DRAFT Technical Guidelines for Environmentally Sound Management of wastes consisting of, containing or contaminated with the pesticides aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene, Mirex or Toxaphene 7 2005 December 2004
December 2004 DRAFT Technical Guidelines for Environmentally Sound Management of Wastes consisting of, containing or contaminated with the pesticides Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene, Mirex or Toxaphene 7 April 2005
Table of contents ntroduction Description, production, use and wastes (a) Description (c) Use 2. Chlordane (a) Description (c) U 3. Dieldrin (a) Description (b) Produc (c) Use(see also Aldrin) 4. Endrin (a) Description (b) Productio (a) Description 555555666667777777788888888999 (a) Description (b) Production. mIrex (a) Descrip (a) Descrip 99900 4pril,2005
[Document Number!] i April, 2005 Table of Contents I. Introduction ................................................................................................................. 5 A. Scope........................................................................................................................... 5 B. Description, production, use and wastes......................................................................... 5 1. Aldrin.......................................................................................................................... 5 (a) Descriription ................................................................................................................ 5 (b) Production.................................................................................................................... 5 (c) Use.............................................................................................................................. 6 2. Chlordane .............................................................................................................................. 6 (a) Description................................................................................................................... 6 (b) Production.................................................................................................................... 6 (c) Use.............................................................................................................................. 6 3. Dieldrin ................................................................................................................................. 7 (a) Description................................................................................................................... 7 (b) Production.................................................................................................................... 7 (c) Use (see also Aldrin)..................................................................................................... 7 4. Endrin ................................................................................................................................... 7 (a) Description................................................................................................................... 7 (b) Production.................................................................................................................... 7 (c) Use.............................................................................................................................. 7 5 HCB ................................................................................................................................... 8 (a) Description................................................................................................................... 8 (b) Production.................................................................................................................... 8 (c) Use.............................................................................................................................. 8 6 Heptachlor.............................................................................................................................. 8 (a) Description................................................................................................................... 8 (b) Production.................................................................................................................... 8 (c) Use.............................................................................................................................. 8 7 Mirex ................................................................................................................................... 9 (a) Description................................................................................................................... 9 (b) Production.................................................................................................................... 9 (c) Use.............................................................................................................................. 9 8. Toxaphene ............................................................................................................................. 9 (a) Description................................................................................................................... 9 (b) Production.................................................................................................................... 9 (c) Use............................................................................................................................ 10 9 Wastes....................................................................................................................... 10
Relevant provisions of the Basel and Stockholm Conventions Basel Convention Stockholm Convention Issues under the Stockholm Convention to be addressed cooperatively with the basel Convention Low pOP content Levels of destruction and irreversible transformation Methods that constitute environmentally sound disposal Guidance on environmenta ally sound management(ESM Basel Convention Stockholm Convention 3. Organization for Economic Cooperation and Development. 13 Legislative and regulatory framework Waste prevention and minimization... D Identification and inventories Sampling, analysis and monitoring ..... S pling 6 analysis (a) Field tests (b) Laboratory analysis Monitoring 17 Handling, collection, packaging, labelling, transportation and storage 17 2. Collection 3. Packaging 19 Labelling Transportation 6 G Environmentally sound disposal 20 Destruction and irreversible transformation methods 234 Other disposal methods when destruction or irreversible transformation does not represent the environmentally preferable option Other disposal methods when the POP content is low 21 Remediation of contaminated sites 4pril,2005
[Document Number!] ii April, 2005 II. Relevant provisions of the Basel and Stockholm Conventions ....................................... 11 A. Basel Convention ....................................................................................................... 11 B. Stockholm Convention................................................................................................ 12 III. Issues under the Stockholm Convention to be addressed cooperatively with the Basel Convention................................................................................................................. 12 A. Low POP content........................................................................................................ 12 B. Levels of destruction and irreversible transformation .................................................... 12 C. Methods that constitute environmentally sound disposal................................................ 12 IV. Guidance on environmentally sound management (ESM).............................................. 13 A. General considerations................................................................................................ 13 1. Basel Convention ....................................................................................................... 13 2. Stockholm Convention................................................................................................ 13 3. Organization for Economic Cooperation and Development............................................ 13 B. Legislative and regulatory framework .......................................................................... 13 C. Waste prevention and minimization ............................................................................. 14 D. Identification and inventories...................................................................................... 14 1. Identification.............................................................................................................. 14 2. Inventories................................................................................................................. 15 E. Sampling, analysis and monitoring .............................................................................. 16 1. Sampling.................................................................................................................... 16 2. Analysis..................................................................................................................... 16 (a) Field tests................................................................................................................... 17 (b) Laboratory analysis..................................................................................................... 17 3. Monitoring................................................................................................................. 17 F. Handling, collection, packaging, labelling, transportation and storage ............................ 17 1. Handling.................................................................................................................... 18 2. Collection .................................................................................................................. 18 3. Packaging.................................................................................................................. 19 4 Labelling.................................................................................................................... 19 5. Transportation............................................................................................................ 19 6. Storage ...................................................................................................................... 20 G. Environmentally sound disposal .................................................................................. 20 1. Pretreatment............................................................................................................... 20 2. Destruction and irreversible transformation methods..................................................... 20 3. Other disposal methods when destruction or irreversible transformation does not represent the environmentally preferable option .......................................................................... 20 4. Other disposal methods when the POP content is low.................................................... 21 H. Remediation of contaminated sites............................................................................... 21
Health and safety 21 High-volume, high-concentration or high-risk situations Low-volume low-concentration sites or low-risk situations J Emergency response 23 K. Public participation. Synonyms and trade names for POPs pesticides 24 Annex Il Bibliography 4pril,2005
[Document Number!] iii April, 2005 I. Health and safety........................................................................................................ 21 1. High-volume, high-concentration or high-risk situations............................................... 21 2. Low-volume, low-concentration sites or low-risk situations........................................... 22 J. Emergency response................................................................................................................. 23 K. Public participation.................................................................................................................. 23 Annex I: Synonyms and trade names for POPs pesticides………………………………………………………….24 Annex II: Bibliography………………………………………………………………………………………………30
Abbreviations and acronyms European Agreement of Road Transport Hazardous Waste Materials ATSDR Agency for Toxic Substances and Disease Registr BAT Best Available Techniques Best environmental practice Conference of the parties Dichloro-diphenyl-trichloroethane Environmentally sound management European Union FAO Food and Agriculture Organisation Gas chromatography GCMS cromatography mass spectrometry HEO 1 2,3, 4, 10, 10-hexachloro-6, 7-epoxy-1, 4, 4a, 5, 6, 7, 8, 8a-octahydro- endo-1, 4-exo-5, 8. -dimetha HHDN 1,2,3,4, 1910-hexachloro, 1, 4, 4a.5, 8, 8a-hexachydro-exo-1, 4-endo-5, 8-dimethanonaphtaleleanonaphthalene HCB Hexachlorobenzene Health and safety Plan HPLC High-pressure liquid chromatograph nternational Air Transport Association ICAO nternational Civil Aviation Organisation International Civil Aviation Organisation Technical Instructions for the Transport of Dangerous Goods IMDG Code International Maritime Dangerous Goods Code IMO International Maritime Organisation Intergovernmental Negotiating Committee IPCS International Programme on Chemical Safety IPCS INCHEM International Programme on Chemical Safety Information on Chemicals Mass spectrometry OECD Organization for Economic Cooperation and Development OEWG Open Ended Working Group Occupational Safety and Health Administration acific island countries PCB Polychlorinated biphenyl PCC PCDD Polychlorinated dibenzo-p-dioxins PCDF Polychlorinated dibenzofurans Persistent organic pollutant Pesticide POPs Group of pesticides being: Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene(HCB), Mirex or Toxaphene except DDT PPE Personal protective equipment PVC Polyvinylchloride RID International Regulations Concerning the Carriage of Dangerous Goods by rail SDS Safety data Sheets Stoffdatenbank fur altlasten- /umweltrelevante Stoffe TEQ KHSE Health Safety Executive United Nations code NECE United Nations Economic Commission for Europ NEP United Nations Environment Programme SEPA United States Environmental Protection Agency WHO World Health Organization Units of measurement Milligram(s) per kilogram. Corresponds to parts per million Microgram(s) per kilogram. Corresponds to parts per billion Nanogram(s)per kilogram. Corresponds to parts per trillion mass 叩叩叩 Parts per billion ts per mI rts per trillion tons tons in Si units 4pril,2005
[Document Number!] iv April, 2005 Abbreviations and Acronyms ADR European Agreement of Road Transport Hazardous Waste Materials ATSDR Agency for Toxic Substances and Disease Registry BAT Best Available Techniques BEP Best Environmental Practices COP Conference of the Parties DDT Dichloro-diphenyl-trichloroethane ESM Environmentally sound management EU European Union FAO Food and Agriculture Organisation GC Gas chromatography GCMS Gas chromatography mass spectrometry HEOD 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro- endo-1,4- exo-5,8,-dimethanonaphthalene HHDN 1,2,3,4,1910-hexachloro, 1,4,4a,5,8,8a-hexachydro-exo-1,4-endo-5,8-dimethanonaphtalene HCB Hexachlorobenzene HASP Health and Safety Plan HPLC High-pressure liquid chromatograph IATA International Air Transport Association ICAO International Civil Aviation Organisation ICAO TI International Civil Aviation Organisation Technical Instructions for the Transport of Dangerous Goods IMDG Code International Maritime Dangerous Goods Code IMO International Maritime Organisation INC Intergovernmental Negotiating Committee IPCS International Programme on Chemical Safety IPCS INCHEM International Programme on Chemical Safety Information on Chemicals MS Mass spectrometry OECD Organization for Economic Cooperation and Development OEWG Open Ended Working Group OSHA Occupational Safety and Health Administration PICs Pacific Island Countries PCB Polychlorinated biphenyl PCC Polychlorinated camphenes PCDD Polychlorinated dibenzo-p-dioxins PCDF Polychlorinated dibenzofurans POP Persistent organic pollutant Pesticide POPs Group of pesticides being: Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene (HCB), Mirex or Toxaphene except DDT PPE Personal protective equipment PVC Polyvinylchloride RID International Regulations Concerning the Carriage of Dangerous Goods by Rail SDS Safety Data Sheets STARS Stoffdatenbank für altlasten- /umweltrelevante Stoffe TEQ Toxic equivalent(s) UK HSE Health & Safety Executive UN code United Nations code UNECE United Nations Economic Commission for Europe UNEP United Nations Environment Programme US EPA United States Environmental Protection Agency WHO World Health Organization Units of measurement mg/kg Milligram(s) per kilogram. Corresponds to parts per million (ppm) by mass. μg/kg Microgram(s) per kilogram. Corresponds to parts per billion (ppb) by mass. ng/kg Nanogram(s) per kilogram. Corresponds to parts per trillion (ppt) by mass. ppb Parts per billion ppm Parts per million ppt Parts per trillion tons tons in SI units
. Introduction These technical guide lines prov ide guidance for the environmentally sound management(ESm)of wastes consisting of, containing or contaminated with the pesticides aldrin, chlordane, dieldrin, endrin, heptachlor, hexachlorobenzene(HCB), mirex or toxaphene(abbreviated as"Pesticide POPs")in accordance with decisions V/8. V1/23 and vIl/13 of the Conference of the parties to the basel Convention on the Control of Transboundary Movements of Hazardous Wastes and Their Disposal, decisions OEWG-1/4, OEWG-11710 and oEwG-111/8 of the Open-ended Working Group of the Basel Convention, and taking into account Resolution 5 of the Conference of Plenipotentiaries on the Stockholm Convention on Persistent Organic Pollutants and decisions INC-675 and INC-7/6 of the Intergovemmental Negotiating Committee for International Legally Binding Instrument for Implementing Intermational Action on Certain Persistent Organic Pollutants. The Conference of the Parties to the Stockholm Convention on Persistent Organic Pollutants may consider these guidelines in accordance with article 6.2 of that convention 2 In these technical guidelines all pesticides listed as Persistent Organic Pollutants(POPs) in Annex A of the Stockholm Convention are addressed. Dichloro-diphenyl-trichloroethane(dDt) has been addressed separately in Annex B of the Stockholm Convention and is addressed in separate technical guidelines owing to its importance for malaria vector control in many tropicalcountries HCB as an unintentionally produced POP and as an industrial chemical is not covered by thes guidelines. HCB as an unintentionally produced POP will be addressed in technical guidelines for the environmentally sound management of wastes consisting of, conta ining or contam inated with PCDDs, PCDFs or unintentionally produced PCBs or HCB HCB asan industrial chemical will be addressed in technical guidelines for the env ironmenta lly sound management of wastes consisting of, conta ining or contaminated /ith HCb as an industrial chem ical 4. This document should be used in conjunction with the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent nature and occurrence of wastes consisting of, conta iningor contaminated with pesticide POPs(exceptIon Organic Pollutants(General Technical Guidelines). This document provides more detailed information on the for purposes of their identification and management B. Description, production, use and wastes Aldrin Aldrin are white, odourless crystals, when they are pure. Technical grades are tan to dark brown with a mild chem ical odour(Ritter, year). Aldrin contains no less than 95%1, 2, 3, 4, 10, 10-hexachloro 1, 4, 4a, 5, 8, 8a-hexahydro-exo-1, 4-endo-5, 8-dimethanonaphtalene(HHDN). HHDN is a white, crystalline odourless solid with a melting point of 104 to 1045C. Technical aldrin is a tan to dark brown solid with a melting range from 49 to 60C. It is practically insoluble in water, moderately soluble in petroleum oil and stable to heat alkali and mild acids(ATSDR, 2002; IPCS, no date, WHO-FAO, 1979). Pure a ldrin is stable at <200C and between a pH-range from 4 to 8, however, oxidizing agents and concentrated acids attack the unchlorinated ring under any conditions. Aldrin is non-corrosive or slightly corrosive to metals because of the slow formation of hydrogen chloride on storage. Aldrin and Dieldrin are the common names oftwo insecticides, which are chem ically closely related. Aldrin is readily converted to dieldrin in the environment ( Global Pesticides Release Database, Environment Canada, no date). See annex I for examples of trade names (a) Production condensation was usually performed at approx ima tely 120C and atatmospheric pressure Excel ctured by Aldrin was first synthesized as a pesticide in the United States in 1948. Aldrin was manufa the Diels-Alder reaction of hexachlorocyclopentadiene with bicyclo[2. 2. 11-2, 5-heptadiene. The fin bicyclohepta diene was removed by distillation. The final product was usually further purified by recrystallization. Aldrin has been manufactured commercially since the 1950, and used throughout the world up to the early 1970s(ATSDR 2002, UNEP 2003 d) April 2005 5
[Document Number] April 2005 5 I. Introduction A. Scope 1. These technical guidelines provide guidance for the environmentally sound management (ESM) of wastes consisting of, containing or contaminated with the pesticides aldrin, chlordane, dieldrin, endrin, heptachlor, hexachlorobenzene (HCB), mirex or toxaphene (abbreviated as “Pesticide POPs”) in accordance with decisions V/8, VI/23 and VII/13 of the Conference of the Parties to the Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and Their Disposal, decisions OEWG-I/4, OEWG-II/10 and OEWG-III/8 of the Open-ended Working Group of the Basel Convention, and taking into account Resolution 5 of the Conference of Plenipotentiaries on the Stockholm Convention on Persistent Organic Pollutants and decisions INC-6/5 and INC-7/6 of the Intergovernmental Negotiating Committee for an International Legally Binding Instrument for Implementing International Action on Certain Persistent Organic Pollutants. The Conference of the Parties to the Stockholm Convention on Persistent Organic Pollutants may consider these guidelines in accordance with article 6.2 of that convention. 2. In these technical guidelines all pesticides listed as Persistent Organic Pollutants (POPs) in Annex A of the Stockholm Convention are addressed. Dichloro-diphenyl-trichloroethane (DDT) has been addressed separately in Annex B of the Stockholm Convention and is addressed in separate technical guidelines owing to its importance for malaria vector control in many tropical countries. 3. HCB as an unintentionally produced POP and as an industrial chemical is not covered by these guidelines. HCB as an unintentionally produced POP will be addressed in technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with PCDDs, PCDFs or unintentionally produced PCBs or HCB. HCB as an industrial chemical will be addressed in technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with HCB as an industrial chemical. 4. This document should be used in conjunction with the General Technical Guidelinesfor Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants (General Technical Guidelines). This document provides more detailed information on the nature and occurrence of wastes consisting of, containing or contaminated with pesticide POPs (except DDT) for purposes of their identification and management. B. Description, production, use and wastes 1. Aldrin (a) Description 5. Aldrin are white, odourless crystals, when they are pure. Technical grades are tan to dark brown with a mild chemical odour (Ritter, year). Aldrin contains no less than 95 % 1,2,3,4,10,10-hexachloro, 1,4,4a,5,8,8a -hexahydro-exo-1,4-endo-5,8-dimethanonaphtalene (HHDN). HHDN is a white, crystalline, odourless solid with a melting point of 104 to 104.5 °C. Technical aldrin is a tan to dark brown solid with a melting range from 49 to 60 °C. It is practically insoluble in water, moderately soluble in petroleum oil and stable to heat alkali and mild acids (ATSDR, 2002; IPCS, no date; WHO-FAO, 1979). Pure aldrin is stable at < 200 °C and between a pH-range from 4 to 8, however, oxidizing agents and concentrated acids attack the unchlorinated ring under any conditions. Aldrin is non-corrosive or slightly corrosive to metals because of the slow formation of hydrogen chloride on storage. Aldrin and Dieldrin are the common names of two insecticides, which are chemically closely related. Aldrin is readily converted to dieldrin in the environment (Global Pesticides Release Database, Environment Canada, no date). See annex I for examples of trade names. (a) Production 6. Aldrin was first synthesized as a pesticide in the United States in 1948. Aldrin was manufactured by the Diels-Alder reaction of hexachlorocyclopentadiene with bicyclo[2.2.1]-2,5-heptadiene. The final condensation was usually performed at approximately 120 °C and at atmospheric pressure. Excess bicycloheptadiene was removed by distillation. The final product was usually further purified by recrystallization. Aldrin has been manufactured commercially since the 1950, and used throughout the world up to the early 1970s (ATSDR 2002, UNEP 2003 d)
b)Use Aldrin has been manufactured commercially since 1950 and used throughout the world up to the early 1970s to control soil pests such as corn rootworm, wireworms, rice water weevil, and grasshoppers. It has also been used to protect wooden structures, plastic and rubber coverings of electrical and telecommunication cables(ATSDR, 2002; UNEP, 2002a). In 1966, aldrin use in the United States peaked at 8, 550,000 kg, but by 1970, use had decreased to 4, 720,000 kg. 8. n 1970, the U.S. Department of Agriculture cancelled all uses of aldrin and dieldrin due to the concern that these chemica ls could cause a severe environmental damage to aquatic ecosystems and their potentially carcinogenic properties. In early 1971, US EPA initiated the cancellation proceedings for aldrin and dieldrin, but did not order the suspension of aldrin and dieldrin use. In 1972, under the authority of the Federal Insecticide, Fungicide and Rodenticide Act as amended by the Federal Pesticide Control Act of 1972, an epa order lifted the cancellation of aldrin and dieldrin use in three cases Subsurface ground insertion for term ite control Dipping of nonfood plant roots and tops and Mothproofing in manufacturing processes using completely closed systems Most of the information on aldrin is also applicable for dieldrin 2. Chlordane (a) Description Technical chlordane is a viscous mixture of at least 23 different components, including chlo dane isomers, other hlorinated hydrocarbons, and by-products. The main constituents of technical chlordanes are trans-chlordane (gamma-chlordane)(share of about 25%), cis-chlordane(alpha-chlordane)(share of about 70%), heptachlor, trans-nonachlor, and cis-nonachlor(share less than 1 %) Heptachlor is one of the most active components of technicalchlordane Chlordane is a viscous, colourless or amber-coloured liquid with a chlorine -like odour Pure chlordane hasa melting point of 104C, is not soluble in water and stable in most organic solvents, including petroleum oils. It is unsta ble in the presence of weak alkalis (ATSDR, 1994; EXTOXNET, Holoubek, 2004; IPCS, no date; UNEP, 2002a; WHO-FAO, 1979). See annex I for examples of trade names b)Production Chlordane is produced by chlorinating cyclopentadiene to form hexachlorocyclopentadiene and condensing the latter with cyclopentadiene to form chlordene. The chlordene is further chlorinated at high temperature and pressure to chlordane(ATSDR, 2002; UNEP, 2003d 10. The raw materials for the manufacturing process are cyclopentadiene, hexachloro-cyclopentadiene and chlorine, or some chlorinating agent Chlordane is manufactured in a two-step reaction. In the first step hexachlorocyclopentadiene reacts with cyclopentadiene in a Diels-Alder reaction. The reaction is exothermic and proceeds readily at a temperature up to about 100C. The intermediate is called"chlordane".In the next step, chlorine is added to the unsubstituted double bond. Various chlorinated agents e.g sulphuryl chloride and catalysts, such as ferrochloride have been described to make addition dominant oversubstitution, but it is believed that only chlorine is used in actual practice(De Bruin, 1979) (c)Use 11. Chlordane, which was introduced on the market for the first time in 1945, is a broad-spectrum contact insecticide that had been employed on agricultural crops, on lawns and gardens. It has also extensively been used in the control of term ites, cockroaches, ants and other household pests (Fiedler, 2000; UNEP 2002a).In China, chlordane is still used asa termicide in buildings and dams. China has requested a specifi 200, ption for the use as a termicide according to Art.4 and Annex A of the Stockholm Convention(UNEP, In 1988. the commercial use of chlordane was cancelled in the United States. Between 1983 and 1988 the sole/core use for chlordane was to control subterranean termites. For this purpose, chlordane was applied primarily as a liquid that was poured or injected around the foundation of a building. Chlordane, in onjunction with heptachlor, was at one time widely used as a pesticide for the control of insects on various types of agricultural crops and vegetation. The use pattern for chlordane in the mid 1970s was as follows 35% used by pest control operators, mostly on termites; 28% on agricultural crops, including com and citrus, 30%for home lawn and garden use; and 7 on turf and ornamentals. In 1978, a final cancellation notice was issued which called for the suspension of the use of chlordane except for subsurface injection to control termites and for dipping roots and tops of nonfood plants. Minor use of chlordane for treating nonfood plants April2005 6
[Document Number] April 2005 6 (b) Use 7. Aldrin has been manufactured commercially since 1950 and used throughout the world up to the early 1970s to control soil pests such as corn rootworm, wireworms, rice water weevil, and grasshoppers. It has also been used to protect wooden structures, plastic and rubber coverings of electrical and telecommunication cables (ATSDR, 2002; UNEP, 2002a). In 1966, aldrin use in the United States peaked at 8,550,000 kg, but by 1970, use had decreased to 4,720,000 kg. 8. In 1970, the U.S. Department of Agriculture cancelled all uses of aldrin and dieldrin due to the concern that these chemicals could cause a severe environmental damage to aquatic ecosystems and their potentially carcinogenic properties. In early 1971, US EPA initiated the cancellation proceedings for aldrin and dieldrin, but did not order the suspension of aldrin and dieldrin use. In 1972, under the authority of the Federal Insecticide, Fungicide and Rodenticide Act as amended by the Federal Pesticide Control Act of 1972, an EPA order lifted the cancellation of aldrin and dieldrin use in three cases: • Subsurface ground insertion for termite control; • Dipping of nonfood plant roots and tops; and • Mothproofing in manufacturing processes using completely closed systems. Most of the information on aldrin is also applicable for dieldrin. 2. Chlordane (a) Description Technical chlordane is a viscous mixture of at least 23 different components, including chlo rdane isomers, other chlorinated hydrocarbons, and by-products. The main constituents of technical chlordanes are trans-chlordane (gamma-chlordane) (share of about 25 %), cis-chlordane (alpha -chlordane) (share of about 70%), heptachlor, trans-nonachlor, and cis-nonachlor (share less than 1 %). Heptachlor is one of the most active components of technical chlordane. Chlordane is a viscous, colourless or amber-coloured liquid with a chlorine-like odour. Pure chlordane has a melting point of 104 °C, is not soluble in water and stable in most organic solvents, including petroleum oils. It is unstable in the presence of weak alkalis. (ATSDR, 1994; EXTOXNET, Holoubek, 2004; IPCS, no date; UNEP, 2002a; WHO-FAO, 1979). See annex I for examples of trade names. (b) Production 9. Chlordane is produced by chlorinating cyclopentadiene to form hexachlorocyclopentadiene and condensing the latter with cyclopentadiene to form chlordene. The chlordene is further chlorinated at high temperature and pressure to chlordane (ATSDR, 2002; UNEP, 2003d). 10. The raw materials for the manufacturing process are cyclopentadiene, hexachloro - cyclopentadiene and chlorine, or some chlorinating agent. Chlordane is manufactured in a two -step reaction. In the first step, hexachlorocyclopentadiene reacts with cyclopentadiene in a Diels-Alder reaction. The reaction is exothermic and proceeds readily at a temperature up to about 100 °C. The intermediate is called “chlordane”. In the next step, chlorine is added to the unsubstituted double bond. Various chlorinated agents e.g. sulphuryl chloride, and catalysts, such as ferrochloride have been described to make addition dominant over substitution, but it is believed that only chlorine is used in actual practice (De Bruin, 1979). (c) Use 11. Chlordane, which was introduced on the market for the first time in 1945, is a broad-spectrum contact insecticide that had been employed on agricultural crops, on lawns and gardens.It has also extensively been used in the control of termites, cockroaches, ants and other household pests (Fiedler, 2000; UNEP, 2002a). In China, chlordane is still used as a termicide in buildings and dams. China has requested a specific exemption for the use as a termicide according to Art.4 and Annex A of the Stockholm Convention (UNEP, 2002b). 12. In 1988, the commercial use of chlordane was cancelled in the United States. Between 1983 and 1988 the sole/core use for chlordane was to control subterranean termites. For this purpose, chlordane was applied primarily as a liquid that was poured or injected around the foundation of a building. Chlordane, in conjunction with heptachlor, was at one time widely used as a pesticide for the control of insects on various types of agricultural crops and vegetation. The use pattern for chlordane in the mid 1970s was as follows: 35 % used by pest control operators, mostly on termites; 28 % on agricultural crops, including corn and citrus; 30 % for home lawn and garden use; and 7 % on turf and ornamentals. In 1978, a final cancellation notice was issued which called for the suspension of the use of chlordane except for subsurface injection to control termites and for dipping roots and tops of nonfood plants. Minor use of chlordane for treating nonfood plants
was cancelled by 1983. The use of chlordane decreased drastically in the 1970s when EPa cancelled all uses other than subterranean term ite control(ATSDR, 2002) 3. Dieldrin (a)Description 13. Dieldrin is a technical product containing 85 %of the chemical known as 1, 2, 3, 4, 10, 10-hexachlorc 6,7-epoxy-1, 4, 4a, 5, 6, 7, 8, 8a-octahydro-endo-1, 4-exo-5,8.dimethanonaphthalene(HEOD). Dieldrin is closely related to its meta bolic precursor aldrin. The pure major ingredient HEOD is a white crystalline solid with melting point of 176/177C. Technical dieldrin is a light tan flaky solid with a melting point of 150C. In water, it is practically insoluble and slightly so luble in alcohol. Pure HEOD is stable in alkali and diluted acids, but reacts with strong acids (ATSDR, 2002; IPCS, year; WHO-FAO, 1975). See annex I for examples of trade b)Production Dieldrin was manufactured by epoxidation of aldrin. The epoxidation of aldrin was obtained by reaction with a peracid(producing dieldrin and an acid byproduct)or with hydrogen peroxide and a tungstic oxide catalyst(producing dieldrin and water). Peracetic acid and perbenzoic acid were genera lly used as the peracid acid. When using a peracid, the epoxidation reaction was performed noncatalytically or with an acid catalyst, such as sulfuric acid or phosphoric acid. When using hydrogen peroxide, tungsten trioxide was genera lly used as the catalyst(ATSDR, 2002; UNEP, 2003d) (c) Use(see also Aldrin) 5. Dieldrin was ma inly used for the control of soil insects such as com rootworms, wireworms and catworms(UNEP, 2002a). Besides, dieldrin was and is still used in public health protection to control several insect vectors(ATSDR, 2002; Fiedler, 2000).In India, its manufacture and import are banned, but marketing and restricted use(locust control) is perm itted fora period of 2 years of the date of expiry, which date is earlier. Restricted use of dieldrin is reported from Bangladesh, Myanmarand Nepal(UNEP, 2002c) 4. Endrin (a) Description Endrin, when pure, is a white crystalline solid and has a melting point of200C. It is decomposed at temperatures above 245C (Boiling point). The technical product is a light tan powder with a characteristic odour. It is practically insoluble in water and slightly soluble in alcohol. It is stable in alkali and acids, but it rearranges to less insecticidally active substances in the presence of strong acids, on the exposure to sunlight or on heating above 200C (ATSDR, 1996; IPCS, year, WHO-FAO, 1975) b) Production Endrin is a stereoisomer of dieldrin produced by the reaction of vinyl chloride and hexachlorocyclopentadiene to yield a product, which is then dehydrochlorinated and condensed with cyclopentadiene to produce isodrin. This intermediate is then epoxidized with pera cetic or perbenzoic acid to yield endrin. An alternative production method involves condensation of hexachlorocyclopentad iene with acetylene to yield the intermediate for condensation with cyclopentadiene(ATSDR, 2002; UNEP, 2003d) 18. It is estimated that 2, 345,000 kgofendrin were sold in the United States in 1962, while less than 450,000 kg were produced in 1971. More recent estimates of domestic production of endrin could not be found. As with many toxic chemicals, information on production or use of pesticides is often proprietary, and quantitative estimates of production of endrin are virtually impossible to obtain. No information on the production of endrin was available from the Toxic Release Inventory (TrD), because endrin is not one of the products, but occurred as impurities ofendrin or as degradation products. While commercial preparations chemicals that producers are required to report on. Endrin aldehyde and endrin ketone never were commercia solid endrin were typically 95-98% pure, the following chemicals(in addition to endrin aldehyde and endrin ketone)have been found as trace impurities in commercialendrin products: aldrin, dieldrin, isodrin heptachloronorbornadiene, and heptachloronorborene(HSDB, 1995). The active ingredient would often be mixed with one or more organic solvents for application in a liquid form. Carriers included xy lene, hexane, and cyclohexane(ATSDR, 2002; UNEP, 2003d). See annex I for examples of trade names Beginning in 1951, endrin was first used as an insecticide, rodenticide, and avicide to control cutworms, mice, voles, grasshoppers, borers, and other pests on cotton, sugarcane, tobacco, apple orchards and grain. It was also used as an insecticide agent on bird perches, but has never been extensively used for April2005 7
[Document Number] April 2005 7 was cancelled by 1983. The use of chlordane decreased drastically in the 1970s when EPA cancelled all uses other than subterranean termite control (ATSDR, 2002). 3. Dieldrin (a) Description 13. Dieldrin is a technical product containing 85 % of the chemical known as 1,2,3,4,10,10-hexachloro- 6,7-epoxy-1,4,4a,5,6,7,8,8a -octahydro- endo-1,4- exo-5,8,-dimethanonaphthalene (HEOD). Dieldrin is closely related to its metabolic precursor aldrin. The pure major ingredient HEOD is a white crystalline solid with a melting point of 176/177 °C. Technical dieldrin is a light tan flaky solid with a melting point of 150 °C. In water, it is practically insoluble and slightly soluble in alcohol. Pure HEOD is stable in alkali and diluted acids, but reacts with strong acids (ATSDR, 2002; IPCS, year; WHO-FAO, 1975). See annex I for examples of trade names. (b) Production 14. Dieldrin was manufactured by epoxidation of aldrin. The epoxidation of aldrin was obtained by reaction with a peracid (producing dieldrin and an acid byproduct) or with hydrogen peroxide and a tungstic oxide catalyst (producing dieldrin and wa ter). Peracetic acid and perbenzoic acid were generally used as the peracid acid. When using a peracid, the epoxidation reaction was performed noncatalytically or with an acid catalyst, such as sulfuric acid or phosphoric acid. When using hydrogen peroxide, tungsten trioxide was generally used as the catalyst (ATSDR, 2002; UNEP, 2003d). (c) Use (see also Aldrin) 15. Dieldrin was mainly used for the control of soil insects such as corn rootworms, wireworms and catworms (UNEP, 2002a). Besides, dieldrin was and is still used in public health protection to control several insect vectors (ATSDR, 2002; Fiedler, 2000).In India, its manufacture and import are banned, but marketing and restricted use (locust control) is permitted for a period of 2 years of the date of expiry , which date is earlier. Restricted use of dieldrin is reported from Bangladesh, Myanmar and Nepal (UNEP, 2002c). 4. Endrin (a) Description 16. Endrin, when pure, is a white crystalline solid and has a melting point of 200 °C. It is decomposed at temperatures above 245 °C (Boiling point). The technical product is a light tan powder with a characteristic odour. It is practically insoluble in water and slightly soluble in alcohol. It is stable in alkali and acids, but it rearranges to less insecticidally active substances in the presence of strong acids, on the exposure to sunlight or on heating above 200 °C (ATSDR, 1996; IPCS, year; WHO-FAO, 1975). (b) Production 17. Endrin is a stereoisomer of dieldrin produced by the reaction of vinyl chloride and hexachlorocyclopentadiene to yield a product, which is then dehydrochlorinated and condensed with cyclopentadiene to produce isodrin. This intermediate is then epoxidized with peracetic or perbenzoic acid to yield endrin. An alternative production method involves condensation of h exachlorocyclopentadiene with acetylene to yield the intermediate for condensation with cyclopentadiene (ATSDR, 2002; UNEP, 2003d). 18. It is estimated that 2,345,000 kg of endrin were sold in the United States in 1962, while less than 450,000 kg were produced in 1971. More recent estimates of domestic production of endrin could not be found. As with many toxic chemicals, information on production or use of pesticides is often proprietary, and quantitative estimates of production of endrin are virtually impossible to obtain. No information on the production of endrin was available from the Toxic Release Inventory (TRI), because endrin is not one of the chemicals that producers are required to report on. Endrin aldehyde and endrin ketone never were commercial products, but occurred as impurities of endrin or as degradation products. While commercial preparations of solid endrin were typically 95-98 % pure, the following chemicals (in addition to endrin aldehyde and endrin ketone) have been found as trace impurities in commercial endrin products: aldrin, dieldrin, isodrin, heptachloronorbornadiene, and heptachloronorborene (HSDB, 1995). The active ingredient would often be mixed with one or more organic solvents for application in a liquid form. Carriers included xy lene, hexane, and cyclohexane (ATSDR, 2002; UNEP, 2003d). See annex I for examples of trade names. (c) Use 19. Beginning in 1951, endrin was first used as an insecticide, rodenticide, and avicide to control cutworms, mice, voles, grasshoppers, borers, and other pests on cotton, sugarcane, tobacco, apple orchards, and grain. It was also used as an insecticide agent on bird perches, but has never been extensively used for
termite-proofing or other applications in urban areas, even if it has many chemicalsimilarities with aldrin dieldrin. Endrin's toxicity to nontarget populations of raptors and migratory birds was a major reason for cancellation asa pesticide agent. Except for use as a toxicant on bird perches, which was cancelled n 1991 the manufacturer voluntarily canceled all other uses of endrin in the United States in 1986. It has been estimated that 6, 250 kg of endrin were used annually in the United States prior to 1983. Both the EPA and FDA revoked all food tolerances for endrin in 1993(ATSDR 2002, Fiedler 2000) 5 HCB (a)Description 20. Hexachlorobenzene(HCB)consists of a colourless white powder or needles with a melting range of 229 to 326C Products in technical or agricultural grade contain% HCB and up to 2% impurities(1.8% pentachlorobenzene and 0. 2 %1, 2, 4, 5-tetrachlorobenzene including higher chlorinated dibenzo-p-dioxins, dibenzofurans and bipheny ls ). Its melting point is over 200C. HCB is practically insoluble in water, slightly soluble in cold alcohol. It is stable in strong acids and its decomposition in a lka lis continues very slowly (ATSDR, 2002; IPCS, year, WHO-FAO, 1977, Holoubek et al, 2004). See annex I for examples of trade b)Production The compound can be produced commercially by reacting benzene with excess chlorine in the presence of ferric chloride at 150-200C Hexachlorobenzene is currently produced asa by-product or impurity in the production process of several pesticides, including pentachloronitrobenzene(PCNB), tetrachloroisophthalonitrile(chlorothalonil), 4-amino-3, 5, 6-trichloropicolinic acid(picloram ) pentachlorophenol(PCP)(only in Europe)and dimethy ltetrachloroterephthalate DCPA or Dacthal)and was also produced as a by-product during the production of atrazine, propazine, simazine, and mirex(De Bruin 1979;, ATSDR,2002) (e)Use Hexachlorobenzene (HCB)was used world-wide as a fungicide for agricultural purposes from 1915 on. HCB was widely used as a pesticide, mainly as a seed dressing to prevent fungal disease on gra in and field crops such as wheat and rye. Its use in industry is not described here(Holoubek, 2004 ). HCB has been extensively applied in the Russian Federation and is therefore a pesticide of serious environmental concern in that area. (ATSDR, 2002; Fiedler, 2000; UNEP, 2002b) 6 Heptachlor (a)Description Pure heptachlor is a white crystalline solid with a melting point of 95/96C. Technical heptachlor is a soft waxy solid with a melting range between 46 and 74C. It is practically insoluble in water and slightly soluble in alcohol. It is stable up to temperatures between 150 and 160C as well as towards light, air moisture, alkalies and acids. It is not readily dechlorinated, but is susceptible to epoxidation (ATSDR 1993 IPCS, no year, WHO-FAO, 1975). See annex I for examples of trade names (b) Production HeptachlorwasfirstregisteredforuseasaninsecticideintheUnitedStatesin1952.commercial production began in 1953. Heptachlor is commercially produced by free-radical chlorination of chlordene in benzene containing 0.5%to 5.0%of fuller's earth. The production process is run for up to 8 hours, since the reaction rate is very low. The chlordene starting material is prepared by the Diels-Alder condensation of hexachlorocyclopentadiene with cyclopentadiene Technical-grade heptachlor usually consists of 72% heptachlor and 28% impurities such as trans-chlordane, cis-chlordane, and nonachlor (De Bruin, 1979 ATSDR, 1993) (c)Use 25 Heptachlor is a persistent dermal insecticide with some fumigant action. It is nonphytotoxic at insecticidal concentrations. Heptachlor was used extensively from 1953 to 1974 as a soil and seed treatment to protect com, small grains, and sorghum from pests. It was used to control ants, cutworms, maggots, termites, thrips, weevils, and wireworms in both cultivated and uncultivated soils. Heptachlor was also used a white to brown naturally occurring earthy substance, that has a substantial ability urities orcolouring bodies from fats, oils. Its name originated with the textile industry, in which textile workers(or fullers)cleaned raw wool by kneading it in a mixture of water an earth that adsorbed oil, dirt, and other contaminants from the April 2005 8
[Document Number] April 2005 8 termite-proofing or other applications in urban areas, even if it has many chemical similarities with aldrin and dieldrin.. Endrin’s toxicity to nontarget populations of raptors and migratory birds was a major reason for its cancellation as a pesticide agent. Except for use as a toxicant on bird perches, which was cancelled in 1991, the manufacturer voluntarily canceled all other uses of endrin in the United States in 1986. It has been estimated that 6,250 kg of endrin were used annually in the United States prior to 1983. Both the EPA and FDA revoked all food tolerances for endrin in 1993 (ATSDR 2002, Fiedler 2000). 5 HCB (a) Description 20. Hexachlorobenzene (HCB) consists of a colourless white powder or needles with a melting range of 229 to 326 °C. Products in technical or agricultural grade contain 98 % HCB and up to 2 % impurities (1.8 % pentachlorobenzene and 0.2 % 1,2,4,5-tetrachlorobenzene including higher chlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls). Its melting point is over 200 °C. HCB is practically insoluble in water, slightly soluble in cold alcohol. It is stable in strong acids and its decomposition in alkalis continues very slowly (ATSDR, 2002; IPCS, year; WHO-FAO, 1977; Holoubek et al, 2004). See annex I for examples of trade names. (b) Production 21. The compound can be produced commercially by reacting benzene with excess chlorine in t he presence of ferric chloride at 150–200 °C. Hexachlorobenzene is currently produced as a by-product or impurity in the production process of several pesticides, including pentachloronitrobenzene (PCNB), tetrachloroisophthalonitrile (chlorothalonil), 4-amino-3,5,6-trichloropicolinic acid (picloram), pentachlorophenol (PCP) (only in Europe) and dimethyltetrachloroterephthalate (DCPA or Dacthal®) and was also produced as a by-product during the production of atrazine, propazine, simazine, and mirex (De Bruin , 1979; ATSDR, 2002). (c) Use 22. Hexachlorobenzene (HCB) was used world-wide as a fungicide for agricultural purposes from 1915 on. HCB was widely used as a pesticide, mainly as a seed dressing to prevent fungal disease on grain and field crops such as wheat and rye. Its use in industry is not described here (Holoubek, 2004). HCB has been extensively applied in the Russian Federation and is therefore a pesticide of serious environmental concern in that area. (ATSDR, 2002; Fiedler, 2000; UNEP, 2002b). 6 Heptachlor (a) Description 23. Pure heptachlor is a white crystalline solid with a melting point of 95/96 °C. Technical heptachlor is a soft waxy solid with a melting range between 46 and 74 °C. It is practically insoluble in water and slightly soluble in alcohol. It is stable up to temperatures between 150 and 160 °C as well as towards light, air moisture, alkalies and acids. It is not readily dechlorinated, but is susceptible to epoxidation (ATSDR 1993; IPCS, no year; WHO-FAO, 1975). See annex I for examples of trade names. (b) Production 24. Heptachlor was first registered for use as an insecticide in the United States in 1952. Commercial production began in 1953. Heptachlor is commercially produced by free-radical chlorination of chlordene in benzene containing 0.5 % to 5.0 % of fuller’s earth1 . The production process is run for up to 8 hours, since the reaction rate is very low. The chlordene starting material is prepared by the Diels-Alder condensation of hexachlorocyclopentadiene with cyclopentadiene. Technical-grade heptachlor usually consists of 72 % heptachlor and 28 % impurities such as trans-chlordane, cis-chlordane, and nonachlor (De Bruin, 1979; ATSDR, 1993). (c) Use 25. Heptachlor is a persistent dermal insecticide with some fumigant action. It is nonphytotoxic at insecticidal concentrations. Heptachlor was used extensively from 1953 to 1974 as a soil and seed treatment to protect corn, small grains, and sorghum from pests. It was used to control ants, cutworms, maggots, termites, thrips, weevils, and wireworms in both cultivated and uncultivated soils. Heptachlor was also used 1A white to brown naturally occurring earthy substance, that has a substantial ability to adsorb impurities or colouring bodies from fats, grease, or oils. Its name originated with the textile industry, in which textile workers (or fullers) cleaned raw wool by kneading it in a mixture of water and fine earth that adsorbed oil, dirt, and other contaminants from the…
nonagriculturally during this time period to control termites and household insects (ATSDR, 1993; Fiedler, 2000 7 Mirex (a)Description Mirex is a white, odourless crystalline with a melting point of 485C and as such fire resistant. It is soluble in several organic solvents including tetrahydrofuran (30 %), carbon disulfide(18%), chloroform (17%), and benzene(12 %) but is practically insoluble in water. Mirex is considered to be extremely stable It does not react with sulfuric, nitric, hydrochloric or other common acids and is unreactive with bases chlorine or ozone In the environment, it degrades to photom irex, when exposed to sunlight(ATSDR, 1995 IPCS, year, USEPA, 2000b). See annex I for examples of trade names b) Production 27 Although it was originally synthesized in 1946, mirex was not commercially introduced in the United States until 1959, when it was produced under the name GC-1283 for use in pesticide formulatic as an industrial fire retardant under the trade name Dechlorane(R Mirex was produced as a result oftheonsand dimerization of hexachlorocyclopentadiene in the presence of an alum num chloride catalyst(ATSDR, 1995) Technical grade preparations of mirex conta ined about 95%mirex with about 2. 6 mg/kg chlordecone asa contaminant. Several formulations of mirex have been prepared in the past forvarious pesticide uses. Some of the more commonly used formulations of m irex used as baits were made from corn cob grit impregnated with vegetable oil and various concentrations of mirex Insect bait formulations for aerial or ground applications contained 3-0.5%mirex, and fire ant formulations contained 0.075-0.3% mirex (ARC 1979) Because it is nonflammable, mirex was marketed primarily as a flame retardant additive in the United States from 1959to 1972 under the trade name dechlorane R for use in various coatings, plastics ubber, paint, paper, and electrical goods Mirex was most commonly used in the 1960s asan insecticide to control the imported fire ants in 9 Southen States in the U.S. Mirex was chosen for fire ant eradication programs because of its effectiveness and selectiveness forants. It was originally applied aerially at concentrations of.3-0.5%. However, aerial application of mirex was replaced by mound application because of suspected toxicity to estuarine species. As well, the goal of the fire ant program was shifted/changed from eradication to selective control. Mirex was also used successfully in controlling populations of leaf cutter ants in South America, harvester termites in South Africa, Western harvesterants in the U.S., mealybugs in pineapples in Hawaii, and yellowjacket wasps in the US. All registered products containing mirex were effectively cancelled in December 1977. However, selected ground application was allowed until June 1978, at which time the product was banned in the U.s with the exception of continued use in Hawaii on pineapples until stocks on hand were exhausted. China has applied for an exemption from the Stockholm Convention for the production and use of mirex as a termicide. There is a limited production and some local use as a termicide(ATSDR, 1995; UNEP, 2002b) 8. Toxaphene (a)Description Toxaphene is an insecticide conta ining over 670 polychlorinated byciclic terpenes consisting predominantly of chlorinated camphene. Toxaphene formulations included wettable powders, emulsifiable concentrates, dusts, granules, baits, oils, and emulsions(IARC 1979, ATSDR 1996). In its original form, it is a yellow to am ber waxy solid that smells like turpentine. (see below) Its melting range is from 65 to 90C boiling point in water is above 120%C which is the temperature where it starts to decompose Toxaphene s tends to evaporate when in solid form or when mixed with liquids and does not bum Toxaphene is also nown as camphechlor, chlorocamphene, polychlorocamphene, and chlorinated camphene(ATSDR, 1996 Fiedler, 2000; IPCS, no year, USEPA, 2000b). See annex I for examples of trade names Technical toxaphene can be produced commercially by reacting chlorine gas with technical camphene in the presence of ultraviolet radiation and catalysts, yielding chlorinated camphene containing 67 69% chlorine by weight. It has been available in various forms: a solid containing 100% technical toxaphene a 90% solution in xylene or oil; a wettable powder containing 40% toxaphene, dusts conta ning 5 to 20 and 40% toxaphene, granules containing 10 or 20 toxaphene emulsifia ble concentrates in concentrations of 4, 6
[Document Number] April 2005 9 nonagriculturally during this time period to control termites and household insects (ATSDR, 1993; Fiedler, 2000). 7 Mirex (a) Description 26. Mirex is a white, odourless crystalline with a melting point of 485 °C and as such fire resistant. It is soluble in several organic solvents including tetrahydrofuran (30 %), carbon disulfide (18 %), chloroform (17 %), and benzene (12 %), but is practically insoluble in water. Mirex is considered to be extremely stable. It does not react with sulfuric, nitric, hydrochloric or other common acids and is unreactive with bases, chlorine or ozone. In the environment, it degrades to photomirex, when exposed to sunlight (ATSDR, 1995; IPCS, year; USEPA, 2000b). See annex I for examples of trade names. (b) Production 27. Although it was originally synthesized in 1946, mirex was not commercially introduced in the United States until 1959, when it was produced under the name GC-1283 for use in pesticide formulations and as an industrial fire retardant under the trade name Dechlorane®. Mirex was produced as a result of the dimerization of hexachlorocyclopentadiene in the presence of an aluminum chloride catalyst (ATSDR, 1995). Technical grade preparations of mirex contained about 95 % mirex with about 2.6 mg/kg chlordecone as a contaminant. Several formulations of mirex have been prepared in the past for various pesticide uses. Some of the more commonly used formulations of mirex used as baits were made from corn cob grit impregnated with vegetable oil and various concentrations of mirex. Insect bait formulations for aerial or ground applications contained 0.3-0.5% mirex, and fire ant formulations contained 0.075-0.3% mirex (IARC 1979). (c) Use 28. Because it is nonflammable, mirex was marketed primarily as a flame retardant additive in the United States from 1959 to 1972 under the trade name Dechlorane® for use in various coatings, plastics, rubber, paint, paper, and electrical goods. 29. Mirex was most commonly used in the 1960s as an insecticide to control the imported fire ants in 9 Southern States in the U.S. Mirex was chosen for fire ant eradication programs because of its effectiveness and selectiveness for ants. It was originally applied aerially at concentrations of 0.3 -0.5 %. However, aerial application of mirex was replaced by mound application because of suspected toxicity to estuarine species. As well, the goal of the fire ant program was shifted/changed from eradication to selective control. Mirex was also used successfully in controlling populations of leaf cutter ants in South America, harvester termites in South Africa, Western harvester ants in the U.S., mealybugs in pineapples in Hawaii, and yellowjacket wasps in the US. All registered products containing mirex were effectively cancelled in December 1977. However, selected ground application was allowed until June 1978, at which time the product was banned in the U.S. with the exception of continued use in Hawaii on pineapples until stocks on hand were exhausted. 30. China has applied for an exemption from the Stockholm Convention for the production and use of mirex as a termicide. There is a limited production and some local use as a termicide (ATSDR, 1995; UNEP, 2002b). 8. Toxaphene (a) Description 31. Toxaphene is an insecticide containing over 670 polychlorinated byciclic terpenes consisting predominantly of chlorinated camphenes. Toxaphene formulations included wettable powders, emulsifiable concentrates, dusts, granules, baits, oils, and emulsions (IARC 1979, ATSDR 1996). In its original form, it is a yellow to amber waxy solid that smells like turpentine. (see below) Its melting range is from 65 to 90 °C. Its boiling point in water is above 120 °C, which is the temperature where it starts to decompose. Toxaphene tends to evaporate when in solid form or when mixed with liquids and does not burn. Toxaphene is also known as camphechlor, chlorocamphene, polychlorocamphene, and chlorinated camphene (ATSDR, 1996; Fiedler, 2000; IPCS, no year; USEPA, 2000b). See annex I for examples of trade names. (b) Production 32. Technical toxaphene can be produced commercially by reacting chlorine gas with technical camphene in the presence of ultraviolet radiation and catalysts, yielding chlorinated camphene containing 67 - 69% chlorine by weight. It has been available in various forms: a solid containing 100% technical toxaphene; a 90% solution in xylene or oil; a wettable powder containing 40 % toxaphene; dusts containing 5 to 20 and 40 % toxaphene;granules containing 10 or 20 % toxaphene;emulsifiable concentrates in concentrations of 4 , 6
