Endosulfan residues were measured in fish at 1.41 ug/g (max alpha- + beta-) in fish of the species Labeo rohita and Catla catla collected from markets in Calcutta between 1993 and 1998. 269 Aktar et al. (2008) measured total Endosulfan residues up to 2.95 ppm in fish collected from the Ganga at Uluberia in West Bengal in 2005.270 Levels of 23 + 3 ppb (wet weight) of total Endosulfan were recorded in fish collected from the Cochin Coast.271 In a study of pesticide bioaccumulation in fish in rivers in north India, Singh & Singh (2007) found that “The tissue bioaccumulation of aldrin and endosulfan were high in liver, brain and ovary of R. rita and M. tengara captured from the polluted rivers 262 Westbom R, Hussen A, Megersa N, Retta N, Mathiasson L, Bjorklund E. 2008. Assessment of organochlorine pesticide pollution in Upper Awash Ethiopian state farm soils using selective pressurised liquid extraction. Chemosphere 72(8):1181-7. 263 Gonçalves C, Alpendurada MF. 2005. Assessment of pesticide contamination in soil samples from an intensive horticulture area, using ultrasonic extraction and gas chromatography–mass spectrometry. Talanta 65(5):1179-89. 264 Shegunova P, Klanova J, Holoubek I. 2007. Residues of organochlorinated pesticides in soils from the Czech Republic. Environ Pol 146:257-61. 265 Gamón M, Sáez E, Gil J, Boluda R. 2003. Direct and indirect exogenous contamination by pesticides of rice-farming soils in a Mediterranean wetland. Arch Environ Contam Toxicol 44(2):141-51. 266 GEF CAC. 2002. Regionally Based Assessment of Persistent Toxic Substances – Central America and the Caribbean Regional Report. Global Environment Facility, United Nations Environmental Programme, Geneva. http://www.chem.unep.ch/Pts/. 267 Rissato SR, Galhiane MS, Ximenes VF, de Andrade RMB, Talamoni JLB, Libanio M, de Almeida MV, Apon BM, Cavalari AA. 2006. Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of Sao Paulo State, Brazil. Chemosphere 65:1949-58. 268 Otchere FA. 2005. Organochlorines (PCBs and pesticides) in the bivalves Anadara (Senilis) senilis, Crassostrea tulipa and Perna perna from the lagoons of Ghana. Sci Total Environ 348(1-3):102-14. 269 Kole RK, Banerjee H, Bhattacharyya A. 2001. Monitoring of market fish samples for endosulfan and hexachlorocyclohexane residues in and around Calcutta. Bull Environ Contam Toxicol 67:554-59. 270 Aktar MW, Paramasivam M, Sengupta D, Purkait S, Ganguly M, Banerjee S. 2008. Impact assessment of pesticide residues in fish of Ganga river around Kolkata in West Bengal. Environ Monit Assess [Epub August 30]. 271 Muralidharan S, Dhananjayan V, Jayanthi P. 2009. Organochlorine pesticides in commercial marine fishes of Coimbatore, India and their suitability for human consumption. Environ Res 109(1):15-21. Annex E information on ENDOSULFAN 47 UNEP/POPS/POPRC.1/4 Gomti and Ganga, respectively, when compared to the same species captured from the reference site.” 272 190. Menone et al. (2000)273 found residues of Endosulfan sulfate in the liver, gonads, fat and muscle of fish from a coastal lagoon in Argentina, at levels ranging up to 0.018 ug/kg of tissue. 191. In a study measuring atmospherically deposited chemicals in fish in the western US national parks, Ackerman et al. (2008) stated that “dacthal and endosulfan sulfate were among the most concentrated and frequently detected SOCs [semivolatile organic compounds] in this study . . ..”274 192. In a review of data on organochlorine pesticide residues in the marine environment of tropical coastal India, Sarkar et al. (2008) reported the following data on Endosulfan, all figures ng/g wet weight: zooplankton from the Bay of Bengal (0.1-0.4), oysters and clams (0.8-5.7), and fish (0.02-2.47).275 193. Concentrations of Endosulfan in oyster samples from Laguna de Terminos, Mexico ranged from 162 to 670 pg/g dry weight. Residues in lagoon sediments ranged from 0 to 50.3 pg/g dry weight (mean 13 pg/g). Residues in filtered water taken from the lagoon ranged from 0 to 37 pg/l. “Endosulfan was measured in most water samples of Laguna de Terminos with maximal values in the estuaries of rivers and near Ciudad del Carmen.” ... “Accumulation of this pesticide by oysters takes place from the water fraction and allows accumulation of the two endosulfan isomers and of endosulphan sulphate in oyster tissues.” The levels of Endosulfan in the oysters were significantly higher than the water from which it was accumulated.276 194. In a study measuring the levels of organochlorine contamination of Anuran amphibians in an artificial lake in the semiarid midwest of Argentina, Endosulfan (alpha- + beta-) was found at levels ranging 0.5-24.4 ng/g wet mass and 18.11406.8 ng/g fat.277 272 Singh PB, Singh V. 2007. Pesticide bioaccumulation and plasma sex steroids in fishes during breeding phase from north India. Environ Toxicol Pharmacol 55(3-4):223-37. 273 Menone ML, Aizpun de Moreno JE, Moreno VJ, Lanfranchi AL, Metcalfe TL, Metcalfe CD. 2000. PCBs and organochlorines in tissues of silverside (Odontesthes bonariensis) from a coastal lagoon in Argentina. Arch Environ Contam Toxicol 38:202-8. 274 Ackerman LK, Schwindt AR, Simonich SLM, Koch DC, Blett TF, Schreck CB, Kent ML, Landers DH. 2008. Atmospherically deposited PBDEs, pesticides, PCBs, and PAHs in western U.S. National Park fish: concentrations and consumption guidelines. Environ Sci Technol 42:2334-41. 275 Sarkar SK, Bhattacharya BD, Bhattacharya A, Chatterjee M, Alam A, Satpathy KK, Jonathan MP. 2008. Occurrence, distribution and possible sources of organochlorine pesticide residues in tropical coastal environment of India: An overview. Environ Int 34(7):1062-71. 276 Carvalho FP, Villeneuve J-P, Cattini C, Rendon J, Mota de Oliveira J. 2008. Pesticide and PCB residues in the aquatic ecosystems of Laguna de Terminos, a protected area of the coast of Campeche, Mexico. Chemosphere [Epub November 18]. 277 Jofre MB, Anton RI, Caviedes-Vidal EC. 2008. Organochlorine contamination in anuran amphibians of an artificial lake in the semiarid Midwest of Argentina. Arch Environ Contam Toxicol 55(3):471-80. Annex E information on ENDOSULFAN 48 UNEP/POPS/POPRC.1/4 195. In a study of pesticide residues in amphibia in California (USA), “all sites had adults with measurable levels of endosulfan” . . . “up to 86% of some populations had measurable endosulfan concentrations”. The maximal concentration was 21.9 ppb. “Thus, the detection of endosulfan in frogs denotes recent exposure and suggests risk”.278 196. Fish in the Everglades region of Florida have concentrations as high as 395 ng/g dry weight. Mussels from the region have some of the highest concentrations measured in the US, with 3.4–8.1 ng/g dry weight. One study found concentrations in small fish range from 0.3–20.1 ng/g, and in oysters from 3.3–21.3 ng/g dry weight. Another reported a maximum concentration in oysters of 41.4 ng/g dry weight.279 197. It has also been found in freshwater fish in a number of countries including Australia, 280 Zambia, 281 Benin and Kenya, 282 Tanzania , 283 Uganda, 284 and in estuarine fish in Argentina. 285 It has been found in farmed prawns in India (Amaranemi 2006).286 Terrestrial species 198. In Zimbabwe, Endosulfan was found to accumulate in the tissues of wild rats feeding in soya bean fields to which Endosulfan was applied. Levels in liver 278 Sparling DW, Fellers GM, McConnell LL. 2001. Pesticides and amphibian population declines in California USA. Environ Toxicol Chem 20(7):1591-95. 279 NPS. 2008. Comments on Petition to Revoke All Tolerances for Endosulfan. U.S. National Parks Service. October 29, 2008. Available in the public docket at http://www.regulations.gov under Document ID No. EPA-HQ-OPP-2008-0615-0041.1. 280 Nowak B. 1990. Residues of endosulfan in the livers of wild catfish from a cotton growing area. Environ Monitor Assess 14(2-3):347-51. 281 Syakalima M, Choongo K, Mwenechanya R, Wepener V, Yamasaki M, Maede Y. 2006. Pesticide/herbicide pollutants in the Kafue River and a preliminary investigation into their biological effect through catalase levels in fish. Jpn J Vet Res 5(2-3):119-28. 282 (a) Pazou EY, Boko M, van Gestel CA, Ahissou H, Laleye P, Akpona S, van Hattum B, Swart K, van Straalen NM. 2006a. Organochlorine and organophosphorous pesticide residues in the Oueme River catchment in the Republic of Benin. Environ Int 32(5):616-23. (b) Pazou EY, Laleye P, Boko M, van Gestel CA, Ahissou H, Akpona S, van Hattum B, Swart K, van Straalen NM. 2006b. Contamination of fish by organochlorine pesticide residues in the Oueme River catchment in the Republic of Benin. Environ Int 32(5):594-99. 283 Henry L, Kishimba MA. 2006. Pesticide residues in Nile tilapia (Oreochromis niloticus) and Nile perch (Lates niloticus) from Southern Lake Victoria, Tanzania. Environ Pollut 140(2):348-54. 284 Kasozi GN, Kiremire BT, Bugenyi FW, Kirsch NH, Nkedi-Kizza P. 2006. Organochlorine residues in fish and water samples from Lake Victoria, Uganda. J Environ Qual 35(2):584-89. 285 Lanfranchi AL, Menone ML, Miglioranza KSB, Janiot LJ, Aizpun JE, Moreno VJ. 2006. Striped weakfish (Cynoscoon guatucupa): a biomonitor of organochlorine pesticides in estuarine and near-coastal zones. Mar Poll Bull 52(74-80). 286 Amaraneni SR. 2006. Distribution of pesticides, PAHs and heavy metals in prawn ponds near Kolleru lake wetland, India. Environ Int 32(3):294-302. Annex E information on ENDOSULFAN 49 UNEP/POPS/POPRC.1/4 were generally higher (0.36-5.8 ug/kg) than those in muscles (0.09-5.17 ug/kg) and fatty tissues (0.08-4.78 ug/kg).287 199. In a study of 3 types of vultures from different localities in South Africa, in total blood samples “the greatest mean value was calculated for African whitebacked vultures from Moholoholo (27.01 ug/l) followed by a substantially lower value for the Dronfield population (11.8 ug/l). However, it should be noted that the latter group displayed a maximum concentration of 37.74 ug/l) and a wide dispersion around the geometric mean was found for individual endosulfan sulfate values of the Dronfield birds.” … “The highest mean value was obtained in kidneys (63.67 ug/l), followed by the livers (43.02 ug/l) and the clotted blood samples (24.3 ug/l). Levels of this toxicant were measured in the kidney, liver and blood samples from the same individuals, which contained quantifiable residues of endosulfan sulfate.”288 200. Cid et al. (2007) carried out an analysis of organochlorine pesticide contamination in three bird species of the Embalse La Florida water reservoir in the semiarid midwest of Argentina. “The highest concentration of a single contaminant was measured in one of the great kiskadees (aldrin at 5245.44 ng/g fat), and this was followed by endosulfan (4276.23 ng/g fat) in a neotropic cormorant.” … “Endosulfan, in the ΣALD family, occurred at a frequency of 92% in the assayed samples and its average concentration was 1226.09 ng/g fat (range: ND to 4276.23 ng/g fat), the highest observed for all OCs determined. This high frequency of incidence and concentration may be due to its intensive and continual use since 1970 as an insecticide in a variety of crops such as tea, vegetables, fruits, and tobacco.” 289 201. Dong et al. (2004) carried out an analysis of organochlorine pesticide levels in the eggs of 4 water bird species from a colony on Tai Lake in China. They found residues of Endosulfan in all species, with the highest frequency and levels in the eggs of little egret (Egretta garzetta): 77.8 % occurrence of alphaEndosulfan (mean 13.84, max 93.30 ng/g dry weight), and 19.4% occurrence of beta-Endosulfan (mean 19.21, max 41.4 ng/gm).290 202. In a cross-taxa survey of organochlorine pesticide contamination in a tropical conservation area in northwest Costa Rica, Klemens et al. (2003) 287 Kuvarega AT, Taru P. 2007. Accumulation of endosulfan in wild rat, Rattus norvegious as a result of application to soya bean in Mazoe (Zimbabwe). Environ Monit Assess 125(1-3):333-45. 288 van Wyk E, Bouwman H, van der Bank H, Verdoorn GH, Hofmann D. 2001. Persistent organochlorine pesticides detected in blood and tissue samples of vultures from different localities in South Africa. Comp Biochem Physiol C 129:243-64. 289 Cid FD, Anton RI, Cavieded-Vidal E. 2007. Organochlorine pesticide contamination in three bird species of the Embalse La Florida water reservoir in the semiarid midwest of Argentina. Sci Total Environ 385:86-96. 290 Dong YH, Wang H, An Q, Ruiz X, Fasola M, Zhang YM. 2004. Residues of organochlorinated pesticides in eggs of water birds from Tai Lake in China. Environ Geochem Health 26:259-68. Annex E information on ENDOSULFAN 50 UNEP/POPS/POPRC.1/4 measured beta-Endosulfan in birds at up to 66 ug/kg, and at lower levels in amphibians.291 203. Martın ́ ez-Lopez et al. (2008) studied pesticide levels in the blood of booted eagle (Hieraaetus pennatus) in Spain over the years 1999-2003. They found levels of alpha-Endosulfan increased annually to the maximum in 2003 (109.04 + 75.42 ug/l), beta-Endosulfan peaked in 2002 (26.53 + 22.64 ug/l), as did the sulphate (50.90 + 63.78 ug/l).292 204. An analysis of whole blood, serum, and liver tissue samples from Kafue lechwe (marsh antelope) in the Lochinvar National Park of Zambia found mean residue levels of Endosulfan of 3.7 (+ 0.1) ug/g wet weight in the liver tissue of males and 4.2 (+ 2.2) in females; 8.6 (+3.2 ug/ml) in the serum of females, ND in males; and 3.8 (+ 1.2 ug/ml) in males, ND in females.293 Non-target Plants 205. Endosulfan has been found in the bark of trees from every one of the 32 countries sampled all over the world between 1992 and 1995, including India (1500 ug/gm), South Korea (1100 ug/gm), Philippines (540 ug/gm), Japan (450 ug/gm), Iran (310 ug/gm), Australia (110 ug/gm), New Zealand (32 ug/gm) and China (14 ug/gm), as well is in Africa, North and South America and Europe (figures are averages for the country for Endosulfan sulphate).294 295 206. Residues of Endosulfan, resulting from atmospheric deposition, were measured in moss in Singapore, geometric mean values 0 to 6.52 ng/g. 296 Food and drink 207. Endosulfan contamination of vegetables and fruit is widespread. Endosulfan and DDT were the most commonly detected residues in an analysis of the 5000 most widely consumed foods in the USA.297 291 Klemens JA, Wieland ML, Flanagin VJ, Frick JA, Harper RG. 2003. A cross-taxa survey of organochlorine pesticide contamination in a Costa Rican wildland. Environ Poll 122(2):245-51. 292 Martinez-Lopez E, Romero D, Maria-Mojica P, Martinez JE, Calvo JF, Garcia-Fernandez AJ. 2009. Changes in blood pesticide levels in booted eagle (Hieraaetus pennatus) associated with agricultural land practices. Ecotox Environ Saf 72(1):45-50. 293 Sichilongo K, Torto N. 2006. Determination of endocrine disruptors in Kafue lechwe (Kobus leche kafuensis) samples from the Lochinvar National Park of Zambia. Environ Int 32:718-23. 294 Simonich SL, Hites RA. 1995. Global distribution of persistent organochlorine compounds. Science 269(5232):1851-4. 295 Simonich SL, Hites RA. 1997. Relationships between socioeconomic indicators and concentrations of organochlorine pesticides in tree bark. Environ Sci Technol 31(4):999-1003. 296 Lim TB, Xu R, Tan B, Obbard JP. 2006. Persistent organic pollutants in moss as bioindicators of atmospheric pollution in Singapore. Chemosphere 64(4):596-602. Annex E information on ENDOSULFAN 51 UNEP/POPS/POPRC.1/4 208. In New Zealand 32% of tomatoes sampled contained Endosulfan with levels up to 972 ug/kg. It has also been found in capsicum, courgette, cucumber, pears, vegetable oil, salad dressing, peanuts and peanut butter.298 209. In India, all of 39 samples of cauliflower, brinjal and okra taken at Ranchi, Jharkhand were found to contain Endosulfan (0.002 - 2.47 mg/kg).299 Seventy six percent of 25 summer vegetable samples, and 92% of 25 winter vegetable samples taken in Agra contained residues of Endosulfan with the highest concentrations being, in summer, 9.02 ppb in spinach and, in winter, 12.42 ppb in cabbage.300 One hundred percent of 28 samples of a complete daily vegetarian diet (tea, milk, breakfast, lunch, snacks, dinner, sweet dish), taken in Hisar city, were contaminated with Endosulfan, with residues levels ranging from 0.026 to 0.354 ppm, and daily intake was estimated to exceed the Acceptable Daily Intake in 4 samples.301 210. In Ghana, 36% of lettuces sampled contained Endosulfan at levels up to 1.3 mg/kg (mean 0.4 mg/kg).302 211. Alpha-Endosulfan was found in pekmez, the traditional grape molasses of Turkey (mean 0.3 ng/g, max 1.3 ng/g).303 212. Endosulfan was measured in 27% of 325 samples of cows' milk taken in the Bundelkhand region of India. Of these, 65% were above the MRL, with the maximum level being 0.3748 mg/kg whole milk.304 213. Butter (45) and ghee (25) samples were collected from rural and urban areas of the cotton growing belt of Haryana, India. Residues of endosulfan 297 Campoy C, Jimenz M, Olea-Serrano MF, Moreno-Frias M, Canabate F, Olea N, Bayes R, Molina-Font JA. 2001. Analysis of organochlorine pesticides in human milk: preliminary results. Early Hum Devel 65(s2):S183-90. 298 NZFSA. 2007. Food Residue Surveillance Programme June 2007. New Zealand Food Safety Authority. Wellington. http://www.nzfsa.govt.nz/science/research-projects/food-residues-surveillanceprogramme/results/2007/index.htm. 299 Shahi DK, Nisha K, Sharma A. 2005. Monitoring of pesticide residues in market vegetables at Ranchi, Jharkhand (India). J Environ Sci Eng 47(4):322-5. 300 Bhanti M, Taneja A. 2005. Monitoring of organochlorine pesticide residues in summer and winter vegetables from Agra, India – a case study. Environ Monit Assess 110(1-3):341-6. 301 Kumari B, Kathpal TS. 2008. Monitoring of pesticide residues in vegetarian diet. Environ Monit Assess [Epub April 2]. 302 Amoah P, Drechsel P, Abaidoo RC, Ntow WJ. 2006. Pesticide and pathogen contamination of vegetables in Ghana's urban markets. Arch Environ Contam Toxicol 50(1):1-6. 303 Erdogrul O. 2008. Pesticide residues in liquid pekmez (grape molasses). Environ Monit Assess 144(13):323-8. 304 Nag SK, Raikwar MK. 2008. Organochlorine pesticide residues in bovine milk. Bull Environ Contam Toxicol 80(1):5-9. Annex E information on ENDOSULFAN 52 UNEP/POPS/POPRC.1/4 exceeded the MRL in 11% of butter (max = 1.668 ug/g total Endosulfan), and 20% of ghee samples (max = 2.975 ug/g total Endosulfan) above the MRL.305 214. Endosulfan was found in New Zealand beef at 0.5 ppm as a result of external application of the insecticide to cattle to control parasites, 306 and in Australian beef as a result of spray drift from cotton fields.307 215. Endosulfan was found in honey samples from Kahramanmaras, Turkey (alpha-Endosulfan - mean 0.09 and max 0.34 ng/g; beta-Endosulfan - mean 0.27 and max 0.46 ng/g).308 It was found in 23.4% of 47 beeswax samples taken from apiaries in 5 sites located in continental France, with the mean concentration of 88.8 ug/kg and a maximum of 243.1 mg/kg.309 216. Sampling in Korea, of herbal medicinal drugs, found 0.349 mg/kg of Endosulfan (MRL = 0.2) in Polygalae radix imported from China.310 217. Endosulfan residues were found in 5 of 25 samples of commercial milkbased infant formula in Spain, with the following concentration range: alphaEndosulfan 1.6-5.03 ug/kg, and beta-Endosulfan 1.18-2.70 ug/kg.311 218. Residues of Endosulfan were found throughout tea ecosystems in the Dooars and Hill regions of West Bengal, India, sampled in April and again in November, with the highest levels in fresh tea leaves. Beta-Endosulfan was found in 100% of fresh tea leaves and ‘made tea’ from Dooars and 40% from Hill region. Maximum levels of beta-Endosulfan found were: fresh tea leaves (0.9238 ppm), ‘made tea’ (0.2858 ppm), the soil (0.7601 ppm) and water bodies (0.0022 ppm). Lower levels of alpha-Endosulfan and Endosulfan sulphate were also found in all samples with the exception of the sulphate in water.312 219. Endosulfan residues were found in every village bore well and open well sampled in the Thiruvallur district of Tamil Nadu, India. Alpha-Endosulfan levels 305 Kumari B, Singh J, Singh S, Kathpal TS. 2005. Monitoring of butter and ghee (clarified butter fat) for pesticidal contamination from cotton belt of Haryana, India. Environ Monit Assess 105(1-3):111-20. 306 NZFSA. 2007. Endosulfan: the story unfolds. Food Focus August. New Zealand Food Safety Authority, Wellington. http://www.nzfsa.govt.nz/publications/food-focus/2007-08/page-13.htm. 307 NRA. 2000. Media Release - NRA Gets Tough on Endosulfan to Protect Australian Beef. National Registration Authority for Agricultural and Veterinary Chemicals. 30 June. http://www.apvma.gov.au/media/mr0007.shtml. 308 Erdogrul O. 2007. Levels of selected pesticides in honey samples from Kahramanmaras, Turkey. Food Control 18:866-71. 309 Chauzat MP, Faucon JP. 2007. Pesticide residues in beeswax samples collected from honey bee colonies (Apis mellifera L.) in France. Pest Manag Sci 63(11):1100-6. 310 Oh CH. 2007. Multi residual pesticide monitoring in commercial herbal crude drug materials in South Korea. Bull Environ Contam Toxicol 78(5):314-8. 311 Mezcua M, Repetti MR, Aguera A, Ferrer C, Garcia-Reyes JF, Fernandez-Alba AR. 2007. Determination of pesticides in milk-based infant formulas by pressurised liquid extraction followed by gas chromatography tandem mass spectrometry. Anal Bioanal Chem 55(26):10548-56. 312 Bishnu A, Chakrabarti K, Chakraborty A, Saha T. 2008. Pesticide residue level in tea ecosystems of Hill and Dooars regions of West Bengal, India. Environ Monit Asses [Epub February 20]. Annex E information on ENDOSULFAN 53 UNEP/POPS/POPRC.1/4 ranged from 0.1 to 4.5 ug/l, beta-Endosulfan from 0.2 to 13 ug/l and Endosulfan sulphate from 1.1 to 19.2 ug/l. Maximum total Endosulfan level was 32.1 ug/l.313 220. All samples from 28 domestic well supplies in the city of Hyderabad, India contained alpha- and beta-Endosulfan, with the maximum level found being 11.3 ug/l.314 221. Levels of 1.85 ug/l of Endosulfan were found, in 2003, in water samples from the Selangor River in Malaysia, which is used for drinking purposes.315 - as a result of long-range environmental transport Air For evidence of exposure to residues in air through long-range environmental transport, see under: How are chemical/physical properties and persistence linked to environmental transport, transfer within and between environmental compartments, degradation and transformation to other chemicals? Snow 222. In a study of contaminants in Arctic snow collected over northwest Alaskan sea ice of the Beaufort and Chukchi seas in 1995-6, alpha-Endosulfan was consistently present, in nearly every sample, with beta-Endosulfan detected in some samples from one site. The levels found were higher than for DDT and any of the other POPS pesticides, with the exception of Chlordane which had similar levels.316 223. Endosulfan sulfate has been found in an ice core sample from the Antarctic region at a concentration of 300 ng/l.317 313 Jayashree R, Vasudevan N. 2007. Organochlorine pesticide residues in ground water of Thiruvallur district, India. Environ Monit Assess 128(1-3):209-15. 314 Shukla G, Kumar A, Bhanti M, Joseph PE, Taneja A. 2006. Organochlorine pesticide contamination of ground water in the city of Hyderabad. Environ Int 32(2):244-47. 315 Leong KH, Tan LL, Mustafa AM. 2007. Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003. Chemosphere 66(6):1153-59. 316 Garbarino JR, Synder-Conn E, Leiker T, Hoffman GL. 2002. Contaminants in Arctic snow collected over northwest Alaskan sea ice. Water Air Soil Poll 139:183-214. 317 Deger AB, Gremm TJ, Frimmel FH, Mendez L. 2003. Optimization and application of SPME for the gas chromatographic determination of endosulfan and its major metabolites in the ngL -1 range in aqueous solutions. Anal Bioanal Chem 376:61-8. Annex E information on ENDOSULFAN 54 UNEP/POPS/POPRC.1/4 224. In 2002-03 Endosulfan residues were amongst the most frequently detected in snowpack in seven national parks in arctic, sub-arctic and alpine regions of the US. The highest concentration was 1500 ng/m 3 at Sequoia National Park. Residues in the Arctic region (peaking at 170 ng/m 3) were regarded as the result of long-range transport.318 225. Alpha- and beta-Endosulfan were consistently detected in snowpack near Lake Superior in 1999-2000, at concentrations ranging up to 0.181 ng/l alphaEndosulfan, plus 0.035 ng/l beta-Endosulfan.319 226. Alpha-Endosulfan was one of the most frequently detected pesticides in snow in the Rocky Mountain and Glacier National Parks in the Western US, found at levels up to 2.5 ng/l.320 227. Alpha-Endosulfan was found in 100% of samples of snow taken from the Punta Indren glacier in the Italian Alps at concentrations ranging from 0.05 to 0.168 ng/l.321 Marine sediments and seawater 228. Endosulfan contamination of Arctic seawater has been observed since early 1993, 322 and is now so widespread in the surface water that it has been described as ubiquitous.323 229. A study evaluating concentrations of endosulfan in Arctic seawater demonstrated: “Surface seawater concentrations for alpha- and beta-endosulfan ranged from <0.1-8.8 (mean 2.3) pg/L and 0.1-7.8 (mean 1.5) pg/L. … Geographical distributions for alpha-endosulfan revealed the highest 318 Hageman KJ, Simonich SL, Campbell DH, Wilson GR, Landers DH. 2006. Atmospheric deposition of current-use and historic-use pesticides in snow at national parks in the western United States. Environ Sci Technol 40:3174-80. 319 Burniston DA, Strachan WJM, Wania F. 2007. Changes in surface area and concentrations of semivolatile organic contaminants in aging snow. Environ Sci Technol 42:4932-37. 320 Mast MA, Foreman WT, Skaates SV. 2007. Current-use pesticides and organochlorine compounds in precipitation and lake sediment from two high-elevation national parks in the western United States. Arch Environ Contam Toxicol 52:294-305. 321 Herbert BMJ, Halsall CJ, Fitzpatrick L, Villa S, Jones KC, Thomas GO. 2004. Use and validation of novel snow samplers for hydrophobic, semi-volatile organic compounds (SVOCs). Chemosphere 56:22735. 322 Jantunen LMM, Bidleman TF. 1998. Organochlorine pesticides and enantiomers of chiral pesticides in Arctic Ocean water. Arch Environ Contam Toxicol 35:218–28. 323 Bidleman T, Macdonald R, Stow J. 2003. Canadian Arctic Contaminants Assessment Report II: Sources, Occurrence, Trends and Pathways in the Physical Environment. Northern Contaminants Programme, Indian and Northern Affairs Canada, Ottawa. http://www.aincinac.gc.ca/nth/ct/ncp/pubs/phy/phy-eng.pdf. Annex E information on ENDOSULFAN 55 UNEP/POPS/POPRC.1/4 concentrations in the western Arctic, specifically the Bering and Chukchi Seas.” [emphasis added]324 Dust 230. Monitoring in the Caribbean, at the Virgin Islands and Trinidad, identified Endosulfan at all sites, and it was shown to have blown there in dust from Mali in the African Sahara/Sahel region.325 Animals 231. A North Pacific Research Board report published in 2008 reported alphaand beta-Endosulfan in common murre eggs of the North Pacific. Levels in murre eggs measured in 2003 at St. Lazuria Island for beta-Endosulfan ranged from 3.04 to 11.2 ng/g (mean 5.89 ng/g) and for alpha-Endosulfan from 0.116 to 0.428 ng/g (mean 0.236 ng/g). At Middleton Island in the Gulf of Alaska, measured levels in 2004 in murre eggs for beta-Endosulfan ranged up to 11.8 ng/g (mean of 6.74 ng/g). Alpha- and beta-Endosulfan were also found in common murre eggs at East Anatuli Island, Duck Island, Gull Island, Cape Denbigh, Cape Pierce, Sledge Island, Bluff and Bogoslov Island.326 232. The Cook Inlet, Alaska, Contaminants Study found the following Endosulfan levels in Chinook and sockeye salmon:327 Table 7: Endosulfan residues in salmon, Cook Inlet Alaska (ng/kg) Maximum Minimum Average Chinook 780 308 544 Sockeye 1610 252 664 No of samples 2 4 233. Braune et al. (2005) reported that over 20 years monitoring of POPs in the Canadian Arctic, there was a 3-fold increase in age-adjusted concentrations of Endosulfan sulfate in beluga at the same time as most other POPs were 324 Weber J, Halsall CJ, Muir DCG, Teixeira C, Burniston DA, Strachan WMJ, Hung H, Mackay N, Arnold D, Kylin H. 2006. Endosulfan and γ-HCH in the Arctic: an assessment of surface seawater concentrations and air-sea exchange. Environ Sci Technol 40:7570-6. 325 Garrison VH, Foreman WT, Genualdi S, Griffin DW, Kellogg CA, Majewski MS, Mohammed A, Ramsubhag A, Shinn EA, Simonich SL, Smith GW. 2006. Saharan dust – a carrier of persistent organic pollutants, metals and microbes to the Caribbean? Rev Biol Trop 54(Suppl 3):9-21. 326 Roseneau DG, Becker PR, Vander Pol SS, Day RD, Point D, Simac KS, Moors AJ, Ellisor MB, Pugh RS, York GS. 2008. Expanding the Seabird Tissue Archival and Monitoring Project (STAMP) in the North Pacific: Geographic Patterns in Contaminant Residues in Seabird Eggs Used in Rural Subsistence Diets. North Pacific Research Board Project Final Report (NPRB Project 0534). http://doc.nprb.org/web/05_prjs/534_Final%20Report%20(Mar%202008)%20(2).pdf 327 Survey of Chemical Contaminants in Fish, Invertebrates, and Plants Collected in the Vicinity of Tyonek, Seldovia, Port Graham, and Nanwalek in Cook Inlet, Alaska. December 2003. Prepared by the U.S. Environmental Protection Agency Region 10 Office of Environmental Assessment (EPA 910-R-01-003). http://yosemite.epa.gov/r10/oea.nsf/Risk+Assessment/Cook+Inlet+Seafood+Study. Annex E information on ENDOSULFAN 56 UNEP/POPS/POPRC.1/4 declining.328 234. Stern & Ikonomou (2003) reported a 3.2-fold increase of Endosulfan sulfate measured in Cumberland Sound beluga blubber over the 20-year time period from 1982-2002.329 235. Similarly, Evans et al. (2005) reported increasing residues of Endosulfan in the freshwater fish char—they were 2.2 times higher in 2002 than 1992.330 236. The geographic trend of increasing concentrations of Endosulfan in seawater of the western Arctic, specifically the Chukchi and Bering Seas, corresponds to levels of alpha-Endosulfan found in ringed seals, with the highest levels found in the western Arctic off Barrow, Alaska (geometric mean in ringed seal blubber combined males and females of 22.6 ng/g alpha-Endosulfan with the upper concentration at 43.39 ng/g).331 237. Endosulfan was measured in the blubber of beluga at 15 sites in the Canadian arctic between 1993 and 2001, at levels reaching 94 ug/kg.332 238. Bentzenen et al. (2008) found alpha-Endosulfan in the fat, but not the blood, of polar bears sampled along the Alaskan Beaufort Sea coast in spring, 2003. The levels measured were: mean 2 and range <0.1-21 ng/g wet weight fat, and mean 4 and range <0.1-36 ng/g lipid weight.333 239. Vorkamp et al. (2004) found residues of Endosulfan in every species they tested in Greenland. In the following results, the values are all for total Endosulfan, ng/g live weight, and are the highest median and maximum for various tissues and locations per species. In terrestrial species the residues were ptarmigan (median 1.9 and max 3.0 in liver), hare (median 0.55 and max 0.64 in liver), lamb (median n.d. and max 0.65 in liver), caribou (median 0.17 and max 328 Braune BM, Outridge PM, Fisk AT, Muir DCG, Helm PA, Hobbs K, Hoekstra PF, Kuzyk ZA, Kwan M, Letcher RJ, Lockhart WL, Norstrom RJ, Stern GA, Stirling I. 2005. Persistent organic pollutants and mercury in marine biota of the Canadian Arctic: an overview of spatial and temporal trends. Sci Total Environ 351-352: 4-56. 329 Stern GA, Ikonomou MG. 2003. Temporal trends of OC contaminants in south eastern Baffin (Pangnirtung) beluga. Synopsis of research conducted under the 2001-2003 Northern Contaminants Program. Ottawa: Department of Indian Affairs and Northern Development. p 181-90. http://www.aincinac.gc.ca/nth/ct/ncp/pub-eng.asp 330 Evans MS, Muir D, Lockhart WL, Stern G, Ryan M, Roach P. 2005. Persistent organic pollutants and metals in the freshwater biota of the Canadian Subarctic and Arctic: an overview. Sci Total Environ 351352:94-147. 331 Mackay N, Arnold D. 2005. Evaluation and Interpretation of Environmental Data on Endosulfan in Arctic Regions. Draft Report for Bayer CropScience Report Number CEA.107. 332 Stern GA, Macdonald CR, Armstrong D, Dunn B, Fuchs C, Harwood L, Muir DCG, Rosenburg B. 2005. Spatial trends and factors affecting variation of organochlorine contaminants levels in Canadian Arctic beluga (Delphinapterus leucas). Sci Total Environ 351-352:344-68. 333 Bentzen TW, Muir DCG, Amstrup SC, O’Hara TM. 2008. Organohalogen concentrations in blood and adipose tissue of Southern Beaufort Sea polar bears. Sci Total Environ 406:352-67. Annex E information on ENDOSULFAN 57 UNEP/POPS/POPRC.1/4 0.39 in muscle), muskox (median 0.016 and max 1.8 in blubber). In freshwater fish, Arctic char they found residues at all 3 locations sampled, with the highest residues being at Ittoqortoormiit (median 21 and max 92 in muscle tissue). In marine invertebrates they measured residues in shrimp (median 3 and max 5.2 in muscle), snow crab (median 19 in muscle and max 95 in liver), and Iceland scallop (median 0.36 and max 1.6 in muscle). In marine fish they measured residues in Atlantic cod, redfish, Atlantic salmon, Greenland halibut, wolfish, capelin, shorthorn sculpin, with the highest median value being in the muscle of capelin sampled at Nuuk (50 ng/g), and the highest single measurement being in the muscle of Atlantic cod also sampled at Nuuk (780 ng/g). In seabirds they measured residues in common eider (median 4.9 and max 8.6 in liver), king eider (median 3.7 in liver and max 10 in muscle), kittiwake (median 62 and max 130 in muscle), thick-billed murre (median 8.8 and max 15 in liver). In marine mammals they measured residues in ringed seal (median 5.6 in liver at Qeqertarsuaq and max 25 in muscle at Ittoqqortoomiit), harp seal (median 12 and max 45 in blubber), minke whale (median 12 and max 29), beluga (median 45 and max 83 in skin), and narwhal (median 81 and max 120 in skin).334 240. Contamination is also occurring in Antarctica: both alpha-Endosulfan and Endosulfan sulphate have been found in blubber of elephant seals in Antarctica with significantly higher relative proportions in pups compared with adults, thought to be due to maternal transfer. The levels found (median 3.02 and 2.68 ug/kg lipid for adult males and females) are similar to those found in Greenland.335 241. Alpha-Endosulfan was found in 40% of samples of Antarctic krill (Euphausia superba) taken from 12 sites between 300 and 800E (60-700S) in 2006. “Antarctic krill (Euphausia superba) is a keystone species in the Antarctic with the majority of Antarctic predators feeding either exclusively or opportunistically on the krill swarms that form during the austral summer.” The geometric mean level detected was 418 pg/g lw, the maximum was 451 pg/g lw.336 Plants 242. In measurements conducted in five western US national parks, including Denali National Park in Alaska, Endosulfan sulphate accumulated preferentially 334 Vorkamp K, Riget F, Glasius M, Pecseli M, Lebeuf M, Muir D. 2004. Chlorobenzenes, chlorinated pesticides, coplanar chlorobiphenyls and other organochlorine compounds in Greenland biota. Sci Total Environ 331(1-3):157-75. 335 Miranda-Filho KC, Metcalfe TL, Metcalfe CD, Robaldo RB, Muelbert MMC, Colares EP, Martinez PE, Bianchini A. 2007. Residues of persistent organochlorine contaminants in southern elephant seals (Mirounga leonina) from Elephant Island, Antarctica. Environ Sci Technol 41:3829-35. 336 Bengston Nash SM, Poulsen AH, Kawaguchi S, Vetter W, Schlabach M. 2008. Persistent organohalogen contaminant burdens in Antarctic krill (Euphausia superba) from the eastern Antarctic sector: A baseline study. Sci Total Environ 407(1):304-14. Annex E information on ENDOSULFAN 58 UNEP/POPS/POPRC.1/4 in lichen when compared with other media including conifer needles, passive air samplers, and snow.337 243. In a study measuring residues of persistent organic contaminants in Himalayan spruce needles in central Himalayas (Zhangmu-Nyalam), alphaEndosulfan was found to be one of the 3 most ubiquitous contaminants, in more than 95% of samples, with levels increasing with altitude.338 244. Endosulfan was measured in grasses in the Himalayas, in the Mt. Qomolangma (Everest) region of the Tibetan Plateau: alpha-Endosulfan (range 0.29-3.14 ng/g) and beta-Endosulfan (range 0.10-1.54 ng/g). There were no detectable residues in the soil, indicating that the source of the residues in plants was deposition from the air.339 245. Endosulfan was measured in lichen in the mountains of western Canada. Of the three forms, Endosulfan sulphate was present in the highest quantities (range 1,621-15,399 pg/g dry weight), with alpha- (range 403-1,678 pg/g) and betaEndosulfan (range 694-4,632 pg/g) also present in all samples.340 246. In a study of orographic cold-trapping of POPs by vegetation, specifically in conifer needles, in the mountain areas of Alberta and British Columbia, Canada, Endosulfan was found in conifer needles at levels of 11-2930 pg/g dry weight, with the level increasing with altitude.341 Modelling data - information regarding bio-availability (f) National and international risk evaluations, assessments or profiles and labelling information and hazard classifications, as available (provide summary information and relevant references) 337 Schrlau J. 2007. Comparison between Lichen, Conifer Needles, Resin-Based Passive Air Sampling Devices (PASDs), and Snow to Monitor Semi-Volatile Organic Compounds(SOCs) in the Atmosphere. Masters Thesis, Oregon State University. http://ir.library.oregonstate.edu/dspace/handle/1957/7442. 338 Wang XP, Yao TD, Cong ZY, Yan XL, Kang SC, Zhang Y. 2006. Gradient distribution of persistent organic contaminants along northern slope of central-Himalayas, China. Sci Total Environ 372:193-202. 339 Wang XP, Yao TD, Cong ZY, Yan XL, Kang SC, Zhang Y. 2007. Distribution of persistent organic pollutants in soil and grasses around Mt. Qomolangma, China. Arch Environ Contam Toxicol 52(2):153062. 340 Daly GL, Lei YD, Teixeira C, Muir DCG, Wania F. 2007. Pesticides in western Canadian mountain air and soil. Environ Sci Technol 41:6020-5. 341 Davidson DA, Wilkinson AC, Blais JM. 2003. Orographic cold-trapping of persistent organic pollutants by vegetation in mountains of western Canada. Environ Sci Technol 37(2):209-15. Annex E information on ENDOSULFAN 59 UNEP/POPS/POPRC.1/4 247. The recent decision, by New Zealand’s Environmental Risk Management Authority, to revoke the registration of Endosulfan contains the following statements about risk:342 “Based on their hazardous properties and their lifecycles and use patterns, endosulfan and endosulfan formulations have the potential to cause adverse effects to: workers involved in the manufacture of the substances; workers and bystanders should an incident occur in transportation or storage of the substances; users of the substances; the public from spray drift; the public who use any sports grounds, golf courses or bowling greens that have been treated; the public through exposure to residues in food; the public through long range transport, through food residues, leading to breast milk and fat tissue residues; the environment from spillage, seepage, runoff or long range transport; the relationship of Maori [indigenous people of New Zealand] to the environment through exposure of water, soil and native flora and fauna to the substances.” “There is a high acute and chronic risk to aquatic species (fish and invertebrates) from all current uses of endosulfan in New Zealand.” “The Committee considers there are significant risks to Maori cultural wellbeing, society and the community and to New Zealand’s international relationships.” “The Committee considers that there are no significant benefits associated with the availability of endosulfan and endosulfan formulations.” “Taking into account, the approach to risk, the precautionary approach and the effects of the substances being unavailable, the Committee considers that the high level of adverse effects (risks and costs) to the environment, human health, the relationship of Maori to the environment and New Zealand’s international relationships outweigh any positive effects (benefits) associated with the availability of endosulfan and endosulfan formulations in New Zealand.” (g) Status of the chemical under international conventions 342 ERMANZ. 2008. Environmental Risk Management Authority Decision. Application Code HRC07003. 10 December 2008. http://www.ermanz.govt.nz/search/registers.html?id=23290. Annex E information on ENDOSULFAN 60