BC

UNEP/CHW.7/INF/21

Distr.: General4 October 2004

English only

Conference of the Parties to the Basel Conventionon the Control of Transboundary Movements ofHazardous Wastes and Their DisposalSeventh meetingGeneva, 25-29 October 2004Item 6 of the provisional agenda

Report on the implementation of the decisions adoptedby the Conference of the Parties at its sixth meeting

German comments of 19 November 2004

Comments are made on some issues in revision mode. More comments may be made at a later stage when these guidelines have been brought in line with the General technical guideline and the technical guideline regarding PCBs. For the comments invited by the COP by 31

January 2005 a revised document should be made available if possible.

Draft technical guidelines for environmentally sound management of wastes consisting of, containing or contaminated with the pesticides Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene, Mirex and Toxaphene

Attached is a first draft of the technical guidelines for environmentally sound management of pesticides wastes arising from the production of Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene (HCB), Mirex and Toxaphene, prepared by the Secretariat for the information of the meeting.

UNEP/CHW.7/1.

121004

For reasons of economy, this document is printed in a limited number. Delegates are kindly requested to bring their copies to meetings and not to request additional copies.

UNEP/CHW.7/INF/21

Table of Contents

1.0 Introduction............................................................................................................................................6

1.1 Scope......................................................................................................................................................6

1.2 Description, production, use and wastes................................................................................................6

1.2.1 Description.............................................................................................................................................6

1.2.2 Production..............................................................................................................................................8

1.2.3 Use.......................................................................................................................................................10

2.0 Relevant provisions of the Basel and Stockholm Conventions......................................................12

2.1 Basel Convention.................................................................................................................................12

2.2 Stockholm Convention........................................................................................................................13

3.0 Issues under the Stockholm Convention to be addressed cooperatively with the Basel Convention..........................................................................................................................................13

3.1 Low POP content.................................................................................................................................13

3.2 Levels of destruction and irreversible transformation.........................................................................14

3.3 Methods that constitute environmentally sound disposal....................................................................14

4.0 Guidance on Environmentally Sound Management (ESM)..........................................................15

4.1 General considerations.........................................................................................................................15

4.1.1 Basel Convention.................................................................................................................................15

4.1.2 Stockholm Convention........................................................................................................................15

4.1.3 Organization for Economic Cooperation and Development (OECD).................................................15

4.2 Legislative and regulatory framework.................................................................................................15

4.3 Waste prevention and minimization....................................................................................................16

4.4 Identification and inventories..............................................................................................................16

4.4.1 Identification........................................................................................................................................16

4.4.2 Inventories...........................................................................................................................................17

4.5 Sampling, analysis and monitoring......................................................................................................18

4.5.1 Sampling..............................................................................................................................................18

4.5.2 Analysis...............................................................................................................................................18

4.5.3 Monitoring...........................................................................................................................................19

4.6 Handling, collection, packaging, labelling, transportation and storage...............................................19

4.6.1 Handling .............................................................................................................................................20

4.6.2 Collection.............................................................................................................................................20

4.6.3 Packaging.............................................................................................................................................20

4.6.4 Labelling..............................................................................................................................................21

4.6.5 Transportation......................................................................................................................................21

4.6.6 Storage.................................................................................................................................................22

4.7 Environmentally sound disposal..........................................................................................................22

4.7.0 Introduction..........................................................................................................................................22

4.7.1 Reformulation......................................................................................................................................22

4.7.2 Pre-treatment........................................................................................................................................23

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4.7.2 Destruction and irreversible transformation methods..........................................................................24

4.7.3 Other disposal methods when destruction or irreversible transformation does not represent the environmentally preferable option.................................................................................44

4.7.4 Other disposal methods when the POP pesticide content is low.........................................................45

4.8 Remediation of contaminated sites......................................................................................................46

4.8.1 Contaminated site identification..........................................................................................................46

4.8.2 Environmentally sound remediation....................................................................................................46

4.9 Health and safety.................................................................................................................................46

4.9.2. High-volume, high-concentration or high-risk situations....................................................................47

4.9.3. Low-volume, low-concentration sites or low-risk situations..............................................................48

4.10 Emergency response............................................................................................................................48

4.11 Public participation..............................................................................................................................49

Appendix 2: References.............................................................................................................................................50

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Abbreviations and AcronymsABS Acrylonitrile butadiene styreneADR European Agreement of Road Transport Hazardous Waste MaterialsATSDR Agency for Toxic Substances and Disease RegistryBAT Best Available TechniquesBCD Base Catalyzed DecompositionBEP Best Environmental PracticesCerOx Cerium OxidationCFC ChlorofluorocarbonsCOP Conference of the PartiesDDT Dichloro-diphenyl-trichloroethaneDE Destruction efficiencyDRE Destruction removal efficiencyESM Environmentally sound managementEU European UnionFAO Food and Agriculture OrganisationFRTR Federal Remediation Technologies RoundtableFTO Flameless Thermal OxidizerGAC Granular Activated CarbonGC Gas chromatographyGCMS Gas chromatography mass spectrometryGEF Global Environmental FacilityGPCR Gas phase chemical reductionGTZ Gesellschaft für Technische Zusammenarbeit, (Germany)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,-dimethanonaphthaleneHHDN 1,2,3,4,1910-hexachloro, 1,4,4a,5,8,8a-hexachydro-exo-1,4-endo-5,8-dimethanonaphtaleneHCB HexachlorobenzeneHASP Health and Safety PlanHPLC High-pressure liquid chromatographICV In-Situ Container VitrificationIMDG Code International Maritime Dangerous Goods CodeIMO International Maritime OrganisationINC Intergovernmental Negotiating CommitteeIPPC Integrated Pollution Prevention ControlISTD In-Situ Thermal DesorptionIPCS International Programme on Chemical SafetyLWPS Liquid Waste Pre-heater SystemMEO Mediated electro-chemical oxidationMS Mass spectrometry OECD Organization for Economic Cooperation and DevelopmentOEWG Open Ended Working GroupOSHA Occupational Safety and Health Administration OTGS Off-Gas Treatment SystemPACT Plasma Arc Centrifugal TreatmentPAH Polycyclic aromatic hydrocarbonsPBB Polybrominated biphenylPCB Polychlorinated biphenyl PCC Polychlorinated camphenesPCDD polychlorinated dibenzo-p-dioxinsPCDF Polychlorinated dibenzofuransPCP PentachlorphenolPCT Polychlorinated terphenylPOP Persistent organic pollutantPOPs pesticides Group of pesticides being: Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene (HCB), Mirex and ToxaphenePPE Personal protective equipmentPVC PolyvinylchloridePWC Plasma Waste ConverterSCWO Super-critical water oxidationSDS Safety Data SheetsSPV Subsurface Planar In-Situ Vitrification TCLP Toxicity Characteristics Leaching ProcedureTEQ Toxic equivalent(s)TSCA Toxic Substances Control Act TRBP Thermal Reduction Batch Processor

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UNECE United Nations Economic Commission for EuropeUNEP United Nations Environment ProgrammeUS EPA United States Environmental Protection AgencyWHO World Health Organization

Units of measurementmg/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 billionppm Parts per millionppt Parts per trillion

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1.0 Introduction

1.1 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 and toxaphene (abbreviated as “pesticide POPs except DDT”) in accordance with decisions V/8, VI/23, VII/[…] and VIII/[…] of the Conference of the Parties (COP) to the Basel Convention on the Control of Transboundary Movement of Hazardous Wastes and Their Disposal, I/4, II/10 and III/8 of the Open-ended Working Group of the Basel Convention (OEWG), and INC-6/5 and INC-7/6 of the Stockholm Convention on Persistent Organic Pollutants Intergovernmental Negotiating Committee for an International Legally Binding Instrument for Persistent Organic Pollutants. The Conference of the Parties to the Stockholm Convention will consider the guidelines in accordance with article 6, paragraph 2, of that Convention.

2. The pesticide 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) is not covered by these technical guidelines, because it is contained in Annex B to the Stockholm Convention whereas the other pesticide POPs except DDT are contained in Annex A to the Stockholm Convention. It will be addressed in technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with DDT.

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 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) (including unintentionally produced PCBs and 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 industrial chemical. 4.

5. 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 Organic Pollutants (General Technical Guidelines). This document provides more detailed information on the nature and occurrence of wastes consisting of, containing or contaminated with the pesticide POPs except DDT for purposes of identification and their management.

6.

1.2 Description, production, use and wastes

1.2.1 Description

1.2.1.1 Aldrin

7. White, odourless crystals when pure; technical grades are tan to dark brown with a mild chemical odour. (Ritter) Aldrin contains no less than 95% HHDN. HHDN is a white, crystalline, odourless solid with a melting point from 104 -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 to mild acids (ATSDR 2002, IPCS, WHO-FAO 1979). Aldrin is stable at < 200 °C and at pH 4 - 8, but oxidizing agents and concentrated acids attack the unchlorinated ring. 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 that are closely related chemically. Aldrin is readily converted to dieldrin in the environment (Global Pesticides Release Database, Environment Canada).

1.2.1.2 Chlordane

8. Technical chlordane is actually a mixture of at least 23 different components, including chlordane isomers, other chlorinated hydrocarbons, and by-products. The main constituents in technical Chlordanes are trans-chlordane (gamma-chlordane) with ca. 25%, cis-chlordane (alpha-chlordane) with ca 70%, heptachlor with less than 1%, trans-nonachlor, cis-nonachlor. Heptachlor is one of the most active components of technical chlordane. Chlordane is a viscous, colorless or amber-colored liquid with a chlorine-like odor. Chlordane has a melting point of 103 -105 °C and is not soluble in water, but stable in most organic solvents, including

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petroleum oils. It is unstable in the presence of weak alkalis. (ATSDR 1994, E X T O X N E T, Holoubek 2004, IPCS, UNEP 2002a,WHO-FAO 1979).

1.2.1.3 Dieldrin

9. Dieldrin is a technical product containing 85% of the chemical known as HEOD. Dieldrin is closely related to its metabolic precursor aldrin. The pure major ingredient HEOD is a white crystalline solid with melting point of 176-177 °C. Technical dieldrin is a light tan flaky solid with a melting point of 150 °C. It is practically insoluble in water and slightly soluble in alcohol. Pure HEOD is stable in alkali and diluted acids but reacts strong with acids (ATSDR 2002, IPCS, WHO-FAO 1975).

1.2.1.4 Endrin

10. Endrin, when pure, is a white crystalline solid with a melting point above 200 °C (with decomposition). The technical product is a light tan powder with a characteristic odor. 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, WHO-FAO January 1975).

1.2.1.6 HCB

11. Hexachlorobenzene (HCB) is a colorless white powder or needles with a melting range of 229 to 326 °C. Technical agricultural grade contains 98% HCB and upto 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, WHO-FAO 1977, Holoubek et al, 2004)

1.2.1.5 Heptachlor

12. Heptachlor is, when pure, a white crystalline solid with melting point of 95 to 96 °C. Technical chlordane is a soft waxy solid with a melting range of 46 to 74 °C and practically insoluble in water and slightly soluble in alcohol. It is stable towards heat to 150 to 160 °C and towards light, air moisture, alkalies and acids, it is not readily dechlorinated, but is susceptible to epoxidation (ATSDR 1993, IPCS, WHO-FAO 1975).

1.2.1.7 Mirex

13. Mirex is a white crystalline, odourless solid with a melting point of 485 °C and as such fire resisitant. 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, USEPA, 2000b).

1.2.1.8 Toxaphene

14. Toxaphene is an insecticide containing over 670 chemicals. It is usually found as a solid or gas, and in its original form, it is a yellow to amber waxy solid that smells like turpentine. It has been available in various forms: a solid containing 100% technical toxaphene; a 90% solution in xylene or oil; a 40% wettable powder; 5-20% and 40% dusts; 10% and 20% granules; 4%, 6%, and 9% emulsifiable concentrates; 1% baits; a 2: 1 toxaphene; DDT emulsion; and a 14% dust containing 7% DDT. Its melting range is from 65-90 °C. Its boiling point in water is above 120 °C (decomposes). Toxaphene tends to evaporate when in solid form or when mixed with liquids and will not burn. Toxaphene is also known as camphechlor, chlorocamphene, polychlorocamphene, and chlorinated camphene (ATSDR 1996, Fiedler 2000, IPCS, USEPA, 2000b). Other synonyms trade names can be found in Appendix 1.1.2.2 Production

1.2.2.1 Aldrin

15. Aldrin was first synthesized in the United States as a pesticide in 1948. Aldrin was manufactured by the Diels-Alder condensation of hexachlorocyclopentadiene with bicyclo[2.2.1]-2,5-heptadiene. The final

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condensation reaction 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 upto the early 1970s (ATSDR 2002, UNEP 2003 d).

1.2.2.2 Chlordane

16. 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).

17. 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 is reacted 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 unsubstitute 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). 1.2.2.3 Dieldrin

18. Dieldrin was manufactured by the epoxidation of aldrin. The epoxidation of aldrin was obtained by reacting it either 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 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).

1.2.2.4 Endrin

19. 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 hexachlorocyclopentadiene with acetylene to yield the intermediate for condensation with cyclopentadiene (ATSDR 2002, UNEP 2003d).

20. It is estimated that 2,345 tons of endrin were sold in the United States in 1962, while less than 450 tons 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 facilities are required to report. Endrin aldehyde and endrin ketone were never 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: aldrin, dieldrin, isodrin, heptachloronorbornadiene, and heptachloronorbornene (HSDB 1995). The active ingredient would often be mixed with one or more organic solvents for application in a liquid form. Carriers included xylene, hexane, and cyclohexane (ATSDR 2002, UNEP 2003d). Question: Have PCBs also been used as carrier?

1.2.2.5 HCB

21. The compound can be produced commercially by reacting benzene with excess chlorine in the presence of ferric chloride at 150–200 °C. Hexachlorobenzene is currently produced as a by-product or impurity in the manufacture of several 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).

1.2.2.6 Heptachlor

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22. Heptachlor was first registered for use in the United States as an insecticide in 1952 and commercial production began the following year. Heptachlor is produced commercially by the free-radical chlorination of chlordene in benzene containing from 0.5% to 5.0% of fuller’s earth. The reaction is run for up to 8 hours. 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)

1.2.2.7 Mirex

23. 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 95.18% mirex, with 2.58 mg/kg chlordecone as a contaminant. 24.25.

1.2.2.8 Toxaphene

26. 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 40% wettable powder; 5-20% and 40% dusts; 10% and 20% granules; 4%, 6%, and 9% emulsifiable concentrates; 1% baits; a 2: 1 toxaphene; DDT emulsion; and a 14% dust containing 7% DDT. In 1982, EPA canceled the registrations of toxaphene for most uses as a pesticide or pesticide ingredient, except for certain uses under specific terms and conditions (ATSDR, 1996).

27. Especially in the United States, the definition of “technical toxaphene” was patterned after the Hercules Incorporated product (Hercules Code Number 3956) marketed under the trademark name of “Toxaphene.” In recent years, Hercules Incorporated has essentially let the name of toxaphene lapse into the public domain so that many products with similar properties are referred to as toxaphene. Other companies used slightly different manufacturing processes, leading to a chlorinated camphene mixture with degrees of total chlorination and a distribution of specific congeners that are not the same as the Hercules Incorporated product. For instance, the toxaphene-like product commonly marketed under names like “Stroban(e)” had a slightly lowered degree of chlorination and used slightly different camphene or pinene feedstocks. In 1996, Toxaphene-like pesticide agents were still produced and were widely used in many countries. While it is impossible to quantify production figures or usage rates, India and many countries in Latin America, Eastern Europe, the former Soviet Union, and Africa were still using various toxaphene products as pesticides (ATSDR). Any more recent information on this available????

28. Toxaphene was introduced in 1949, and became the most heavily used organochlorine pesticide in the United States until its ban in 1982. High production rates were also reported for Brazil, the former Soviet Union and the former German Democratic Republic as well as for Central America (Voldner and Lie, 1993). While most attention has been focused on the intentional production of polychlorinated camphenes (PCCs) as pesticide agents, there is growing evidence that PCC congeners may be an unintentional byproduct of manufacturing processes that use chlorination, such as those for paper and pulp. Studies from places as far-flung as New Zealand, Japan, the Great Lakes region of the United States, and Scandinavia suggest that PCCs can be found in many parts of the world where toxaphene mixtures were never used as pesticide agents (ATSDR 1996).

1.2.3 Use

1.2.3.1 Aldrin

29. 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 tons, but by 1970, use had decreased to 4,720 tons.

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30. In 1970, the U.S. Department of Agriculture canceled all uses of aldrin and dieldrin based on the concern that these chemicals could cause severe aquatic environmental change and are potentially carcinogenic. Early in 1971, EPA initiated 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 moth-proofing in manufacturing processes using completely closed systems. Most of the information on aldrin is also applicable for dieldrin.

1.2.3.2 Chlordane

31. Chlordane is a broad-spectrum contact insecticide that had been employed on agricultural crops, and on lawns and gardens. Chlordane appeared in 1945 and it has also been used extensively in the control of termites, cockroaches, ants and other household pests (Fiedler, 2000, UNEP 2002a). In Asia, chlordane is still used in China as a termicide in buildings and dams and in Japan for the use as termicide in structure of houses. Both countries have requested exemption from the Stockholm Convention for the use as a termicide (UNEP 2002b).

32. In 1988, all commercial use of chlordane in the United States was canceled. Between 1983 and 1988 the sole 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 omamentals. 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 canceled by 1983. The use of chlordane decreased drastically in the 1970s when EPA moved to cancel all uses other than subterranean termite control (ATSDR 2002).

1.2.3.3 Dieldrin (See also under 1.2.3.1 Aldrin )

33. Dieldrin was used mainly 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).

1.2.3.4 Endrin

34. Endrin was first used as an insecticide, rodenticide, and avicide beginning in 1951 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. Unlike aldrin/dieldrin, with which it has many chemical similarities, endrin apparently was never used extensively for termite-proofing or other applications in urban areas. 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 canceled in 1991, all other uses of endrin in the United States were voluntarily canceled by the manufacturer in 1986. It has been estimated that 6.250 tons 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).

1.2.3.5 HCB

35. Hexachlorobenzene (HCB) was used world-wide as a fungicide for agricultural purposes from 1915. 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 is a pesticide of serious concern in the Russian Federation as it has been extensively applied (ATSDR 2002, Fiedler 2000, UNEP 2002b).

1.2.3.6 Heptachlor

36. 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,

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and wireworms in both cultivated and uncultivated soils. Heptachlor was also used nonagriculturally during this time period to control termites and household insects (ATSDR 1993, Fiedler 2000).

1.2.3.7 Mirex

37. 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).

38. 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 and because the goal of the fire ant program was 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 canceled 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. Until August 1976, chlordecone was registered in the United States for use on banana root borer (in the U.S. territory of Puerto Rico); this was its only registered food use. Additional registered formulations included non-food use on non-fruit bearing citrus trees to control rust mites; on tobacco to control tobacco and potato wireworms; and for control of the grass mole cricket, and various slugs, snails, and fire ants in buildings, lawns, and on ornamental shrubs. The highest reported concentration of chlordecone in a commercial product was 50%, which was used to control the grass mole cricket in Florida. Chlordecone has also been used in household products such as ant and roach traps at concentrations of approximately 0.125%. The concentration used in ant and roach bait was approximately 25%. All registered products containing chlordecone were effectively canceled as of May 1978 (ATSDR 1995, Fiedler 2000).

39. 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 use as a termicide (ATSDR, UNEP 2002b).

1.2.3.8 Toxaphene

40. Toxaphene was one of the most heavily used insecticides in the United States until 1982, when it was canceled for most uses; all uses were banned in 1990. Voldner and Lie (1993) estimated a global usage of 1.3 million tons from 1950 to 1993.

41. Toxaphene was formerly used as a nonsystemic stomach and contact insecticide with some acaricidal activity. Being nonphytotoxic (except to cucurbitus), it was used to control many insects thriving on cotton, corn, fruit, vegetables, and small grains and to control the Cussia obtusifola soybean pest. Toxaphene was also used to control livestock ectoparasites such as lice, flies, ticks, mange, and scab mites. Its relatively low toxicity to bees and its long-persisting insecticidal effect made it particularly useful in the treatment of flowering plants. Toxaphene was not used to control cockroaches because its action on them is weaker than chlordane. Toxaphene was used at one time in the United States to eradicate fish. The principal use was for pest control on cotton crops. In 1974, an estimated 20 million kg used in the United States was distributed as follows: 85% on cotton; 7% on livestock and poultry; 5% on other field crops; 3% on soybeans; and less than 1% on sorghum. Based on estimates of von Rumker et al. (1974) for 1972, 75% of the toxaphene production for that year was for agricultural use; 24% was exported; and 1% was used for industrial and commercial applications. Toxaphene solutions were often mixed with other pesticides partly because toxaphene solutions appear to help solubilize other insecticides with low water solubility. Toxaphene was frequently applied with methyl or ethyl parathion, DDT, and lindane. Through the early 1970s toxaphene or mixtures of toxaphene with rotenone were used widely in lakes and streams by fish and game agencies to eliminate biologic communities that were considered undesirable for sport fishing (ATSDR 1996).

1.2.4 Wastes

42.

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43. Wastes consisting of, containing or contaminated with the pesticide POPs except DDT are found in a number of physical forms including:

i. obsolete stockpiles of pesticides in original packages which are no longer usable because of their exceeded shelf life and/or because of deteriorated packages;

ii. liquids consisting of, containing or contaminated with pesticide POPs (technical grade pesticide diluted with specific solvents like gas oil and others);

iii. solid materials consisting of, containing or contaminated with pesticide POPs (technical grade pesticide mixed with inert materials), including application equipment and empty packaging equipment;

iv. demolition wastes (storage walls and slabs, foundations, beams etc.) containing or contaminated with pesticide POPs

v. equipment containing or contaminated with pesticide POPs (shelves, spray pumps, hoses, personal protective materials, vehicles, storage tanks, etc.);

vi. empty packaging materials contaminated with pesticide POPs (like metal drums, paper bags, plastic bottles, glass bottles, etc.);

vii. soil and water contaminated with pesticide POPs (soil, sediment, groundwater, drinking water, open water).

2.0 Relevant provisions of the Basel and Stockholm Conventions

2.1 Basel Convention

44. Article 1 (“Scope of Convention”) outlines the waste types subject to the Basel Convention. Article 1 paragraph 1(a) of the Basel Convention contains a 2-step process for determining if a “waste” is a “hazardous waste” subject to the Convention. First, the waste must belong to any category contained in Annex I (“Categories of Wastes to be Controlled”). Second, the waste must posses at least one of the characteristics listed in Annex III (“List of Hazardous Characteristics”).

45. Annex I lists some of the wastes that may consist of, contain or be contaminated with the pesticide POPs except DDT, these include:

Y2 Wastes from the production and preparation of pharmaceutical productsY4 Wastes from the production, formulation and use of biocides and phytopharmaceuticalsY18 Residues arising from industrial waste disposal operations

46. Wastes contained in Annex I are presumed to exhibit an Annex III hazardous characteristic—which include H11: “Toxic (Delayed or Chronic)”; H12 “Ecotoxic”; and H6.1 “Poisonous (Acute)”—unless, through “national tests,” they can be shown to not exhibit the characteristics. National tests may be used until such time as the hazardous characteristics of Annex III are fully defined.

47. List A of Annex VIII describes wastes that are “characterized as hazardous under Article 1, paragraph 1(a)” although “their designation on this Annex does not preclude the use of Annex III to demonstrate that a waste is not hazardous.” The B list of Annex IX lists wastes that will not be wastes covered by Article 1, paragraph 1(a), unless they contain Annex I material to an extent causing them to exhibit an Annex III characteristic. The following wastes are applicable to POPs pesticides:

A4030 Wastes from the production, formulation and use of biocides and phytopharmaceuticals, including waste pesticides and herbicides which are off-specification, outdated (unused within the period recommended by the manufacturer), or unfit for their originally intended use

48. Annex VIII’s List A includes a number of wastes or waste categories that have the potential to contain or be contaminated with the pesticide POPs except DDTowing to past applications of these substances, such as:

A4130 Waste packages and containers containing Annex I substances in concentrations sufficient to exhibit Annex III hazard characteristics

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A4140 Wastes consisting of or containing off specification or outdated chemicals corresponding to Annex I categories and exhibiting Annex III hazard characteristics. (“Outdated” as defined by the accompanying footnote 7 to this entry means “unused within the period recommended by the manufacturer.”)

49. For further information please refer to section 2.1 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutant.

2.2 Stockholm Convention

50. The Stockholm Convention outlines in: Annex A, ELIMINATION, Part I the specific requirements with respect to POPs pesticides.

51. However Specific exemptions can be allowed for Parties in the Register. Till present the only exemption, listed in the Provisional Register of Specific Exemptions, is made for Mirex for Australia which is allowed to use Mirex till 17 May 2009. Mirex is listed herunder with the following note: “Mirex is used under licence in northern Australia as a bait control for the giant termite (Mastotermes darwiniensis).  Research is underway to find a suitable alternative with the aim of phasing out the use of mirex”Futher can amendments of the annex be made according to Article 21 and 22.

52. For further information please refer to section 2.2 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutant.

3.0 Issues under the Stockholm Convention to be addressed cooperatively with the Basel Convention

3.1 Low POP content

53.

54.

55. The following provisional definition for low POP content should be applied for aldrin, chlordane, dieldrin, endrin, heptachlor, HCB, mirex and toxaphene: 50 mg/kg for each of these POPs (Remark: Insert same footnote as in the General guidelines: “Determined according to national or international methods and standards”).

3.2 Levels of destruction and irreversible transformation

56.

57.

3.3 Methods that constitute environmentally sound disposal

58. Section 4.7 contains a description of methods which may constitute environmentally sound disposal of wastes consisting of, containing or contaminated with POPs pesticides.

4.0 Guidance on Environmentally Sound Management (ESM)

4.1 General considerations

4.1.1 Basel Convention

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59. One of the main vehicles for the promotion of ESM is the preparation and dissemination of technical guidelines such as this one and the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants. For further information please refer to section 4.1.1 of the General Technical Guidelines.

4.1.2 Stockholm Convention

60. The term ESM is not defined in the Stockholm Convention. However, environmentally sound methods for disposal of wastes consisting of, containing or contaminated with POPs pesticides is to be determined by the COP in cooperation with the appropriate bodies of the Basel Convention.

61. Parties should consult Interim guidance for developing a national implementation plan for the Stockholm Convention (UNEP, 2003b).

4.1.3 Organization for Economic Cooperation and Development (OECD)

62. The OECD also promotes ESM through its “Core Performance Elements” (OECD, 2004). For further information please refer to section 4.1.3 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants.

4.2 Legislative and regulatory framework

63. Parties to the Basel and/or Stockholm Conventions should examine national controls, standards and procedures to ensure these are in line with Convention provisions and their obligations under them, including as these pertain to ESM of wastes consisting of, containing or contaminated with POPs pesticides.

64. Elements of a regulatory framework applicable to POPs pesticides could also include the following:

i. enabling environmental protection legislation (sets release limits and environmental quality criteria);

ii. prohibitions on the manufacture, sale, import and export (for use) of POPs pesticides

iii. phase-out dates for POPs pesticides that are in use, inventory or storage;

iv. hazardous materials and waste transportation requirements;

v. specifications for containers, equipment, bulk containers and storage sites;

vi. specification of acceptable analytical and sampling methods for POPs pesticides;

vii. requirements for waste management and disposal facilities;

viii.general requirement for public notification and review of proposed government regulations, policy, certificates of approval, licenses, inventory information and national emissions data;

ix. requirements for identification and remediation of contaminated sites;

x. requirements for health and safety of workers; and

xi. other potential legislative controls (waste prevention and minimization, inventory development, emergency response).

65. A link should be established in legislation between the phase-out date for production and use of POPs pesticides (including in products and articles) and the disposal of the POPs pestcides once it has become a waste. This should include a time limit for disposal of the waste consisting of, containing or contaminated with POPs pesticides, so as to prevent massive stockpiles from being created that have no clear phase-out date.

66. For further information please refer to section 4.2 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants.

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4.3 Waste prevention and minimizationThis section should be shortened. Duplication with the General guidelines should be avoided. However, measures specific for pesticide POPs should be recommended, such as:- Obsolete pesticides should be concentrated in safe stores- Collection systems for empty pesticide packages and used equipments should be established

67. Prevention and minimization of wastes consisting of, containing or contaminated with POPs pesticides is the first and most important step in the overall ESM of such wastes. Article 4, paragraph 2 of the Basel Convention calls on Parties to “ensure that the generation of hazardous wastes and other wastes within it is reduced to a minimum”.

68. Elements of a waste prevention and minimization programme include the following:

i. identification of processes that use POPs pesticides and generate wastes consisting of, containing or contaminated with POPs pesticides, in order to:a. determine whether process modifications, including updating older equipment, could reduce

waste generation; andb. identify alternative processes that are not linked to the production of wastes consisting of,

containing or contaminated with POPs pesticides;

ii. identification of products and articles consisting of, containing or contaminated with POPs pesticides materials and non-POPs pesticides alternatives; and

iii. minimization of the volume of waste generated through:a. performance of regular maintenance of equipment to increase efficiency and prevent spills and

leaks; b. containment of spills and leaks in a prompt manner;c. decontamination of containers and equipment containing wastes consisting of, containing or

contaminated with POPs pesticides; andd. isolation of wastes consisting of, containing or contaminated with POPs pesticides in order to

prevent contamination of additional materials.

69. Generators of wastes and significant downstream industrial users (e.g., pesticide formulators) of products and articles containing POPs pesticides could be required to develop waste management plans. Logically, such a plan should cover all hazardous wastes, with wastes consisting of, containing or contaminated with POPs pesticides wastes taken into consideration as one component of such a plan.

70. Mixing of wastes with a POPs pesticides content above a defined low POPs pesticide content with another material solely for the purpose of generating a mixture with a POPs pesticide content below the defined low POPs pesticide content is not environmentally sound. However, mixing of materials prior to waste treatment may be necessary in order to optimize treatment efficiencies.

71. It should be mentioned that FAO has developed guidelines in order to protect farmers in rural areas and urban dwellers who often use small quantities of pesticides as opposed to bulk quantities with no awareness of the inherent dangers of pesticides (FAO)

4.4 Identification and inventories

4.4.1 Identification

72. The identification of POPs pesticides can not be considered as an isolated activity, even though the POPs pesticides fall under the obligation of the Stockholm Convention. It is highly recommended when identifying POPs pesticides to include DDT (not included in these Technical Guidelines but dealt with in a separate guideline) and all other obsolete pesticides, thus making sure that the problem as whole is taken into account. Present experiences indicate that between 15 and 30 % of the obsolete pesticides can be POPs pesticides.

73. POPs pesticides are typically found in the following locations:

i. Storage and mixing places for agriculture chemicals (stores, farm sheds, warehouses);

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ii. Warehouses and stores of distributing agencies (central warehouses, commercial shops, Government distribution warehouses);

iii. Contaminated spraying or application equipment (normally stored in farmers’ stores, warehouses, etc.);

iv. Contaminated empty packaging materials (originally containing POPs pesticides, like bags, bottles, metal drums, gas cylinders, etc.);

v. Dumpsites (buried into the ground as –unsound- disposal practice);

vi. In and around (former) manufacturing plants (in stores, in the facility as spillage and/or contamination, open air storage sites of contaminated chemicals)

vii. soil and groundwater (contaminated by spills);

viii. sediment (contaminated by spills);

ix. Commercial products containing POPs pesticides (Paints, household insect spray, mosquito coils, etc.)

74. It is important to note that normally experienced and well trained technical persons will be able to determine the nature of an effluent, substance, container or piece of equipment by its appearance or markings. However, in many countries larger stocks of unidentified agricultural chemicals exist. If identification will be needed for sound environmental management (this will not always be the case) the correct identification can only be done through chemical analysis. Experienced inspectors may be able to determine the original contents from information on the container labels, type and color of the original containers and/or by smell or appearance of the chemical (color, physical characteristics).

75. When identifying POPs pesticides common trade names outlined in Appendix 1 may be useful.

4.4.2 Inventories

76. Inventories are a necessary tool in identifying, quantifying and characterizing POPs pesticides and related wastes (contaminated application equipment, contaminated soil/water) with implications for development of management strategies. A national inventory is necessary to establish a baseline quantity of POPs pesticides, to establish an information registry that assists with safety and regulatory inspections and the preparation of emergency plans, and to track progress with respect to minimization and phase-out of these chemicals. The initial inventory will allow each country to assess the extent and condition of POPs pesticides.

77. The development of a national inventory requires the long-term commitment of the national government, cooperation of POPs pesticide owners and (in case of no ownership) the collaboration of local government and/or private property managers, and a sound administrative process for collection of information on an ongoing basis according to United Nations Food and Agriculture Organisation (FAO) guidelines and standardised methods , storage of the information in a computerised database with retrieval options and preparation of useful reports regarding the progress of phase-out and disposal. In some cases, government regulations may be required to ensure that POPs pesticide owners report their holdings and cooperate with government inspectors. Information on the basic steps in the development of an inventory can be found in section 4.4.2 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants.

78. A complete inventory of all POPs pesticides is a time consuming activity and involves physical visits of the inventory team to all locations where POPs pesticides, obsolete pesticides and related wastes are stored.

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4.5 Sampling, analysis and monitoring

4.5.1 SamplingRevise section based on General and PCB guideline. Why is the term “agrochemical” used in this section?79. As a rule of thumb, sampling should only take place in situations where relatively large amounts of unidentified agrochemical are discovered during the inventory process. The identification of the chemical, the physical structure and the active ingredient concentration indicates whether the agrichemical can still be applied or not based on its properties.

80. As chemical analyses are costly, sampling should not take place for relative small amounts not worth spending analysis costs. It is preferred to reduce the number of samples of agrochemicals in the field to a minimum

81. Unknown quantities of agrichemicals will be referred to in the inventory database as ‘unknown’. At a later stage, a disposal contractor or international shipping company might want to know the characteristics of the ‘unknown’ agrichemicals.

82. In this document “sampling” refers to the taking of a sample of liquid or solid for later analysis either in the field or in a laboratory. Gases are not sampled.

83. The types of matrices that can be sampled for analysis of the pesticide POPs except DDT are shown below.

i. Liquids and solids:

a. Pure products (in stores in containers, lose products in stores, products outside stores in the open air, buried quantities of agrochemicals);

b. suspected contaminated water (surface water, rainwater, groundwater, soil pore water, drinking water, industrial process water, effluent water, condensate);

c. suspected contaminated soil (in and outside warehouses and storageplaces, around open air storage sites, dumpsites, etc.);

d. suspected contaminated plant materials (crops) and food e. suspected contaminated buildings and building parts

84. For further information please refer to section 4.5.1 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutant.

4.5.2 Analysis

85. Analysis refers to the determination of the physical, chemical or biological properties of a material using documented, peer-reviewed and “accepted” laboratory methods.

86. Each country should identify, through guidelines or legislation, standard methods that are required to be used for POPs pesticides and the situations in which the methods should be used.

87. The methods specified should cover all aspects of the analytical process for each type of sample that could be collected, as per the list of sample materials in subsection 4.5.1. The steps in analysis are some or all of the following:

i. sample handling and storage;ii. sample preparation (drying, weighing, grinding, chemical digestion, etc.);iii. extraction of contaminants (organic solvent extraction, leachate production);iv. dilution or concentration of sample or extract;v. calibration of equipment;vi. the actual analytical or bioassay test method;vii. calculation or determination of results; andviii.reporting of results.

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Field tests

88. Field testing refers to the determination of physical, chemical or biological properties of a material or site using portable, real-time instruments or devices. Field test instruments and devices typically collect a sample and analyse it within a very short period of time. Generally, field test instruments and devices also have a lower degree of accuracy and precision than sampling and analysis in a laboratory.

89. Field test instruments are nevertheless extremely valuable for field work in identifying materials that are likely to be wastes consisting of, containing or contaminated with POPs pesticides. They are also useful in assisting with decisions about where to take additional samples, in detecting dangerous atmospheres (explosive, flammable, toxic), and in locating the sources of spills and leaks. Portable units with photo-ionization detectors or flame ionization detectors are available to detect total organic vapours or even individual organic substances. For POPs pesticides the various GC’s can be used such as:

i. Thin-layer chromatography – typically for waste, soils and liquids (not the most precise method);

ii. Packed-column gas chromatography (GC)/electron capture – typically for waste, soil and liquid

iii. GC/Hall electrolytic conductivity detector – for solids and liquids

Laboratory analysis

90. There are numerous methods available for each step of the process. The key for any country is to adopt standard methods and to then require their use by commercial, government and research laboratories. In very general terms, the methods available for chemical analysis for POPs pesticides are the following:

iv. Capillary column GC/electron capture – for solids and liquids;

v. GC/mass spectrometry (MS) –. May not be able to detect low concentrations; apart from GC/electron capture the most applied technique for organochloro pesticides.

vi. High-pressure liquid chromatograph (HPLC) – commonly used for N- and P-pesticides, but can also be applied for organochloro pesticides.

91. Accreditation of laboratories is a minimum requirement of a national analytical programme. All laboratories should be able to meet quality standards set by (EN-)ISO/IEC 17025 and any relevant additional requirements as set by government. Meeting the ISO/IEC 17025 requirements should be assessed by a national accreditation body which has signed the Multilateral Agreement for Testing.

4.5.3 Monitoring

92. Monitoring programs should be implemented for operations managing wastes consisting of, containing or contaminated with POPs pesticides. For further information please refer to section 4.5.3 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants.

4.6 Handling, collection, packaging, labelling, transportation and storageRevise section based on General and PCB guideline.93. Handling and transport are critically important steps as the risk of a spill, leak or fire during handling and transport (e.g., in preparation for storage or disposal) is equal to or greater than that during the normal operation of the equipment. In addition, movement of hazardous wastes is carefully regulated under international agreement and national laws. The Basel Convention: Manual for Implementation (UNEP, 1995a), the International Maritime Dangerous Goods Code (IMO, 2002), the International Air Transport Association Dangerous Goods Regulations (IMDG) and the United Nations Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria (“Orange Book”) should be consulted to determine specific requirements for transport and transboundary movement of hazardous wastes. For the following chapters 4.6 to 4.10, detailed information can be obtained from Destruction and Decontamination Technologies for PCBs and other POPs wastes under the Basel Convention, a Training Manual for Hazardous Waste Project Managers, Volume A and B of the Secretariat of the Basel Convention (SBC, 2002)

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4.6.1 Handling

94. Handling of obsolete pesticides and related wastes (as empty contaminated containers, old spraying equipment) should be done with the objective of minimizing releases to the environment and contamination of additional materials. In addition, obsolete pesticides waste should also be handled separate from other waste types in order to prevent contamination of non-obsolete pesticides waste streams. Recommended practices for this purpose include (and should as such be verified/supervised/monitored):

i. inspecting containers for leaks, holes, rust, high temperature;ii. handling wastes at temperatures below 25oC, if possible, due to the increased volatility at higher

temperatures;iii. ensuring that spill containment measures are in good shape and adequate to contain liquid wastes if

spilled;iv. placing plastic sheeting or absorbent mats under containers before opening containers if the surface

of the containment area is not coated with a smooth surface material (paint, urethane, epoxy, v. removing the liquid wastes either by removing the drain plug or by pumping with a peristaltic pump

(safeguarded against ignition- and fire risks) and suitable chemical resistant tubing;vi. using dedicated pumps, tubing and drums to transfer liquid wastes (not used for any other purpose);vii. cleaning up any spills with cloths, paper towels or specific absorbing materials;viii.triple rinsing of contaminated empty packaging materials (like metal drums) with a solvent such as

kerosene to remove all of the residual obsolete pesticides in order to dispose of the rinsed containers to a dedicated local iron melting plant; and

ix. treating all absorbents, disposable protective clothing, plastic sheeting as obsolete pesticides waste when appropriate.

95. Staff should be trained in the correct methods for handling hazardous wastes according to United Nations Food and Agriculture Organisation (FAO) guidelines and methods.

4.6.2 Collection

96. A significant amount of the total national inventory of obsolete pesticides may be held in small quantities by small storage sites of farmers’ cooperatives, distributors, business owners and homeowners. It is difficult for small quantity owners to dispose of these materials. For example, logistical considerations may prevent or discourage pick up (e.g., no hazardous waste pick-up available, no suitable disposal facility available in the country), and costs may be prohibitive. In some countries national, regional or municipal governments may wish to consider establishing collection stations for these small quantities so that each small-quantity owner does not have to make individual transport and disposal arrangements.

97. Collection depots and/or collection activities related to obsolete pesticides should be separate from those for all other wastes. Obsolete pesticide wastes should not be mixed with other wastes as they may contaminate the other wastes and cause them to become obsolete waste. It is imperative that collection depots not become long-term storage facilities for obsolete pesticide wastes. The risk of environmental and human health impairment is higher for a large stockpile of wastes, even if properly stored, than from small quantities scattered over a large area. Collection is done after (re-)packaging.

4.6.3 Packaging

98. POPs pesticide wastes should be packaged prior to storage or transport in United Nations approved (and as such certified) packaging materials for both national and international transports. International regulations governing transport specify clearly containers of certain quality (e.g., 16-gauge steel coated inside with epoxy). Therefore, containers used for storage should meet transport requirements in anticipation that they may be transported in the future.

99. Small pieces of equipment whether drained or not, should be placed in drums with an absorbent material. Numerous small pieces of equipment may be placed in one drum, as long as an adequate amount of absorbent material is present in the drum. Loose absorbents may be purchased from safety suppliers or sawdust, vermiculite or peat-moss may also be used.

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100.Waste packages and consignments shall be handled in a way which prevents damage during processing, loading or transportation, and shall conform to the national and international requirements of relevant legislation.

101.Equipment plays an important role for PCB transformers, but could in certain cases also be important for pesticides and is therefore described in the following. Equipment should be fully drained of any liquid waste. Drums and equipment may be placed on pallets for movement by forklift truck and for storage. Equipment and drums should be strapped to the pallets prior to movement.

102.Repackaged obsoletes wastes should be fixed with wooden structures and/or straps in sea containers prior to shipping.

103.Normally used UN codes on packaging materials for obsolete pesticides (should be embossed in steel drum, printed on plastic bags etc.):

UN1H1/….. for PE drums for liquid wastes (closed top)UN1H2/….. for PE drums for solid wastes (open top)UN1A1/….. for steel drums for liquid wastes (closed top)UN1A2/….. for steel drums for solid wastes (open top)

104.See IMDG for details and other codes. Certificates for the used UN code should be requested for with the contractor. In case no UN codes visibly available on new packaging materials, these materials should be considered as not UN approved.

105.Repackaging should be executed as such that different types of hazard caused by the chemicals are not mixed. Packaging materials to be used in the EU should comply with ADR 2005 (latest European Agreement of Road Transport of Hazardous Materials). Certificate of packaging material should always be checked.

106.In case of air transportation: ICAO TI (latest version), in case of railway transport: RID (latest version).

4.6.4 Labelling

107.All containers containing obsoletes pesticides should be clearly labelled with both a hazard warning label and a label that gives the details of the container. The details includes preferably the contents of the container (exact counts of volume and weight), the type of waste, the trade name, the name of the active ingredient (including percentage), the name of the original manufacturer, the name of the site it originates from in order to allow traceability, the date of repackaging, and the name of the responsible person during re-packaging,. Each new package should bear identification labels as mentioned in FAO, 2001, Training Manual on inventory taking of obsolete pesticides, Series No 10 and ref No X9899).

108.Additional and separate labels are required for materials classified as ‘marine pollutant’.It is recommended to mark on each container a serial number, the origin (site number and name), the total weight (including the packaging materials) and the name of the product.

4.6.5 Transportation

109.Transportation of dangerous goods and wastes is regulated in most countries and the transboundary movement of wastes is controlled by the Basel Convention and Bamako Convention (in Africa).

110.Persons transporting wastes within their own country should be qualified and/or certified as a shipper of hazardous materials and wastes.

111.Persons proposing to ship hazardous wastes across an international border should notify their national regulatory agency of their intent and follow national and international standards (in particular IMDG Code). In EU member states, means of transport should be licensed for transport of hazardous materials in EU member states.

Point of attention during supervision:

check local relevant safety instructions (for example: is transport by night allowed ?);

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check certificate of instruction / permit / licence of the driver related to transport of hazardous material;

check whether Safety Data Sheets (SDS) are with each transport (on each truck or vehicle);

check whether instructions in case of accidents are available;

verify if the precautions taken by the contractor are sufficient in case of a transport accident

check again if the packaging materials used comply with IMDG and ADR regulations.

4.6.6 Storage

112.Few countries have adopted obsolete pesticides storage regulations or have developed guidelines for such storage. Most do not have specific storage regulations or guidance for obsolete pesticide wastes. In general, the United Nations Food and Agriculture Organisation (FAO) technical guidelines for pesticide storage and stock control and the technical guidelines for the design and structure of pesticide stores should be followed as a minimum. However, in certain countries obsolete pesticides (which are considered as hazardous wastes) should be stored as hazardous waste. This is valid as well for temporarily storage sites. Authorization from local authorities will be needed.

113.Verify authorisation documents (for example: maximum quantities, repackaging allowed on temporarily storage site?, maximum period of temporarily storage ?, sub-standard temporarily storage conditions allowed ?, etc.). such as: For further information, please refer to section 4.6.6 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants.

4.7 Environmentally sound disposal

Remark: Although the information in paras. 114 and 115 may be interesting, it should not be included in these TECHNICAL guidelines. Similar information is not contained in the General and the PSB guidelines.114.

115.

Remark: Although the information in paras. 116 - 118 may be interesting, it should not be included in these technical guidelines because issues not dealing with wastes are beyond its scope.116.

117.

118.

4.7.2 Pre-treatmentRevise section based on General and PCB guideline.119.This section presents commercially available pre-treatment technologies that may be required for the proper and safe operation of the disposal technologies described in sections 4.7.2 to 4.7.4. Where only part of a product or waste, such as waste packages, contains or is contaminated with pesticides, it should be separated and then disposed of according to sections 4.7.1 to 4.7.4 as appropriate.

4.7.1.1 Adsorption / absorption

120.Sorption is the general term for both absorption and adsorption processes. Sorption is a pre-treatment method that uses solids for removing substances from liquids or gases. Adsorption involves the separation of a substance (liquid, oil) from one phase and its accumulation at the surface of another (activated carbon, zeolite, silica, etc.) Absorption is the process whereby a material transferred from one phase to another interpenetrates the second phase to form a solution (e.g., contaminant transferred from liquid phase onto activated carbon).

121.Adsorption/absorption is used to concentrate contaminants and separate them from aqueous wastes. The concentrate and the adsorbent or absorbent may require treatment prior to disposal.

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4.7.1.2 Dewatering

122.Dewatering is a pre-treatment process that partially removes water from the wastes to be treated. Dewatering can be employed for disposal technologies which are not suitable for aqueous wastes. For example, over a certain temperature and pressure environment, water can react explosively with molten salts or sodium. Depending on the nature of the contaminant, resulting vapours may require condensation or scrubbing and/or further treatment.

4.7.1.3 Oil/water separation

123.Some treatment technologies are not suitable for aqueous wastes; others are not suitable for oily wastes. Oil/water separation can be employed in these situations to separate the oily phase from the water. Both the water and the oily phase may be contaminated after the separation and both may require treatment.

4.7.1.4 pH adjustment

124.Some treatment technologies are most effective in a defined pH range and in these situations, alkali, acid or CO2 are often used to control pH levels. Some technologies may also require pH adjustment as a post-treatment step.

4.7.1.5 Screening

125.Screening as a pre-treatment step can be used to remove larger-sized debris from the waste stream or for technologies that may not be suitable for both soils and solid wastes.

4.7.1.6 Shredding

126.Some technologies are only able to process wastes within a certain size limit. For example, some may handle POP-contaminated solid wastes only if less than 200 microns in diameter. Shredding can be used in these situations to reduce the waste components to a defined diameter. Other disposal technologies require slurries to be prepared prior to waste injection into the main reactor. Note that shredders may become contaminated when shredding wastes consisting of, containing or contaminated with POPs. Precautions should therefore be taken to prevent subsequent contamination of POP-free waste streams.

4.7.1.7 Solvent washing

127.Solvent washing can be used to remove POPs from electrical equipment such as capacitors and transformers. This technology has also been used for the treatment of contaminated soil and sorption materials used in adsorption/absorption pre-treatment.

4.7.1.8 Thermal desorption

128.Low-temperature thermal desorption (LTTD), also known as low-temperature thermal volatilization, thermal stripping and soil roasting, is an ex-situ remedial technology that uses heat to physically separate volatile and semi-volatile compounds and elements (most commonly petroleum hydrocarbons) from contaminated media (most commonly excavated soils). Such processes have been used for the decontamination of the non-porous surfaces of electrical equipment such as transformer carcasses that formerly contained PCB-containing dielectric fluids. Thermal desorption of wastes consisting of, containing or contaminated with POPs may result in the formation of unintentional POPs, which may require additional treatment.

4.7.2 Destruction and irreversible transformation methodsRevise section based on General and PCB guideline. Technologies regarding remediation of contaminated sites (In-situ Thermal Desorption and Vitrification) are beyond the scope of this section.129.The following disposal operations, as provided for in Annex IVA and IVB of the Basel Convention, should be permitted for the purpose of destruction and irreversible transformation of the POP content in wastes when applied in such a way as to ensure that the remaining wastes and releases do not exhibit the characteristics of POPs:

D9 Physico-chemical treatment,D10 Incineration on land, and

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R1 Use as a fuel (other than in direct incineration) or other means to generate energy.

130.This section describes commercially available operations for the environmentally sound destruction and irreversible transformation of the POP content in wastes. Further information regarding these technologies of others currently in the pilot or test phase can be found within Review of Emerging, Innovative Technologies for the Destruction and Decontamination of POPs and the Identification of Promising Technologies for Use in Developing Countries (UNEP, 2004a).

4.7.2.1 Alkali reduction

131.Process description: Alkali reduction involves the treatment of wastes with dispersed alkali metals. Alkali metals react with chlorine in halogenated waste to produce salt and non-halogenated waste. Typically, the process operates at atmospheric pressure and temperatures between 100˚C and 180˚C. Treatment for POPs pesticides can take place ex-situ in a reaction vessel. There are several variations of this process (Piersol, 1989). Although potassium has been utilized, metallic sodium is the most commonly used reducing agent. The remaining information is based on experiences with the metallic sodium variation.

132.Efficiency: Neither DE nor DRE has been reported. However the sodium reduction process has been demonstrated to meet regulatory criteria in the EU, United States, Canada, South Africa, Australia and Japan for PCB transformer oil treatment, i.e. less than 2 ppm in solid and liquid residues (Piersol, 1989; UNEP, 2004a).

133.Waste types: Sodium reduction has been demonstrated with PCB-contaminated oils containing concentrations up to 10,000 ppm (UNEP, 2004a). Most of the belowlisted vendors had never requests for pesticides treatment and have thus not treated pesticides. Existing plants for processing liquid PCB or solids containing PCB should be able to process POPs pesticides with minimal modifications. Only adjustments in the reaction recipe may be necessary. Successful laboratory tests on hexachlorobenzene, pentachlorophenol, bromochloromethane and tetrachloroethylene have been performed (Communications Powertech, 25 August 2004).

134.Pre-treatment: In-situ treatment as for PCB transformers is not applicable for pesticides POPs. Pre-treatment should include de-watering to avoid explosive reactions with metallic sodium. Larger particles need to be removed by sifting and crushed to reduce their size; input in powder from smaller that 1 mm is suitable.

135.Potential emissions and residues: Air emissions include nitrogen and hydrogen gas. Emissions of organics are expected to be relatively minor (Piersol, 1989). Residues produced during the process include sodium chloride, polybiphenyls and water (UNEP 2004a). In some variations, a solidified polymer is also formed (UNEP, 2000).

136.Post-treatment: After the reaction, the by-products can be separated out from the oil through a combination of filtration and centrifugation. The decontaminated oil can be reused, the sodium chloride can either be reused as a neutralizing agent or is disposed of as an aqueous solution (Communication Powertech 25 August 2004).

137.Disposal of sodiumchoride of in a landfill is not suited to landfill, due to its solubility. The solidified polymer can be disposed of in a landfill (UNEP, 2000).

138.Energy requirements: Energy requirements are expected to be relatively low due to low operating temperatures associated with the sodium reduction process.

139.Material requirements: sodium dispersion in oil is required to operate this process (UNEP, 2004a). The amount of dispersion required increases with the level of PCB (Communication with Powertech 25 August 2004).

140.Portability: This process is available in transportable and fixed configurations (UNEP, 2004a).

141.Health and safety: Dispersed metallic sodium can react violently and explosively with water, presenting a major hazard to operators. Metallic sodium can also react with a variety of other substances to produce hydrogen – a flammable gas that is explosive in admixture with air. Great care must be taken in process design and operation to absolutely exclude water (and certain other substances, e.g. alcohols) from the waste and from any

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other contact with the sodium.

142.Capacity: Mobile facilities are capable of treating 15,000 litres/day of transformer oil (UNEP, 2004a). Stationary facilities upto 30,000 litres/day (communication with Powertech 25 August 2004)

143.Other practical issues:

144.Economics: Cost estimates for PCB’s provided by vendors include: i. transformer oils: US$0.15/L, £500 - £1000/t, CAN$4/gallon, CAN$0.90/kg; andii. waste oils: CAN$0.60/kg (UNEP, 2000).

It is not clear whether these estimates include costs associated with pre-treatment or disposal of residues.

145.State of commercialization: This process has been used commercially for approximately 20 years (Piersol, 1989).

146.Vendor(s): Include:

i. Envio Germany GmbH & Co. KG - www.envio-group.com ii. EarthFax Engineering Inc. - www.earthfax.com;iii. Kinectrics Inc.- www.kinectrics.com;iv. Powertech Labs Inc.- www.powertechlabs.com; andv. Sanexen Environmental Services Inc.- www.sanexen.com.vi. Decoman srl, Italy - www.decoman.itvii. Orion BV, Netherlands - www.orionun2315.nl/en/index.php

147.Additional information: Available from UNEP, 1998b; UNEP, 2000; and UNEP, 2004a.

4.7.2.2 Base catalyzed decomposition (BCD)

148.Process description: The BCD process involves treatment of wastes in the presence of a reagent mixture consisting of hydrogen donor oil, alkali metal hydroxide and a proprietary catalyst. When the mixture is heated to above 300°C, the reagent produces highly reactive atomic hydrogen. The atomic hydrogen reacts with the waste to remove constituents that confer the toxicity to compounds.

149.Efficiency: DEs of 99.99 – 99.9999% have been reported for DDT, HCB, PCBs, PCDDs and PCDFs (UNEP, 2004a). It has also been reported that reduction of chlorinated organics to less than 2 mg/kg is achievable (UNEP, 2001).

150.Waste types: As noted above, BCD has been demonstrated with DDT, HCB, PCBs, PCDDs and PCDFs. BCD should also be applicable to other POPs (UNEP, 2004a; Vijgen, 2002). BCD should be capable of destroying high concentration wastes, with demonstrated applicability to wastes containing greater than 30% PCBs (Vijgen, 2002). Former statements expressing that in practice, it has been noted that the formation of salt within the treated mixture can limit the concentration of halogenated material able to be treated (CMPS&F – Environment Australia, 1997; Rahuman, 2000; UNEP 2001), are corrected with newest information stating that the formation of salt within the treated mixture can limit the amount of waste fed to the reactor for each batch. The concentration of the halogenated material can be up to 100% (Communications Fairweather 25 August 2004). Applicable waste matrices include soil, sediment, sludge and liquids. BCD Group, Inc. also claims that the process has been demonstrated to destroy PCBs in wood, paper and metal surfaces of transformers.

151.Pre-treatment: Soils may be treated directly. However, different types of soil pre-treatment may be necessary:

i. larger particles may need to be removed by sifting and crushed to reduce their size; orii. pH and moisture content may need to be adjusted.

Thermal desorption has also been used in conjunction with BCD to remove POPs from soils prior to treatment. In these situations the soil is premixed with sodium bicarbonate prior to being fed into the thermal desorption unit (CMPS&F – Environment Australia, 1997). Water will need to be evaporated from aqueous media, including wet sludge, prior to treatment. Capacitors can be treated following size reduction through shredding

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(CMPS&F – Environment Australia, 1997; UNEP 2001). If volatile solvents are present, such as occurs with pesticides, they should be removed by distillation prior to treatment (CMPS&F – Environment Australia, 1997).

152.Potential emissions and residues: Air emissions are expected to be relatively minor. The potential to form PCDDs and PCDFs during the BCD process is relatively low. Other residues produced during the BCD reaction include sludge containing primarily water, salt, unused hydrogen donor oil and carbon residue. The vendor claims that the carbon residue is inert and non-toxic (BCD Group, Inc. literature).

153.Post-treatment: Depending on the type of hydrogen donor oil utilized, the slurry residue may be treated in different ways. If No. 6 fuel oil has been used, the sludge may be disposed of as a fuel in a cement kiln. If more refined oils are used, these may be removed from the sludge by gravity or centrifuge separation. The oils can then be re-used and the remaining sludge can be further treated for usage as a neutralizing agent or disposed of in a landfill (UNEP, 2004a). In addition, BCD plants are equipped to with activated carbon traps to minimize releases of volatile organics in gaseous emission (BCD Group, Inc. literature). The volume of waste gas, nitrogen released is very low so that actual mass emissions are minimal (Communications Fairweather August 2004).

154.Energy requirements: Energy requirements are expected to be relatively low due to low operating temperatures associated with the BCD process.

155.Material requirements: Include:

i. Hydrogen donor oil, such as No. 6 fuel oil or Sun Par oils No. LW-104, LW-106 and LW-110.ii. Alkali or alkali earth metal carbonate, bicarbonate or hydroxide, such as sodium bicarbonate.

Amounts range from 1 to about 20% by weight of the contaminated medium. The amount of alkali required is dependent on the concentration of the halogenated contaminant contained in the medium (CMPS&F – Environment Australia, 1997; UNEP 2001).

iii. Proprietary catalyst amounting to 1% by volume of the hydrogen donor oil.

Equipment associated with this process is thought to be readily available (Rahuman, 2000).

156.Portability: Modular, transportable or fixed plants have been built.

157.Health and safety: In general the health and safety risks associated with operation of this technology are thought to be low (CMPS&F – Environment Australia, 1997; Rahuman, 2000), although a BCD plant in Melbourne, Australia was rendered inoperable following a fire in 1995. The fire is thought to have resulted from the operation of a storage vessel without a nitrogen blanket (CMPS&F – Environment Australia, 1997). Some associated pre-treatments such as alkaline pre-treatment of capacitors and solvent extraction have significant fire and explosion risks, although they can be minimised through appropriate precautions (CMPS&F – Environment Australia, 1997). Modern designs also cool the reagents after reaction before emptying so that the chance of fire is now reduced to a mininum. (Communications Fairweather August 2004)

158.Capacity: BCD can process as much as 2600 gallons per batch, with a capability of treating 2-4 batches/day (Vijgen, 2002; UNEP, 2004a). Latest reactor design can treat up to 2 tonnes per batch of contaminated material or 1.5 tonnes of pure POPs (Communication Fairweather August 2004).

159.Other practical issues: Since the BCD process involves stripping chlorine from the waste compound, the treatment process may result in an increased concentration of lower chlorinated species. This can be of potential concern in the treatment of PCDDs and PCDFs, where the lower congeners are significantly more toxic than the higher congeners. It is therefore important that the process be appropriately monitored to ensure that the reaction continues to completion. In the past, it has been reported that the BCD process was unable to treat high concentration wastes due to salt build-up (CMPS&F – Environment Australia, 1997). More recently, however it has been reported that this problem has been overcome (Vijgen, 2002).

160.Economics: The following cost estimates have been reported by BCD Group, Inc.:

i. Licence fees vary;ii. Operating royalties range from 5 to 10% of gross revenues/sales;iii. Capital costs range from US$800,000 to US$1,400,000 for a 2,500 gallon BCD liquid reactor; An

EU standard plant with full oil recovery and residue treatment, a 3500 US Gallon reactor and automated to treat all types of wastes costs about € 3,500,000 and

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iv. Operating costs range from US$728 to US$1,772 depending on the POP concentration.

It is not clear whether these estimates include potential costs associated with pre-treatment and disposal of residues.

161.State of commercialization: BCD has been used at two commercial operations within Australia. Another commercial system has been operating in Mexico for the past two years. In addition BCD systems have been utilized for short-term projects in Australia, Spain and the United States. A BCD unit for the treatment of both PCCD/F contaminated soil and pesticides chemicals wastes is now under construction in the Czech Republic, after having passed all the necessary pilot tests as required by the Czech Government (Communications Fairweather, August 2004).

162.Vendor(s): The patent for this technology is held by BCD Group, Inc., Cincinnati, OH 45208, USA (www.bcdinternational.com). BCD Group, Inc. sells licences to operate the technology. Currently, licences are held by companies based in Australia, Japan, Mexico, Czech Republic and the United States.

163.Additional information: Available from CMPS&F – Environment Australia, 1997; Costner, 1998; Rahuman, 2000; UNEP, 1998b; UNEP, 2001; UNEP, 2004a; Vijgen 2002a.

4.7.2.3 Incineration in Industrial Processes

There are a number of industrial furnaces and other processes such as industrial boilers, cement kilns, smelters, etc., where pesticides (and other POPs as PCBs) can be effectively destroyed. (See Brunner, 2004, for additional information regarding the application of industrial furnaces to PCBs destruction). One of these systems is described below.

4.7.2.3.1Cement kiln co-incineration

164.Process description: In short, cement is made by heating a mixture of calcareous and argillaceous materials to a temperature of about 1450oC. In this process, partial fusion occurs and nodules of so-called clinker are formed. The cooled clinker is mixed with a few percent of gypsum, and sometimes other cementitious materials, and ground into a fine meal - cement. The main components of clinker are lime (CaO), silica (SiO2), alumina (Al2O3) and iron oxide (Fe2O3). In clinker burning, the raw meal (or raw meal slurry in the wet process) is fed to the rotary kiln system where it is dried, pre-heated, calcined and sintered. In the clinker burning process it is essential to maintain kiln charge temperatures of about 1450oC and gas temperatures of about 2000 °C. Also, the clinker needs to be burned under oxidising conditions. Therefore an excess of air is required in the sintering zone of a cement clinker kiln (EU Commission 2001; Environment Agency 2001; Federal Register, 1999).

165.Efficiency: DREs of greater than 99.99998 percent have been reported for PCBs in several countries (Ahling, 1979; Benestad, 1989; Lauber, 1987; Mantus, 1992. US EPA, 1986; Lauber, 1982; von Krogbeumker, 1994; Black, 1983).

166.Waste types: As mentioned above cement kilns have been demonstrated with PCBs, but will also be applicable to other POPs. Cement kilns are capable of treating both liquid and solid wastes (Chadborne, 1997; Karstensen, 2004a.; CMPS&F – Environment Australia, 1997; Rahuman et al., 2000; UNEP, 2004b). Cement kilns are also constrained to produce a viable cement product. Holcim has confirmed that chlorides have an impact on the quality of the cement and so have to be limited to 350-500 grams of chlorine per tonne of cement clinker. Chlorine can be found in all the raw materials used in cement manufacture, so the chlorine levels in the hazardous waste can be critical. However if they are blended down sufficiently, cement kilns can destroy highly hazardous chlorinated waste

167.Pre-treatment: Liquids and oils can and should be fed directly through the main burner (von Krogbeumker, 1988; Karstensen, 2004b)

168.Pre-treatment can involve:

i. thermal desorption of solid wastes prior; and/orii. homogenization of solid and liquid wastes through drying, shredding, mixing and grinding.

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169.Potential emissions and residues: Potential emissions include carbon dioxide, cement kiln dust, hydrogen chloride, PCBs, PCDDs, PCDFs and water vapour (CMPS&F – Environment Australia, 1997; Karstensen, 2001). It should be noted however, that cement kilns can comply with PCDD and PCDF air emission levels below 0.1 ng TEQ/Nm3 (UNEP, 2004b). In most cases, primary measures (integrated process optimisation) have shown to be sufficient to comply with an emission level of 0.1 ng I-TEQ/Nm3 in existing installations. A smooth and stable kiln process, operating close to the process parameter set points, is beneficial for all kiln emissions as well as the energy use. Quick cooling of kiln exhaust gases to a temperature lower than 200oC is considered to be the most important measure to avoid PCDD/F emissions in wet kilns (already inherent in suspension preheater and precalciner kilns). It also considered important to limit alternative raw material feed as part of raw-mix if it includes organics (Karstensen, 2004). Residues include cement kiln dust captured by the air pollution control system.

170.Post-treatment: Process gases require treatment to remove heat (to minimize formation of PCDDs and PCDFs), cement kiln dust and organic compounds from process gases. Treatments include usage of electrostatic precipitators, fabric filters and activated carbon filters (CMPS&F – Environment Australia, 1997; Karstensen, 2001; UNEP, 2004b). It has been reported that PCDD and PCDF concentrations within cement kiln dusts range between 0.4 and 2.6 ppb1 (UNEP, 2004b). Therefore recovered cement kiln dusts should be put back into kilns to the maximum extent practicable, while the remainder may require disposal in a specially engineered landfill.

171.Energy requirements: Due to the high operating temperatures and long retention times the fossil fuel requirements for cement kilns are likely to quite high. New kiln systems with 5 cyclone preheater stages and precalciner will require on average of 2900-3200 MJ to produce 1 Mg of clinker (European Commission, 2001.; UNEP, 2004b).

172.Material requirements: Cement manufacturing requires large amounts of materials including limestone, silica, alumina, iron oxides and gypsum (CMPS&F – Environment Australia, 1997).

173.Portability: Cement kilns are available only in fixed configurations. . The cement industry is widely distributed throughout the world and produced in 2003 approximately 1,940 million tons of cement (Cembureau 2004).

174.Health and safety: Treatment of wastes within cement kilns can be regarded as relatively safe if properly designed and operated (Mantus, 1992; von Krogbeumker, 1988, CMPS&F – Environment Australia, 1997).

175.Capacity: Some cement kilns in the US are licensed to substitute 100% of its conventional fuel with hazardous wastes. (Cement kilns can potentially treat significant quantities of waste due to their high through-put (UNEP, 1998).

176.Other practical issues: Fuel and wastes that are fed through the main burner will be decomposed in the primary flame burning zone at temperatures up to 2,000°C and a retention time of up to 8 seconds. Waste fed to a secondary burner, preheater or precalciner will be burnt at temperatures up to 1,200°C. Potential feed points for supplying fuel and co-fuel (wastes) to the kiln system are:

- via the main burner at the rotary kiln outlet end;- via a feed chute at the transition chamber at the rotary kiln inlet end (for lump fuel);- via secondary burners to the riser duct;- via precalciner burners to the precalciner;- via a feed chute to the precalciner/preheater (for lump fuel);- via a mid kiln valve in the case of long wet and dry kilns (for lump fuel).

177.Expert advice is required to assess whether any kiln can be used for treatment of hazardous waste (Smith, 2003; Karstensen, 2004a; Karstensen, 2001; Rahuman et.al, 2000).

178.Economics: Prices for waste disposal in cement kilns will depend on local conditions and the market. Generally, cement plants will charge between 10 and 20% of the price usually charged by hazardous waste incinerators (GTZ 2004).

1 TEQ were not indicated.

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179.State of commercialization: Cement kilns are currently used in a number of countries for hazardous waste treatment (Karstensen, 2004, Karstensen, 2001).

180.Vendor(s): A number of existing cement kiln co-incineration operations are identified within Inventory of World-wide PCB Destruction Capacity (UNEP, 1998).

181.Additional information: Available from CMPS&F – Environment Australia, 1997; Costner et al., 1998; Karstensen, 2001; Rahuman et al., 2000; Stobiecki 2001; UNEP, 1998 In addition, information on BAT and BEP with respect to cement kilns firing hazardous waste is available from the European Commission (2001) and UNEP (2004b).

4.7.2.4 Gas phase chemical reduction (GPCR)

182.Process description: The GPCR process involves the thermo-chemical reduction of organic compounds. At temperatures greater than 850°C and low pressures, hydrogen reacts with chlorinated organic compounds to yield primarily methane and hydrogen chloride.

183.Efficiency: DEs of 99.9999% have been reported for DDT, HCB, PCBs, PCDDs and PCDFs (CMPS&F – Environment Australia, 1997; Kümmling, Gray, Power and Woodland, 2001; Rahuman et al., 2000; UNEP, 2004a; and Vijgen, 2002).

184.Waste types: As noted above, GPCR has been demonstrated with DDT, HCB, PCBs, PCDDs and PCDFs. However, GPCR should also be capable of treating wastes consisting of, containing or contaminated with all other POPs (CMPS&F – Environment Australia, 1997; UNEP, 2004a; Vijgen, 2002). GPCR is capable of treating high-strength POP wastes (UNEP, 2004a; Vijgen, 2002). GPCR is capable of treating any type of POP waste, including aqueous and oily liquids, soils, sediments, transformers and capacitors (CMPS&F – Environment Australia, 1997; UNEP, 2004a; Vijgen, 2002).

185.Pre-treatment: Depending on the waste type, one of the following three pre-treatment units is used to volatilize wastes prior to treatment in the GPCR reactor:

i. thermal reduction batch processor (TRBP) for bulk solids, including those in drums;ii. the TORBED reactor for contaminated soils and sediments, but also adapted for liquids; andiii. liquid waste pre-heater system (LWPS) for liquids (CMPS&F – Environment Australia, 1997;

Kümmling et al., 2001; UNEP, 2001; UNEP, 2004a; Vijgen, 2002.

In addition, other pre-processing is required for large capacitors and building rubble. Large capacitors are punctured and drained, while rubble and concrete must be reduced in size to less than one square metre (CMPS&F – Environment Australia, 1997).

186.Potential emissions and residues: Potential emissions include hydrogen chloride, methane and low molecular weight hydrocarbons. Residues from the GPCR process include used liquor and water. Solid residues will also be generated from solid waste inputs (UNEP, 2004a; Vijgen, 2002). Since the GPCR process takes place in a reducing atmosphere the possibility of PCDD and PCDF formation is said to be limited (CMPS&F – Environment Australia, 1997; Rahuman et al., 2000).

187.Post-treatment: Gases leaving the reactor are scrubbed to remove water, heat, acid and carbon dioxide (Kümmling et al., 2001; CMPS&F – Environment Australia, 1997; Rahuman et al., 2000). Scrubber residue and particulate will require disposal off-site (Rahuman et.al, 2000; Vijgen, 2002). Solid residues generated from solid waste inputs should be suitable for disposal in a landfill (UNEP, 2004a).

188.Energy requirements: Methane produced during the process can provide much of the fuel needs (CMPS&F – Environment Australia, 1997; Rahuman et al., 2000; UNEP, 2001; UNEP, 2004a, Vijgen, 2002). It has been reported that electricity requirements range from 96 kWh per tonne of soil treated to around 900 kWh per tonne of pure organics treated (CMPS&F – Environment Australia, 1997).

189.Material requirements: There is a possible need for hydrogen supplies, at least during start-up. It has been reported that methane produced during the GPCR process can be used to form enough hydrogen to operate the process (CMPS&F – Environment Australia, 1997; Rahuman et al., 2000; UNEP, 2004a; Vijgen, 2002). However, the hydrogen production unit has been plagued by reliability problems in the past (CMPS&F –

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Environment Australia, 1997). Other material requirements include caustic for the acid scrubber (UNEP, 2004a).

190.Portability: GPCR is available in fixed and transportable configurations (UNEP, 2001; UNEP, 2004a; Vijgen, 2002).

191.Health and safety: Use of hydrogen gas under pressure requires suitable controls and safeguards to ensure that explosive air-hydrogen mixtures are not formed (CMPS&F – Environment Australia, 1997). Operating experience gained to date has indicated that the GPCR process can be undertaken safely (CMPS&F – Environment Australia, 1997; UNEP, 2004a).

192.Capacity: GPCR process capacity is dependent on the capacity of the three pre-treatment units.

i. TRBP has a capacity of up to 100 tonnes of solids per month or up to 4 litres per minute of liquids. Two TRBPs can be used in parallel to double capacity.

ii. TORBED reactor has a capacity of up to 5000 tonnes of soils and sediments per month, although this pre-treatment unit is still in the development stage.

iii. LWPS has a capacity of 3 litres per minute (UNEP, 2004a; Vijgen, 2002).

193.Other practical issues: Contaminants such as sulphur and arsenic were found to inhibit treatment in earlier development stages, although it is unclear whether this is an on-going problem (CMPS&F – Environment Australia, 1997).

194.Economics: The following cost estimates have been reported for the GPCR process:

i. AUS$4000 to AUS$6000 per tonne for organochloride pesticide solids;

ii. AUS$4000 to AUS$8000 per tonne for PCBs and organochloride pesticide liquids; andiii. AUS$6000 to AUS $11,000 per tonne for PCB contaminated capacitors (CMPS&F – Environment

Australia, 1997).

195.State of commercialization: Commercial scale GPCR plants have operated in Canada and Australia. The GPCR plant in Australia operated for more than five years. In addition, a semi-mobile GPCR plant has recently been licensed in Japan (CMPS&F – Environment Australia, 1997; Kümmling et al., 2001; Ray, 2001; UNEP, 2004a; Vijgen, 2002).

196.Vendor(s): The patent for this technology is held by ELI Eco Logic International Inc. (www.ecologic.ca). ELI Eco Logic International Inc sells licences to operate the technology.

197.Additional information: Available from CMPS&F – Environment Australia, 1997; Costner et al., 1998; Kümmling et al., 2001; Rahuman et al., 2000; Ray, 2001; UNEP, 2001; UNEP, 2004a; Vijgen 2002.

4.7.2.5 Hazardous Waste Incineration

198.Process description: Hazardous waste incineration uses controlled flame combustion to treat organic contaminants. Typically a process for treatment of halogenated materials involves heating to a temperature greater than 1000°C, with a residence time greater than 2 seconds, under conditions that assure appropriate mixing. Hazardous waste incinerators are available in a number of configurations including rotary kiln incinerators, high efficiency boilers and light weight aggregate kilns (See Brunner, 2004, for additional information regarding the application of these technologies.)

199.Efficiency: DREs of greater than 99.9999 percent have been reported for treatment of wastes consisting of, containing or contaminated with POPs (Federal Remediation Technologies Roundtable, (FRTR) 2002; Rahuman et al., 2000; UNEP, 1998; UNEP, 2001).

200.Waste types: As noted above hazardous waste incinerators are capable of treating wastes consisting of, containing or contaminated with any POP. Incinerators can be designed to accept wastes in any concentration or any physical form, i.e. gases, liquids, solids, sludges and slurries (UNEP, 1995b).

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201.Pre-treatment: Depending upon the configuration, pre-treatment requirements may include: blending, dewatering, screening and shredding of wastes (UNEP, 1995b; UNEP, 1998; UNEP, 2004b).

202.Potential emissions and residues: Potential emissions include carbon monoxide, carbon dioxide, HCB, hydrogen chloride, particulate manner, PCDDs, PCDFs and PCBs and water vapour (UNEP, 1995b; UNEP, 1998; UNEP, 2004b). It has been reported that inappropriate use of incinerators and poor management procedures can cause incinerators to produce and release PCDDs and PCDFs (UNEP, 2001). However, modern incinerators designed for high temperature and equipped with reformation prevention and dedicated PCDD and PCDF removal facilities have removed the problem of dangerous PCDD and PCDF emissions (UNEP, 2001). Residues include bottom ash, fly ash, salts and scrubber water.

203.Post-treatment: Process gases may require treatment to remove hydrogen chloride and particulate matter and to prevent the formation of and remove unintentionally produced POPs. This can be achieved through a combination of types of post-treatments, including: cyclones and multi-cyclones, electrostatic filters, static bed filters, scrubbers, selective catalytic reduction, rapid quenching systems and carbon adsorption (UNEP, 2004b; US EPA, 1998). Depending upon their characteristics, bottom and fly ashes may require disposal within a specially engineered landfill (U S Army Corps of Engineers, 2003).

204.Energy requirements: Fossil fuel requirements are likely to be relatively high due to the high temperatures utilized in hazardous waste incineration. However, the exact amount of combustion fuel required will depend upon the calorific value of the waste.

205.Material requirements: Material requirements include cooling water and lime or another suitable material for removal of acid gases.

206.Portability: Hazardous waste incinerators are available in both portable and fixed units.

207.Health and safety: Health and safety hazards include those associated with high operating temperatures and potentially high pressures (U S Army Corps of Engineers, 2003).

208.Capacity: Hazardous waste incinerators can treat between 82 and 270 tons per day of waste (European Commission, 2004) or between 30,000 and 100,000 tons per year (UNEP, 2004b).

209.Other practical issues: None to report at this time.

210.Economics: The following cost structure has been reported for a 70,000 ton per year hazardous waste incineration (European Commission, 2004).

Investment Costs: EurosPlanning/approval 3,000,000Machine parts 16,000,000Other components 14,000,000Electrical works 10,000,000Infrastructure works 6,000,000Construction time 3,000,000Total Investment Costs 54,000,000

Operational Costs EurosCapital financing costs 5,000,000Personnel 3,000,000Maintenance 4,000,000Administration 300,000Operating resources/energy 1,300,000Waste disposal 800,000Other 300,000Total Operational Costs 14,700,000Per ton incineration costs (without revenues) 200 – 300

Gate fees at hazardous waste incinerators within Europe have been reported to range between 50 and 1500 Euros (European Commission, 2004).

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211.State of commercialization: There is a long history of experience with hazardous waste incineration (UNEP, 2001

212.Vendor(s): A number of existing hazardous waste incineration facilities are identified within Inventory of World-wide PCB Destruction Capacity (UNEP, 1998).

213.Additional information: Available from FRTR, 2002; Rahuman et al., 2000; UNEP, 1995b; UNEP, 1998; UNEP, 2001; United States Army Corps of Engineers, 2003. In addition, information on BAT and BEP with respect to hazardous waste incinerators is available from the European Commission (2004) and UNEP (2004b).

In-Situ Thermal Desorption (ISTD)

214.Process description: ISTD is a non-combustion process, including in its in situ and ex situ applications to the destruction of POP stockpiles such as soil/sludges contaminated with POPs. ISTD offers apart from those technologies which treat the stockpiles ex-situ the possibility to treat in-situ thus avoiding any removal and/or repackaging actions of stockpiles. ISTD is quite different from ex-situ thermal desorption or incineration. ISTD heats soils by thermal conduction from electrical resistive heating elements placed in contact with the soil. While the arrays of heating elements typically operate at temperatures of 700-800C, there is no flame or combustion involved. Contrary to ex-situ treatment, where soils are treated for seconds or minutes, each batch of soil treated by ISTD is typically heated slowly for 1-3 months, under an oxygen deficient environment.

215.Destruction of POPs occurs by thermal decomposition as the temperature of the soil/waste rises to above 300C. Daughter products similarly undergo thermal decomposition. Most ( > 95-99%) of the organic contaminants are destroyed in-situ. Not only are dioxins and furans not created, treatability and field data indicate they too are destroyed, typically to below background levels. USEPA has granted ISTD a draft Nationwide Toxic Substances Control Act (TSCA) Permit.

216.Efficiency: The combination of long residence time at elevated temperature means that 100% of the targeted treatment zone experiences conditions leading to thermal destruction of POPs. This can be in stark contrast to flame-based technologies, in which some portions of the heated material may see variations in temperature. The resulting treated soil typically has non-detect concentrations of POPs, (Stegemeier 2001) despite heterogeneities, clay, high moisture content, and other conditions that represent challenges to conventional in situ technologies. Thus residues do not remain in the treated soil, and it can be used as a soil for growth of plants and other typical uses after confirmation of treatment and cool down.

217.The treatment zone is operated under a continuous vacuum, with the collected vapors treated in an Air Quality Control treatment train that typically includes a Thermal Oxidizer, Heat Exchanger, and Granular Activated Carbon (GAC) vessels placed in series. Source testing of ISTD systems has consistently demonstrated much greater than 99.9999% Destruction and Removal Efficiencies (DRE) for POPs including PCBs, PCDD/Fs, and PCP. (Baker, 2003) In every case where ISTD has been used to treat POPs, stack emissions have consistently been more than 10 times below the most stringent regulatory emission limits (e.g. <0.1 ng/m3 TEQ for dioxins/furans).

218.Waste types: ISTD produces negligible quantities of waste products. No liquid waste streams are generated, and the off-gas treatment has been demonstrated to achieve over 99.999999% DRE. ISTD has been succesfully proven on sites with high concentrations of PCB’s, TPH, PAH and creosote upto 6% (Vijgen 2002, Bierschenk et al 2004.)

219.Utilization of ISTD to treat buried waste pits containing highly chlorinated tars and similar materials needs to be pilot tested to ensure materials compatibility (Todd 2004).

220.Pre-treatment: no pre-treatment needed. However, in order to properly design the treatment system sufficient datamaterial has to be assured. In specific cases pilot trials are recommended before final treatment system is installed.

221.Potential emissions and residues: Field-scale ISTD projects have demonstrated that dioxins or furans remaining after thermally treating PCB-contaminated soils were less than the average concentration in uncontaminated soils in North America (Iben 1966, Vinegar 1999) (i.e., post-ISTD treatment soil samples were below “background” concentrations for North American soils). There has been no evidence from these projects

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that dioxins or furans were formed in or around the soil of the thermal treatment zone during ISTD. USEPA has granted ISTD a draft Nationwide Toxic Substances Control Act (TSCA) Permit (Vijgen, 2002).

222.Post-treatment: ISTD systems are designed to prevent emission of dioxins or furans or their formation in aboveground treatment units. The protective design elements include: (a) insertion heaters to preheat the vapor collection manifolds, thereby preventing condensation of off-gases during conveyance from the well field to the treatment unit; (b) a flameless thermal oxidizer (FTO) operated at 1700F, that provides a large reaction chamber at very uniform high temperature (in contrast to a locally very hot flame/burner in an incinerator and to the lower temperatures of catalytic oxidizers), and a resulting oxidation zone with sufficient supply of free radicals thereby ensuring a high destruction and removal efficiency for organic contaminants including PCDD/Fs and PCDD/F precursors (e.g., 99.99% DRE within the FTO) and the prevention of the formation of PICs; (c) an air-to-air heat exchanger to reduce the temperature of the off-gases at the oxidizer outlet within a fraction of a second to ~250F, well below the dioxin formation range; and, (d) polishing of off-gas with granular activated carbon (GAC) adsorbers prior to the discharge stack. The combined DRE of the in-situ processes and the off-gas treatment achieved using ISTD for the treatment of PCB sites has been demonstrated to be >99.999999%.

223.The ISTD process produces no fly ash, and it does not release POPs in flue gas, fly ash, or other residues (it produces very limited aqueous residues (Stegemeier 2001) so that further treatment of these process outputs is unnecessary.

224.Energy requirements:

225.Material requirements:

226.Portability: ISTD can be implemented in virtually any location with access to adequate grid-based or portable power supplies. The power required depends largely on how much water is present in the soil, the target treatment temperature and the rate at which groundwater seeps into the treatment zone. ISTD can be utilized in remote areas (Vijgen 2002)

227.Health and safety: ISTD has been implemented at many sites without any U.S. Occupational Safety and Health Administration (OSHA) recordables or lost-time accidents to date. The reliability of ISTD at the field scale for pesticide remediation has not yet been confirmed.(Vijgen 2002)

228.Capacity: ISTD, being an in-situ process, can be applied at a wide range of scales. Soil and waste volumes of 500 to 10,000 m3 or more can be remediated in a single, 2- to 3-month batch treatment. Larger sites can be treated in a series of batches, utilizing the same equipment from batch to batch (Vijgen 2002).

229.Other practical issues:

230.Economics: recent large scale project (2003-2004) for approx. 12,390 m3 of predominantly silty soil requiring treatment, to an average depth of 6 m and a maximum depth of 30 m gave costs of approx $460/m3

(PAHs ranged up to 406 mg/kg benzo(a)pyrene toxic equivalents; pentachlorophenol ranged up to 21 mg/kg).

231.Cost for a full-scale application is between $160 and $260 per m3 for “most standard sites. Example PCB average 782 mg/kg (n=92), max 20,000 mg/kg (2%)Projects with smaller amounts of ca 500 tons tend to have higher prices 750-1000 US Dollars per ton due to higher part of mobilisation costs (Vijgen 2002b.)

232.State of commercialization: Due to the robustness and effectiveness of ISTD, and it’s proven track record for designing, installing, and operating these systems, it has already been reliably deployed at full-scale at over a dozen sites throughout the U.S. and is under consideration for projects in Japan and Europe.

233.Vendor(s): TerraTherm, Inc, Web site: http://www.terratherm.com

234.Additional information: Available from Vijgen 2002, Bierschenk 2004, Baker 2003, Todd 2004.

4.7.2.6 Mediated electro-chemical oxidation (MEO)

235.MEO is available in different configurations, two of which are described below.

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4.7.2.6.1 CerOx

236.Process description: The CerOx process uses electrochemical cells for the generation of the active cerium(IV) oxidant at the anode, a liquid phase reactor for primary organic destruction, a gas phase reactor to destroy any fugitive emissions from the liquid reactor and an acid gas scrubber for removal of acid gases prior to venting to the atmosphere. The process operates at low temperature (90-95˚C) and at atmospheric pressure.

237.Efficiency: DEs of greater than 99.995% for chlordane have been reported under pilot scale tests (Nelson, 2001; UNEP 2004a; Vijgen, 2002).

238.Waste types: The CerOx process is applicable to solids, liquids and sludges (UNEP, 2004a). As mentioned above, CerOx has been demonstrated with chlordane under pilot scale tests. In addition, the vendor claims that this process is also applicable to PCDDs, PCBs and all other organic compounds. It has also been reported that the CerOx process should be applicable to all POPs, including high-strength wastes (UNEP, 2004a). The CerOx Process targets organic waste streams that have fairly significant organic loadings, at least >20%and preferably in the 35-40% range. It not suitable for waste water processing (Communications, Nelson, August 2004).

239.Pre-treatment: Solids will require size reduction. Both solids and sludges require homogenization in order that they can be pumped as a liquid. Prior to treatment, liquefied wastes are passed through an ultrasonic mixer which emulsifies immiscible organics (UNEP, 2004a).

240.Potential emissions and residues: Potential air emissions include carbon dioxide and molecular chlorine. The operation of the CerOx process at atmospheric pressure and relatively low temperature, precludes the formation of unintentionally produced POPs during the treatment process (Vijgen, 2002. Residues include hypochlorite in addition to residues from other hetero-atoms present, i.e. nitrate, sulphate and phosphate (Nelson 2001; UNEP, 2004a).

241.Post-treatment: The CerOx process includes an acid gas scrubber for removal of molecular chlorine from gaseous emissions (UNEP, 2004a).

242.Energy requirements: Electrical requirements range from 40 to 80 kWh depending on the size of the operation (UNEP, 2004a, Communication Nelson, 30 August 2004).

243.Material requirements: Process tanks for anolyte solutions are titanium, while process tanks for the catholyte are made of stainless steel. Proprietary electrochemical cells are constructed from poly(vinylidene fluoride). Cerium(IV) utilized during the process is regenerated from the reduced cerium(III) by re-oxidation in the electrochemical cell (CerOx Corporation literature). Nitric acid and sodium hydroxide, a 30% solution, are the consumables by the CerOx process. The level of consumption is a function of the feed composition. For, example, the amount of caustic consumed has a direct relationship to the amount of chlorine fed to the system (Communication Nelson, 30.August 2004).

244.Portability: Potentially transportable in small units (UNEP, 2004a). Preliminary design drawings have been developed for a portable unit. CerOx expects to deliver this unit early in 2005 (Communication Nelson, 30.August 2004).

245.Health and safety: The CerOx process is relatively easy to control, since the reaction requires application of a continuous electrical current. Due to low production of gaseous emissions, all emissions and residues can be contained and analysed prior to release (Norvell, 2001).

246.Capacity: The CerOx process is available in configurations with the following capacities:

i. base unit consisting of two electrochemical cells has a processing capacity of 25 gallons/day;ii. single units based on multiple electrochemical cells are available with a capacity of up to 100

gallons/day; andiii. treatment plants with a bank of 30 electrochemical cells, with a capacity of 2-4000 gallons/per day.

All of the above are based on a 50% organic liquid input. At present, the Company has 2 models in its sales program, the 40 kWh System 2 and the 80 kWh System 4 (Communication Nelson, 30.August 2004).Larger installations can be produced from multiples of the above configurations (UNEP, 2004a).

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Other practical issues: Although the vendor claims that solid wastes can be processed, it is not clear whether the CerOx process could cope with large amounts of inert solids (UNEP, 2001).

247.Economics: No specific information is available regarding economics, although it has been noted that the largest cost component is electricity (UNEP, 2001).

248.State of commercialization: At least two commercial systems have been sold. However, there is no commercial scale experience with wastes consisting of, containing or contaminated with POPs. One system will be installed at Merck Pharmaceuticals and is expected to begin processing waste at the end of 2004 as is another system at Moravek Biochemicals in Brea, California. CerOx expects to ship 2 additional units in early calendar 2005 (Vijgen, 2002, Communication Nelson, 30.August 2004).

249.Vendor(s): CerOx Corporation (www.cerox.com) has several patents for the CerOx process, including the cerium process chemistry and specialized equipment for its practice.

250.Additional information: Additional information is available from Costner, 1998; Nelson, 2001; UNEP, 2001; UNEP, 2004a; Vijgen 2002.

4.7.2.6.2 SILVER II

251.Process description: The SILVER II process uses silver(II) to oxidise organic waste streams. Reactions take place in an electro-chemical cell similar to the type utilized in the chlor-alkali industry. The process operates at low temperature (approximately 90˚C) and at atmospheric pressure.

252.Efficiency: No DEs have been reported for any waste consisting of, containing or contaminated with POPs. However DEs of 99.9999% have been achieved with other wastes (UNEP, 2004a, Vijgen, 2002).

253.Waste types: SILVER II has not been demonstrated with wastes consisting of, containing or contaminated with POPs. However, it has been reported that this technology should theoretically be applicable to all POPs (UNEP, 2004a). SILVER II has been utilized with aqueous wastes, oils, solvents and selected solids (Turner, 2001; UNEP, 2001). There are widely conflicting reports available regarding the effect of waste concentration of the SILVER II process (UNEP, 2001; UNEP, 2004a).

254.Pre-treatment: Solids and some liquids will require significant size reduction and/or mixing (UNEP, 2001).

255.Potential emissions and residues: Potential air emissions include molecular chlorine and carbon dioxide. The operation of the SILVER II process at atmospheric pressure and relatively low temperature, precludes the formation of unintentionally produced POPs during the treatment process (Turner, 2001; Vijgen, 2002). Residues include hypochlorite plus residues from other hetero-atoms present, i.e. nitrate, sulphate and phosphate (Turner, 2001; Vijgen, 2002).

256.Post-treatment: Scrubbing of gas streams will be necessary to remove acid gases prior to discharge to the atmosphere. Acid effluents can be neutralised by lime and the resulting residue can be disposed of in a landfill (Turner, 2001).

257.Energy requirements: Electrical requirements have not been reported, however they are likely similar to the CerOx process.

258.Material requirements: SILVER II utilizes commercial electro-chemical cells also utilized in the chlor-alkali industry. Materials such as water, acid and silver are recycled in the SILVER II process (Turner, 2001).

259.Portability: Self-contained containerised plants; transportable modular containerised plants and large static plants have been developed (Turner, 2001; Vijgen, 2002).

260.Health and safety: The SILVER II process is relatively easy to control, since the reaction requires application of a continuous electrical current. Due to low production of gaseous emissions, all emissions and residues can be contained and analysed prior to release (Turner, 2001).

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261.Capacity: The SILVER II system has been demonstrated with a plant size of up to 12 kW, which equates to a treatment of 30 kg/day (UNEP, 2004a).

262.Other practical issues: Mainly laboratory scale experiences with the treatment of POP-related wastes (Turner, 2001; UNEP, 2004a; Vijgen, 2002). With chlorine-containing wastes, the chloride content will precipitate as silver chloride (Turner, 2001). The silver chloride can be treated to recover the silver. However, it has been reported that the process for silver recovery has not yet been developed (UNEP, 2004b). Oxygen gas is required for nitric acid regeneration (UNEP, 2004a).

263.Economics: Overall costs associated with treatment of chemical warfare agents and other military wastes have been estimated to be 30% of those associated with incineration (UNEP, 2001).

264.State of commercialization: Plants have been demonstrated at bench-top and pilot scale and using full-scale industrial electrolytic cells (Turner, 2001). However there is currently no information available regarding the demonstration of the SILVER II process on wastes consisting of, containing or contaminated with POPs. AEA Technology has proposed the evaluating effectiveness of the SILVER II process on pesticides (Turner, 2001).

265.Vendor(s): Accentus, a subsidiary of AEA Technology, (www.aeat.com) SILVER II process has been patented for the mineralization of a wide range of organic substrates.

266.Additional information: Available from Costner, 1998; Rahuman, 2000; Turner, 2001; UNEP, 2001, UNEP, 2004a; Vijgen 2002.

4.7.2.7 Plasma arc

267.Plasma arc systems are available in several different configurations.

268. On the process description it has to be mentioned here that high efficiencies of plasma for destroying toxic organic compounds are not due entirely to the high operating temperatures. The U.S. National Academy of Sciences has characterized plasma technologies as follows: “…plasma is comprised of molecules, atoms, ions and electrons at temperatures of 1,000ºC to 20,000ºC (1,832ºF to 36,032ºF) depending on the current and voltage, the gaseous environment and the pressure of the constricting gas.  Either physical or magnetic constriction can be used to increase temperatures. Because plasma arcs between electrodes generally involve voltage drops of 100 V or more, chemical bonds (whose strengths range from 2 to 10 electron volts [eV]) will be broken, and ionisation processes (at 4eV to 25 eV) will occur.  Thus, material exposed to a plasma environment will be transformed into atoms, ions and electrons, with only a few molecules remaining.  This makes the potential use for plasma arcs, torches, melters, and other plasma devices attractive for destroying undesirable molecules (e.g., hazardous wastes)”. 

269. Three of these are described below. (See Brunner, 2004, for additional information regarding the application of this technology).

4.7.2.7.1 PLASCON

270.Process description: The PLASCON process utilizes a plasma arc with temperatures in excess of 3000˚C to pyrolyse wastes. Together with argon, wastes are injected directly into the plasma arc. The high temperature causes compounds to dissociate into their elemental ions and atoms. Recombination occurs in a cooler area of the reaction chamber, followed by a quench resulting in the formation of simple molecules (CMPS&F – Environment Australia, 1997).

271.Efficiency: Bench scale tests with PCBs have achieved destruction removal efficiencies ranging from 99.9999 to 99.999999% (Rahuman, 2000; UNEP, 2004a).

272.Waste types: As mentioned above, PLASCON has been demonstrated with PCB oils containing 60% PCBs. Recently, a PLASCON plant in Australia has been configured to destroy pesticide wastes (UNEP, 2004a). Waste types to be treated must be liquid, gas or solids if in the form of a pumpable fine slurry. Very viscous liquids or sludges thicker than 30 to 40 weight motor oil cannot be processed without pre-treatment. Other solid wastes cannot be treated unless some form of pre-treatment is undertaken (CMPS&F – Environment

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Australia, 1997; UNEP, 2004a).

273.Pre-treatment: Pre-treatment is not required for most liquids. Solids such as contaminated soils, capacitors and transformers can be pre-treated using thermal desorption or solvent extraction (CMPS&F – Environment Australia, 1997; UNEP, 2004a).

274.Potential emissions and residues: Emissions include gases consisting of argon, carbon dioxide and water vapour. Residues include an aqueous solution of inorganic sodium salts, i.e. sodium chloride, sodium bicarbonate and sodium fluoride. Bench-scale tests with PCBs, showed PCDD levels in scrubber water and stack gases in the part per trillion (ppt) range (CMPS&F – Environment Australia, 1997; Rahuman et al., 2000). At a PLASCON plant in Australia used to destroy a variety of wastes, the level of PCBs in the effluent discharged complies with the 2 ppb limit (UNEP, 2004a). POP concentrations in solid residues are unknown (UNEP, 2004a).

275.Post-treatment: Currently, there is little information available regarding post-treatment requirements.

276.Energy requirements: A 150 kW PLASCON unit requires 1000 to 3000 kWh of electricity per tonne of waste (CMPS&F – Environment Australia, 1997).

277.Material requirements: Currently, there is little information available regarding material requirements. However, it has been noted that this process does require argon gas, oxygen gas, caustic and cooling water (CMPS&F – Environment Australia, 1997; UNEP, 2004a).

278.Portability: PLASCON is available in transportable and fixed units (UNEP, 2004a).

279.Health and safety: Since the PLASCON process has a low waste inventory, there is a low risk associated with release of partially treated wastes following process failure (CMPS&F – Environment Australia, 1997; UNEP, 2004a). Currently, there is little additional information available regarding health and safety.

280.Capacity: A 150 kW PLASCON unit can process 1 to 3 tonnes/day of waste (CMPS&F – Environment Australia, 1997; UNEP, 2004a).

281.Other practical issues: None to report at this time.

282.Economics: The capital cost of a 150 kW PLASCON unit has been approximated at US$1 million, depending upon the configuration. Operating costs including labour vary, but are estimated to be under AUS$3000. Typically operating costs range from AUS$1500–2000/tonne. The cost will range depending upon factors such as:

i. waste feed – molecular structure, weight and concentration;ii. electricity costs;iii. argon and oxygen costs;iv. geographic location and site specific issues;v. caustic costs; andvi. required emission limits (CMPS&F – Environment Australia, 1997; Rahuman, 2000; UNEP,

2004a).

It is not clear whether the above includes costs associated with the pre-treatment of solid wastes.

283.State of commercialization: BCD Technologies operates two Plasma plants in Australia, one in Brisbane for PCB's and POP's and another in Melbourne for treating CFC's and Halons. BCD Technologies also operates a BCD plant for low level PCB's and POP's and also has two thermal desorbers for treating contaminated solids. SRL Plasma Pty Ltd has so far sold four plants to Japan for PCB treatment and one plant to England for CFC and Halon treatment (Communication with BCD Technologies, 25 August 2004).

284.There are 4 commercial 150 kW PLASCON units operating in Australia. Since 1992 and 1993, two units treat the liquid waste stream from 2,4 D manufacture which comprises 35 % chlorophenols, 45 % chlorophenoxies and 20 % added toluene to reduce the viscosity of the liquid at the Nufarm Ltd Agricultural Chemicals manufacturing complex in Melbourne. One unit was installed in Melbourne in 1997 to destroy Australia’s stockpile of ozone depleting substances, namely halons and freons. The fourth unit was installed by

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BCD Technologies Pty Ltd at their Brisbane facility. This unit is used to destroy concentrated PCB solutions (>10 %) as well as a range POP pesticides.

285.Till today over 13 000 tons have been destroyed at these facilities. One unit is operating in the UK destroying fire retardants and ODS. Mitsubishi Chemical Corporation have installed four PLASCON plants to destroy PC wastes in Japan. The plants became operational in May 2004 (Vijgen, 2004).

286.Vendor(s): Vendor for the Plascon process is SRL Plasma Pty Ltd Narangba Australia (http://www.srlplasma.com.au/) and Commonwealth Scientific Industrial Research Organisation (CSIRO).  The three patents for PLASCON are jointly owned by SRL Plasma PTY LTD and CSIRO.BCD Technologies and SRL Plasma Pty Ltd are both Australian companies which are owned by BCD Holdings Pty Ltd also an Australian company. SRL Plasma Pty Ltd licenses users of the PLASCON technology and builts PLASCON plants to order.

287.Additional information: Available from CMPS&F – Environment Australia, 1997; Costner, 1998; Rahuman, 2000; Ray, 2001; UNEP, 1998b; UNEP, 2000; UNEP, 2001 and UNEP, 2004a and Vijgen 2004.

4.7.2.7.2 Plasma Arc Centrifugal Treatment (PACT)

288.Process description: The PACT process uses heat generated by a plasma arc to melt the inorganic portion of waste while treating the organic portion. Wastes are fed into a centrifugal chamber heated by a plasma torch. The molten materials reach a temperature of approximately 3000˚C, while gas temperatures range between 1000 and 1500˚C. Molten material is drained and cast into a steel slag mould. Process gases are passed into a secondary combustion chamber heated by a fuel burner or another plasma torch. Process gases are maintained within the secondary chamber for a 2-second residence time at a temperature of at least 1100˚C.

289.Efficiency: DRE of 99.99% have been reported with this process (CMPS&F – Environment Australia, 1997; Rahuman, 2000). In addition, the vendor claims that DREs of greater than 99.9999% have been achieved with HCB-contaminated diesel (Womack, 1999).

290.Waste types: As mentioned above, the PACT process has been demonstrated with HCB waste. The PACT process is capable of treating any type of waste at any concentration, i.e. solid, liquid and gaseous wastes (CMPS&F – Environment Australia, 1997).

291.Pre-treatment: As the process is able to directly treat diverse waste types, pre-treatment is not usually required (CMPS&F – Environment Australia, 1997).

292.Potential emissions and residues: The PACT process can be operated under pyrolytic conditions with a reducing atmosphere to avoid or minimize PCDD formation and the volume of gases (CMPS&F – Environment Australia, 1997; Rahuman, 2000). Depending on the waste feed, residues include a solid slag-like material. It has been reported that no data have been found to describe the concentrations of undestroyed chemicals in process residues (CMPS&F – Environment Australia, 1997). However, the vendor claims that the solid slag-like material meets leachability criteria for consideration as a non-hazardous material (Womack, 1999).

293.Post-treatment: Treatment of gaseous emissions will be required prior to release in order to remove acid gases and particulates. Typical gas treatment can consist of a quench tank, a jet scrubber, a packed-bed scrubber and a de-mister (CMPS&F – Environment Australia, 1997).

294.Energy requirements: Depending on the energy-value of the feedstock and the desired feedrate, a typical two-torch system will use between 1000 kW and 4000 kW of electricity.

295.Material requirements: Currently there is little specific information available regarding material requirements. Significant water is needed for cooling of the chambers, but this can be supplied as a recirculating system. If chlorine is present in the feed, saltwalter will be formed in the scrubber which will need to be periodically removed and replaced with fresh scrubber solution.

296.Portability: It has been reported that the PACT process is transportable in smaller plant sizes (CMPS&F – Environment Australia, 1997).

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297.Health and safety: Health and safety risks associated with this technology appear to be low for several reasons, including:

i. waste drums can be fed into the process unopened, eliminating direct exposure to personnel to hazardous wastes;

ii. use of mechanical seals and operation at negative pressure prevents release of fugitive emissions; and

iii. utilization of water-cooled chambers reduces exterior surface temperatures and allows for relatively fast shutdown (CMPS&F – Environment Australia, 1997; Naval Facilities Engineering Service Centre, 2001).

298.Capacity: The vendor has claimed that full-scale systems are able to treat 1000 kg/hr (Retech literature). Feedrates are highly dependent on the type of feed. PCB-containing capacitors for example can be fed at a rate of 350-500 kg/hr (Dyer, 2004).

299.Other practical issues: Removal of volatile metals and particulates which are formed from inorganic portions of the waste may require removal by a conventional gas scrubber or gas treatment system (CMPS&F – Environment Australia, 1997).

300.Economics: It has been reported that the PACT process has a relatively high capital cost (CMPS&F – Environment Australia, 1997; Rahuman, 2000). At that time, operating costs have been reported to be between AUS$4000-8000/tonne (CMPS&F – Environment Australia, 1997; Rahuman, 2000).

Considerably lower costs per tonne capacitor processed have been reported 750-1000 US $ (Dyer, 2004), and 1,440 US $ per ton for hazardous waste disposal (Department of Defense).

301.State of commercialization: At least six production scale operations have been reported (CMPS&F – Environment Australia, 1997; ReTech literature; Womack, 1999). However it is not clear if any of these operations process wastes consisting of, containing or contaminated with POPs. At present PACT system has been selected for the treatment of 12000 PCB capacitors containing 200 tonnes of PCB’s in the Russian Federation for the Artic Council Action Plan (ACAP), which will be presumable started up in 2005 (Dyer, 2004).

302.Vendor(s): Include Retech Systems LLC – www.retechsystemsllc.com.

303.Additional information: Available from CMPS&F – Environment Australia, 1997; Costner , 1998; Naval Facilities Engineering Service Centre, 2001; Rahuman, 2000; Ray, 2001; UNEP, 1998b; UNEP, 2000; UNEP, 2001, Womack, 1999 and Dyer, 2004).

4.7.2.7.3 Plasma Waste Converter (PWC)

304.Process description: PWC forces gas through an electrical field to ionise gas into a plasma. The plasma operates at a temperature in the order of 3000 to 5000˚C. The plasma chamber operates at normal atmospheric pressure. Wastes are reduced to their metallic components, a slag and a gas (CMPS&F – Environment Australia, 1997). It should be noted that

305.Efficiency: For chemical weapons, DRE’s of 99.99999% for Dimethylmethylphosphonate (DMMP), Trinitrotoluene (TNT), Tetryl, Cyclonite (RDX) and 99.99998% for Nitroglycerine are claimed by the vendor.

306.Waste types: The PWC process is capable of treating any type of waste at any concentration, i.e. solid, liquid and gaseous wastes (CMPS&F – Environment Australia, 1997; UNEP, 2004a). It has been reported that PWC is capable of treating pesticide wastes (UNEP, 2004a). The vendor claims that this process is applicable to treatment of PCBs.

307.Pre-treatment: As the process is able to directly treat diverse waste types, pre-treatment is not usually required (CMPS&F – Environment Australia, 1997).

308.Potential emissions and residues: It has been reported that gaseous emissions include carbon monoxide, carbon dioxide and hydrogen (UNEP, 2004a). It has also been reported that gas recovered from the top of the treatment chamber can be treated and re-used as chemical feed stock or fuel gas (CMPS&F – Environment

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Australia, 1997). Solid residues include metals and inert silicate stone (CMPS&F – Environment Australia, 1997).

309.Post-treatment: It is likely that post-treatment of gaseous emissions will be required prior to release in order to remove acid gases and particulates. Typical gas treatment can consist of a quench tank, a jet scrubber, a packed-bed scrubber and a de-mister.

310.Energy requirements: It has been reported that moderate energy inputs are required to operate this process (UNEP, 2004a).

311.Material requirements: It has been reported that moderate cooling water supplies will be required (UNEP, 2004a).

312.Portability: The PWC process is available in both fixed and portable configurations (CMPS&F – Environment Australia, 1997; UNEP, 2004a).

313.Health and safety: It has been reported that there is a risk of explosion from internal cooling water leaks (UNEP, 2004a). In addition, it has been reported that care will be required during handling of the molten metal and slag produced by the process (CMPS&F – Environment Australia, 1997).

314.Capacity: PWC has been demonstrated to treat 50-100kg per hour and that commercial units have been designed for 10 tonnes per day (UNEP, 2004a).

315.Other practical issues: None to report at this time.

316.Economics: A 180 kg/hour unit costs approximately AUS$1.6 million. Operating costs have been reported at approximately AUS$413/tonne, but will depend on the waste being treated (CMPS&F – Environment Australia, 1997).

317.State of commercialization: One vendor has reported the existence of commercial facilities in Japan, with one facility for the treatment of PCB wastes (Startech Environmental Corp. literature). In addition, it has been reported that PWC is a proven, operating, commercial technology (UNEP, 2004a).

318.Vendor(s): Vendors include Startech Environmental Corp. – www.startech.net.

319.Additional information: Available at CMPS&F – Environment Australia, 1997; Costner et al., 1998; UNEP, 1998b; UNEP, 2000; UNEP, 2001 and UNEP, 2004a.

4.7.2.8 Super-critical water oxidation (SCWO)

320.Process description: SCWO treats wastes in an enclosed system, using an oxidant (e.g. oxygen, hydrogen peroxide, nitrite, nitrate, etc.) in water at temperatures and pressures above the critical point of water (374°C and 218 atmospheres). Under these conditions, organic materials become highly soluble in water and are oxidised to produce carbon dioxide, water and inorganic acids or salts.

321.Efficiency: DREs as high as 99.9999% have been demonstrated for POPs in bench-scale tests with PCDDs, pesticides and pesticides (CMPS&F – Environment Australia, 1997; Rahuman, 2000; Vijgen, 2002).

322.Waste types: SCWO is thought to be applicable to all POPs (UNEP, 2004b). Applicable waste types include aqueous wastes, oils, solvents and solids with a diameter less than 200 µm. Organic content of the waste is limited to less than 20% (CMPS&F – Environment Australia, 1997; Rahuman, 2000; Vijgen, 2002).

323.Pre-treatment: Concentrated wastes may have to be diluted prior to treatment in order to reduce the organic content to less than 20 percent. If solids are present they will have to be reduced to less than 200 µm in diameter.

324.Potential emissions and residues: It has been reported that emissions contain no oxides of nitrogen or acid gases such as hydrogen chloride or sulphur oxide and that process residues consist of water and solids if the waste contains inorganic salts or organics with halogens, sulphur or phosphorus (CMPS&F – Environment Australia, 1997). Limited information has been reported regarding potential concentrations of undestroyed

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chemicals (CMPS&F – Environment Australia, 1997; UNEP, 2004a). The process is designed such that emissions and residues can be captured for reprocessing if needed (UNEP, 2004a).

325.Post-treatment: Currently, there is no specific information available regarding post-treatment requirements.

326.Energy requirements: It would be expected that energy requirements would be relatively high due to the combinations of high temperatures and pressures. However, it has been demonstrated that as long as relatively high hydrocarbon content is present in the feed, no energy input is required to heat up the feed to supercritical temperatures (Rahuman, 2000, Communication Johnson, General Atomics 30 August 2004).

327.Material requirements: The SCWO reaction vessel must be constructed of materials capable of resisting corrosion caused by halogen ions (Vijgen, 2002). At the temperatures and pressures utilized in the SCWO process material corrosion can be severe. In the past, the use of titanium alloys has been proposed to address this problem. Current vendors claim to have overcome this problem through the use of advanced materials and engineering designs (Vijgen, 2002).

328.Portability: Currently utilized in a fixed configuration, but SCWO units are thought to be transportable (UNEP, 2004a; Vijgen, 2002).

329.Health and safety: The high temperatures and pressures used in this process require special safety precautions (CMPS&F – Environment Australia, 1997).

330.Capacity: Current SCWO demonstration units are capable of treating 500 kg/hr, while full-scale units are going to be designed to treat 2700 kg/hr (UNEP, 2004a; Vijgen, 2002).

331.Other practical issues: Earlier designs were plagued by reliability, corrosion and plugging problems. However, current vendors claim to have addressed these problems through the use of special reactor designs and corrosion resistant materials (UNEP, 2004a; Vijgen, 2002).

332.Economics: Costs of $120 to $140 per dry ton assuming some pre-treatment have been reported (CMPS&F – Environment Australia, 1997). It is not clear whether this estimate incorporates capital costs or costs associated with the disposal of any residues.

333.State of commercialization: A commercial full-scale plant has recently begun operating in Japan. In addition, the SCWO process has been approved for full-scale development and use in the US Chemical Weapons programme.

334.Vendor(s): Include:

i. General Atomics – www.ga.com, andii. Foster Wheeler Development Corporation – www.fosterwheeler.com

335.Additional information: Available from CMPS&F – Environment Australia, 1997; Costner, 1998; Rahuman, 2000; UNEP, 2001;UNEP, 2004a; Vijgen 2002.

4.7.2.9 Vitrification

336.Process description: The Vitrification process works by establishing a melt between pairs of electrodes inserted into the soil-bound waste materials. Initially, electrical current is passed through a relatively high-conductivity starter path staged in the soil/waste matrix. Heat dissipated in the starter path is transferred to the surrounding soils causing them to melt. Once molten, the soil becomes sufficiently conductive to support the flow of electrical current, thereby dissipating enough joule heat to sustain and propagate the melting process. Electrical energy is continuously supplied to the melt until such time that it has grown to encompass the entire treatment volume.

337.Off gases generated by the process are collected inside a stainless-steel hood covering the treatment area and are drawn-off for processing by an off-gas treatment system (OGTS). The OGTS consists of a combination of filtration, dry & wet scrubbing, and thermal treatment stages. The small quantity of secondary wastes generated by the OGTS (e.g. –filters, scrubber liquids, and personal protective equipment) can be loaded into subsequent

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applications for processing. When electrical power is shut off, the molten mass cools and ultimately solidifies into a vitreous and crystalline, rock-like monolith. The process destroys organic contaminants such as dioxins, pesticides, and PCBs directly. Heavy metals, radionuclide, and other non-volatile constituents are retained in the melt and immobilised in the vitrified monolith. The vitrified product has exceptional physical, chemical, and weathering properties compared to alternative solidification/stabilisation technologies. It is typically ten times stronger than concrete and is extremely leach resistant.

338.The process generates a vitrified product that is far superior (orders of magnitude better) in terms of durability, strength, and leach resistance compared to other stabilisation or encapsulation technologies. The monolith can be safely left in place. Alternatively, it can be readily recovered for transport to a disposal site. In certain applications, the vitrified product can be recycled for subsequent use (e.g. – roadbed materials, breakwater riprap, and roofing tiles)

339.The following principal methods can be used:

1. Subsurface Planar In-Situ Vitrification (SPV), which has normally been applied for site remediation

2. The in-container vitrification(ICV) method is not used in situ and is not normally used for site remediation. This is a batch plant treatment method which is appropriate for the treatment and disposal of stockpiles.

340.The process has treated PCBs commercially under a United States Environmental Protection Agency (U.S. EPA) Toxic Substances Control Act of 1976 (TSCA) permit entitled “Approval to Dispose of Polychlorinated Biphenyls (PCBs). A project for the treatment of 2,800 tonnes of contaminated soil and debris at a private Superfund site in EPA Region 10, Washington State project was evaluated by the USEPA under the provisions of the National Toxic Substances Control Act (TSCA). The project was completed successfully and resulted in the USEPA granting Geosafe a National TSCA Operating Permit for the GeoMelt process to treat PCB-contaminated soils and wastes in 1996.

341.Efficiency: Destruction and removal efficiency values of >99.9999% have been demonstrated in commercial treatment operations for chlorinated organics such as PCBs, dioxins/furans and hexachlorobenzene. Typically, approximately 99% of the chlorinated organics are destroyed in the vitrification step leaving only a small fraction of the inventory to be treated by the off-gas treatment system. (Communications Thompson, September 2004)

342.Waste types: In the US, sites contaminated with pesticides, herbicides, solvents, PCBs, dioxins, furans, and heavy metals have been remediated with the process. High concentrations of organics can be accommodated by the process. Waste loadings of up to 33-wt% in soil have been demonstrated for chlorinated organics such as hexachlorobenzene (Thompson, 2000). Weight percent concentrations of polychlorinated biphenyls and pesticides, such as DDT, in soil have also been successfully treated.

343.In Australia, the ICV process has been selected as the preferred technology for remediation of approximately 8,200 tonnes (60,000-drums) of HCB waste (Thompson, 2002). Vitrification has also successfully remediated soils contaminated with radioactive materials – including plutonium, uranium, cesium, strontium, americium, technetium, and iodine have been remediated.

344.Pre-treatment: Pretreatment is normally not required for contaminated soils. The process can accommodate a wide range of soils including mixtures of gravel, cobble and debris. For non-soil based wastes, the primary pre-treatment requirement is to mix the waste with soil or other glass forming materials to facilitate treatment. Soil provides the source of glass forming materials and is an essential component for the vitrification process (Communications Thompson, September 2004).

345.Potential emissions and residues: The vitrified product normally consists of a mixture of glass and crystalline materials and often has an appearance similar to volcanic obsidian. Following the treatment of mixed low-level radioactive or hazardous wastes, the vitrified product will not be characteristic waste (i.e., it will not exhibit characteristics of RCRA wastes). The product is typically five to ten times stronger than concrete and is extremely leach resistant. The vitrified product readily satisfies the requirements of the US Environmental Protection Agency’s (EPA) Toxicity Characteristic Leaching Procedure (TCLP). Heavy metals, radionuclide, and other non-volatile constituents are retained in the melt and immobilised in the vitrified monolith. The

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vitrified product is normally 10 or more times more durable and leach resistant than typical borosilicate glasses used to immobilize high-level nuclear waste. The durability and leach resistance of the glass is due to a high concentration (up to 90 weight %) of glass formers (SiO2 and Al2O3).

346.A variety of leach tests of the vitrified product from a number of projects have been conducted including vitrified product containing both uranium and plutonium. Leach data from these tests indicate that the normalized leach rates for the vitrified products are extremely low (typically <0.1-g/m2day) for all oxide species and in most cases approach 0.01-g/m2 day (Callow 1991, Geosafe 2001, Luey 1992, McGlinn 2001, Spalding 1997). These values easily satisfy leach criteria typically used to evaluate the performance of nuclear waste glasses. Data from long-term leach tests (>4 year leach duration) indicate the release rates of U and Pu decrease markedly in the long-term (McGlinn, 2001).

347.Post-treatment: Typically, there are no post-treatment or monitoring requirements for the glass product resulting from the treatment of chlorinated organic compounds because no chlorinated organic compounds remain in the vitrified product. For the treatment of wastes contaminated with heavy metals or radionuclides, the long-term monitoring or management requirements are minimal because of the excellent durability and leach resistance of the product. Such monitoring requirements are usually determined within the Environmental Impact Assessment of the project in conjunction with the regulatory authority.

348.Energy requirements: The energy requirements for the vitrification step typically range from 0.6 to 4.0 kWH/kg of material treated depending on the treatment configuration. Energy requirements for ancillary equipment such as the off-gas treatment system, process control and support facilities are in addition (Communications September 2004, Thompson).

349.Material requirements: none

350.Portability: The processing equipment is trailer mounted for ease of portability. The equipment can be easily transported for on-site treatment.

351.Health and safety: There have been no injuries to operating personnel involved in the implementation of the process. Both processes can be conducted on-site which eliminate the risks associated with handling and transportation. The in situ treatment process offers safety benefits because the material can be treated in situ which avoids the risks associated with handling, pre-treatment and transportation. The In-Container Vitrification process offers safety benefits because extensive pre-treatment steps are avoided. For example, the process can accommodate large items of debris, which minimizes the need for size reduction and other handling steps (Communications September 2004, Thompson).

352.Capacity: Melt rates for full-scale treatment plants approaching 100 tonnes per day can be achieved depending on the configuration of the equipment and the material being treated. Individual melts approaching 1,000 tonnes in size can be produced in an in situ treatment configuration. (Thompson, 2002). Individual melts of up to approximately 1,000-tons can be formed. These range in size from 9 to 11 meters in diameter and up to 5 meters thick. With the Subsurface-Planar Vitrification method, the melting process can be initiated at virtually any depth below grade, and can be propagated from this initial start-up depth to the desired treatment depth.

353.Other practical issues: None to report at this time.

354.Economics: The cost of treatment ranges from US$300 per ton to more than US$1000 per tonne of material treated. The costs are influenced by a wide range of site-specific factors and the particular treatment configuration used (Communications September 2004, Thompson).

355.State of commercialization: The process has been in commercial use since the early 1990’s. Numerous projects have been successfully completed in the US, Australia, and Japan.

356.Vendor: AMEC Earth and Environmental Inc., GeoMelt Division, www.geomelt.com

357.Additional information: Available from AMEC Literature; Botany-HCB site website; Thompson, 2000; Thompson, 2002; Vijgen 2002.

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4.7.3 Other disposal methods when destruction or irreversible transformation does not represent the environmentally preferable optionRevise section based on General and PCB guideline.358.Where destruction or irreversible transformation does not represent the environmentally preferable option, for wastes with a POPs pesticides content above the low POPs pesticides content referred to in section 3.1, a country may allow such wastes to be disposed of by other means.

359.Wastes containing or contaminated with POPs pesticides where other disposal methods may be considered include the following:

i. The following construction and demolition waste:a. mixtures of, or separate fractions of concrete, bricks, tiles and ceramics;b. soil including excavated soil from contaminated sites, stones and dredging spoil;c. inorganic fraction of soil and stones;d. construction and demolition wastes containing POPs pesticides

ii. Vitrified wastes and waste from vitrification including: fly ash and other flue-gas treatment wastes and non-vitrified solid phase.

360.The relevant authority of the country concerned should be satisfied that destruction or irreversible transformation of the POPs pesticides content, performed according to best environmental practice or best available techniques, does not represent the environmentally preferable option.

361.Other disposal methods when destruction or irreversible transformation does not represent the environmentally preferable option include those described below.

4.7.3.1 Specially engineered landfill

362.A specially engineered landfill typically has features such as installed drainage to recover leakage, providing for leachate management including recirculation and gas control systems where appropriate. Operational permits should include specifications regarding types and concentrations of wastes to be accepted, leachate and gas control systems, monitoring, on-site security, and closure and post-closure.

363.The following wastes containing or contaminated with POPs pesticides are not suitable for disposal within hazardous waste landfills:

i. liquids and materials containing free liquids,ii. empty containers unless they are crushed, shredded or similarly reduced in volume, andiii. explosives, flammable solids, spontaneously combustible materials, water-reactive materials,

oxidizers and organic peroxides.364. Further information is available within Technical Guidelines on Specially Engineered Landfill (D5) (UNEP, 1995b).

4.7.3.2 Permanent storage in underground mines

365.Permanent storage in facilities located in salt mines (and hard rock) is an option to separate hazardous wastes from the biosphere for geological periods of time. A site-specific security assessment according to pertinent national legislation such as the provisions contained in Appendix A to the Annex of the European “Council Decision 2003/33/EC of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC” should be performed for every planned underground storage.

366.Any waste to be disposed of in an underground storage should be subject to an acceptance procedure laid down by the competent authority. The wastes should be stored in chemically and mechanically secure containers. They should be disposed of in such a way that any undesirable reaction between different wastes as well as between wastes and storage lining is excluded. Wastes that are either liquid, gaseous, causing toxic gases, explosive, flammable or infectious should be excluded from underground storage. The competent authority may define waste types which should be generally excluded.

367.The following should be considered in the selection of permanent storage in underground mines for disposal of wastes consisting of, containing or contaminated with POP pesticides:

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i. caverns or tunnels used for storage should be completely separated from active mining areas and should not to be opened for mining again;

ii. caverns or tunnels should be located in a geologic formation that is well below the zone of available groundwater in the area, or a formation that is completely isolated (by impermeable rock or clay layers) from water bearing zones; and

iii. caverns and tunnels should be located in a geologic formation that is extremely stable and not within an earthquake zone.

4.7.4 Other disposal methods when the POP pesticide content is lowRevise section based on General and PCB guideline.368.In addition to the disposal methods described above, wastes containing or contaminated with POPs pesticides at concentrations beneath the low POPs pesticide content may be disposed in accordance with pertinent national legislation and international rules, standards and guidelines, including those the Specific Technical Guidelines developed under the Basel Convention. Examples of pertinent national legislation can be found in Appendix 2 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants.

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4.8 Remediation of contaminated sites

4.8.1 Contaminated site identification

Poor handling and storage practices may lead to releases of POPs pesticides at sites storing these chemicals, resulting in sites contaminated with high levels of POPs pesticides. Such highly contaminated sites may pose serious health concerns. Identification of such sites is the first step in addressing potential concerns.

369.Identification of such sites can be undertaken using a phased approach, including:

i. identification of suspect sites, e.g. sites involved in the:a. production and usage of POPs pesticides, orb. disposal of wastes consisting of, containing or contaminated with POPs pesticides;

ii. review of current and historical information pertaining to the suspected site;iii. initial testing program to confirm the presence or absence of suspected contaminants and

characterize the physical conditions at the suspected site; andiv. detailed testing program to further define the nature of the site contamination and to gather any

additional information required.

370.The identification and assessment of contaminated sites is a well developed science, although the results of site assessments are often open to interpretation. Many government agencies and standards associations recommend a phased approach to the identification and assessment of contaminated sites. Further information contaminated site identification is available within Assessing soil contamination: a reference manual No. 8 (FAO, 2000) and Guidance Document on the Management of Contaminated Sites in Canada (Canadian Council of Ministers of the Environment, 1997).

4.8.2 Environmentally sound remediation

371.Contaminated site criteria are used as general targets in the site remediation. They can developed by government agencies using risk assessment techniques. Separate criteria can be developed or adopted for soil, sediment and groundwater. Often a distinction is made between industrial (least stringent criteria), commercial, residential and agricultural (most stringent criteria) soils. Examples of these criteria can be found in the German Federal Soil Protection and Contaminated Sites Ordinance, Swiss Soil Burden Ordinance and Canadian Environmental Quality Guidelines (Canadian Council of Ministers of the Environment, 2002).

372.Site-specific risk assessment can also be used to develop the clean-up targets for the site. The results of a site-specific risk assessment may show that clean-up criteria should be higher, or lower, than the generic criteria developed by the regulatory agency. Risk assessments should be carried out by qualified toxicologists with training or certification in conducting environmental and/or human health risk assessments. Local staff involvement is important (capacity building, institutional strengthening).

373.There are several methods currently available for the remediation of sites contaminated with POPs pesticides. Information on these methods is available from a variety of sources including: FRTR (2002), United States Environmental Protection Agency (2000 and 2003) and Vijgen (2002).

4.9 Health and safety

4.9.1. Health and Safety Plan

374.A health and safety plan for an individual storage facility should be developed by a trained health and safety professional with experience in obsolete pesticides management. In general there are three main ways to protect workers from chemical hazards (in order of preference):

i. Keep the workers and population away from all possible sources of contaminationii. Control the contaminants so that the possibility of exposure is minimizediii. Protect the worker using personal protective equipment.

All health and safety plans should adhere to the above principles and recognize local or national labour standards.

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4.9.1.1 Site arrangement

375.Each site has to be set up in accordance with the principles shown in the Instruction document (see also UK HSE) document on the ‘Protection of workers and the general public during the development of contaminated land’).

376.Environmental protection and the prevention of cross contamination has to be achieved by establishing bunded areas using a combination of heavy duty polythene sheeting and plywood panels, plus the installation of a footwear changing station for use on entry into or exit from the working area.

377.Dry powder fire extinguishers have to be supplied and will be sited in each working area. Field staff should preferably qualified fire fighters.

378.Normally there is a great deal of interest from people living close to each site. Their safety should be assured by cordoning off a larger perimeter using high visibility tape and ensuring that one member of the team has the duty of preventing unauthorised access. When the site has been completed, the protective membrane and sheets should be carefully removed for reuse at another site or, if contaminated and damaged, it has to be packaged for disposal. At larger sites (normally where the operations take longer than one day) provision should be made to either secure the site at the end of each day, or through the provision of a security guard.’

379.Further information on health and safety is also available from the International Labour Organization (1999a and 1999b), the World Health Organization (1995 and 1999) and IPCS INCEM (no date).

4.9.1.2 Personnel protection

380.Personnel engaged in the operation shall wear adequate personal protective equipment (PPE) which will include disposable coveralls, PVC or nitrile gloves or similar, eye protection and safety foot wear. In addition, the following equipment will be available for use as circumstances dictate:

- Helmets;- PVC aprons;- Disposable organic vapour masks (for example type 3M 4251 or 3M 4000);- Full face masks (covering face : eyes, nose and mouth) with filter (to protect against dust and gasses).

The code on filter (filtre combiné) should be : A2B2E2K2P3. The expiry date of the filter has to be checked;

- Disposable underwear ;- Air supplied respiratory protective equipment (to be applied in closed, underground or high

temperature situations).

The contractors’ representative is the one responsible to decide which equipment must be worn for each operation. A full first aid Kit, emergency eye wash and emergency shower should preferably be present at each site. Smoking, eating and drinking should be forbidden on the site. At the commencement of all breaks and lunch periods, all PPE should be removed and all personnel shall wash their hands and face. Footwear should be changed on entering/exiting the working areas.

Wheeled/tracked vehicles should not be allowed to traverse contaminated areas. All personal preferably showers at the end of a working day.

4.9.2. High-volume, high-concentration or high-risk situations

381.Situations with high-volume, high-concentration or high-hazard risk POPs pesticides situations include:

i. waste handling areas;

ii. storage sites;

iii. treatment and disposal areas;

iv. and contaminated sites with high concentration of POPs pesticides at or near the surface.

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382.At a minimum, the following should preferably be included in POPs pesticides health and safety plans for high volume/high concentration (check with contractor for contractual obligations):

i. the Health and Safety Plan (HASP) should be in writing, with a copy available at each site containing POPs pesticides;

ii. each worker who is to have access to the “exclusion” zone (see below) should read the HASP and sign that they have read and understood it;

iii. the HASP may be written to encompass all hazards at a site but should have a section or chapter specifically detailing procedures for the POPs pesticides;

iv. workers should only be present in an area containing POPs pesticides (the exclusion zone) when necessary for the inspection, repackaging, removal of stored materials;

v. workers entering an exclusion zone should have appropriate health and safety and operational training for chemical, physical and biological hazards;

vi. health and safety training should be performed annually;

vii. POPs pesticides exclusion zones should be routinely monitored for these contaminants in air;

viii.when appropriate, workers entering an exclusion zone should wear appropriate respiratory protection and POPs pesticides (dust and liquid) impermeable fabric should cover the entire body (i.e., coveralls with hood, face-shield, gloves and boot covers or a full-body suit);

ix. spill cleanup kits and personal decontamination materials should be present in all areas containing POPs pesticides during operations;

x. workers who are, or are expected to be, routinely entering obsolete pesticides exclusion zones or working with these substances should be medically monitored including a baseline medical examination;

xi. where POPs pesticides are to be handled in an open system, or where it is reasonably expected that the protective clothing of a worker may contact POPs pesticides, a “contaminant reduction” zone should be established where workers can be decontaminated and remove their protective equipment; and

4.9.3. Low-volume, low-concentration sites or low-risk situations

383.The recommended health and safety practice in the previous section do not apply to sites that contain POPs pesticides in amounts or concentrations that are not seen as acute or chronically hazardous to human health and the environment. There is no clear definition of low concentration or low volume situations and “low-risk” should be determined by comparing contaminant levels with government guidelines or by conducting a site specific risk assessment. Some examples of low-risk situations to worker health and safety include:

i. commercial storage or inventory rooms that contain small quantities of products (i.e. POPs pesticides) that are to be used in acceptable application situations;

ii. facilities that unintentionally generate and release in very low concentrations with respect to human exposure limits; and

iii. contaminated sites with low levels of POPs pesticides.

Despite the low risk situation, some health and safety measures should be taken to minimize exposure, including health and safety training of personnel who are likely to come into contact with POPs pesticides.

4.10 Emergency response

384.Emergency response plans should be in place for expected POPs pesticides in storage, in transit and at a disposal site. While the emergency response plans will vary for each situation, there are some common elements. The main elements of an emergency response plan are:

i. planning of possible emergency situations and possible responses;

ii. training of personnel in response activities including simulated response exercises;

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iii. maintaining mobile spill response capabilities or retaining the services of a specialized firm for spill response;

iv. notification of fire department, police and other government emergency response agencies of the location of POPs pesticides and the routes of transport;

v. installation of mitigation measures such as fire extinguishing systems, spill containment, fire-fighting water containment, spill and fire alarms;

vi. installation of emergency communication systems including signs indicating emergency exits, telephone numbers, alarm locations and response instructions;

vii. installation and maintenance of emergency response “kits” containing sorbents, personnel protective equipment, portable fire extinguishers, and first aid supplies; and

viii.integration of local plans with national, regional, and international emergency plans if appropriate.

Specific actions that can be taken in the event of a spill, leak or fir can be found in specific manuals dealing with emergency response.

4.11 Public participation

385.Parties to the Basel or Stockholm Convention should have an open public participation process. For further information please refer to section 4.11 of the General Technical Guidelines for Environmentally Sound Management of Wastes Consisting of, Containing or Contaminated with Persistent Organic Pollutants. Many of the failures of the past, were often not concerned with the technical solutions as such, but with the lack of the start of the public participation process at the earliest possible start. See also FAO Guidance Document, The Selection of Waste Management Options for the Disposal of Obsolete Pesticides and Contaminated Materials (Draft under preparation).

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Annex ISynonyms and trade names for POPs pesticides(See also Ritter)

Chemical Some Synonyms and Trade Names a

ALDRIN Aldrec, Aldrex, Aldrex 30, Aldrite, Aldrosol, Altox, Compound 118, Drinox, Octalene, Seedrin

CHLORDANE Aspon, Belt, Chloriandin, Chlorkil, Chlordane, Corodan, Cortilan-neu, Dowchlor, HCS 3260, Kypchlor, M140, Niran, Octachlor, Octaterr, Ortho-Klor, Synklor, Tat chlor 4, Topichlor, Toxichlor, Veliscol-1068

DIELDRIN Alvit, Dieldrite, Dieldrix, Illoxol, Panoram D-31, Quintox ENDRIN Compound 269, Endrex, Hexadrin, Isodrin Epoxide, Mendrin, NendrinHEXACHLOROBENZENE Amaticin, Anticarie, Bunt-cure, Bunt-no-more, Co-op hexa, Granox,

HCB, No bunt, Sanocide, Smut-go, Sniecotox HEPTACHLOR Aahepta, Agroceres, Baskalor, Drinox, Drinox H-34, Heptachlorane,

Heptagran, Heptagranox, Heptamak, Heptamul, Heptasol, Heptox, Soleptax, Rhodiachlor, Veliscol 104, Veliscol heptachlor

MIREX Dechlorane, Ferriamicide, GC 1283, Perchlordecone TOXAPHENE Alltex, Alltox, Attac 4-2, Attac 4-4, Attac 6, Attac 6-3, Attac 8,

Camphechlor, Camphochlor, Camphoclor, Chemphene M5055, chlorinated camphene, Chloro-camphene, Clor chem T-590, Compound 3956, Delicia Fribal, Huilex, Kamfochlor, Melipax,Motox, Octachlorocamphene, Penphene, Phenacide, Phenatox, Phenphane, Polychlorocamphene, Strobane-T, Strobane T-90, Texadust, Toxakil, Toxon 63, Toxyphen, Vertac 90%

a The list of trade names is not intended to be exhaustive.

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Appendix 2: References

Ahling, B., 1979. “Destruction of chlorinated hydrocarbons in a cement kiln”. Environmental Science and technology, 13, 1377

ATSDR, Agency for Toxic Substances and Disease Registry, Toxicological Profile Information Sheets, http://www.atsdr.cdc.gov/toxprofiles for Aldrin and Dieldrin, Update September 2002

ATSDR, Agency for Toxic Substances and Disease Registry, Toxicological Profile Information Sheets, http://www.atsdr.cdc.gov/toxprofiles for Chlordane, Update May 1994

ATSDR, Agency for Toxic Substances and Disease Registry, Toxicological Profile Information Sheets, http://www.atsdr.cdc.gov/toxprofiles for Endrin, Update, Update August 1996

ATSDR, Agency for Toxic Substances and Disease Registry, Toxicological Profile Information Sheets, http://www.atsdr.cdc.gov/toxprofiles for Heptachlor and Heptachlor Epoxide, Update April 1993

ATSDR, Agency for Toxic Substances and Disease Registry, Toxicological Profile Information Sheets, http://www.atsdr.cdc.gov/toxprofiles for Hexachlorobenzene, Update September 2002

ATSDR, Agency for Toxic Substances and Disease Registry, Toxicological Profile Information Sheets, http://www.atsdr.cdc.gov/toxprofiles for Mirex and Chlordecone, Update August 1995

ATSDR, Agency for Toxic Substances and Disease Registry, Toxicological Profile Information Sheets, http://www.atsdr.cdc.gov/toxprofiles for Toxaphene, Update August 1996

Baker, R.S. and J.C. LaChance. 2003. “Performance Relative to Dioxins of the In-Situ Thermal Destruction (ISTD) Soil Remediation Technology.” In: G. Hunt (ed.) Proceedings of the 23rd International Symposium on Halogenated Organic Pollutants and Persistent Organic Pollutants (Dioxin 2003), Boston, MA, Aug. 24-29, 2003

Benestad, C., 1989. “Incineration of hazardous waste in cement kilns”. Waste Management Research, 7, 351;

Bierschenk, John M, Ralph S. Baker, Robert J. Bukowski, Ken Parker and Ron Young, Jennie King and Tony Landler, Douglas Sheppard, 2004, Full-scale Phase 1a Results of ISTD Remediation at former Alhambra, California Wood Treatment Site

Black, W.M. and Swanson, J.R., 1983. “Destruction of PCBs in cement kilns”. Pollution Engineering, June, 50-54.

Botany-HCB site website at http://www.botany-hcb.com/index.html under “The Proposed Technology” and “Trials of the Proposed Technology”

Canadian Council of Ministers of the Environment, 1997. Guidance Document on the Management of Contaminated Sites in Canada. Available at www.ccme.ca

Callow, R.A., et al., “ISV Application to Buried Waste, Executive Summary of Intermediate Field Tests at INEL”, EGG-WTD-9887, Idaho National Environmental and Engineering Laboratory (1991).

Cembureau, 2004. http://www.cembureau.be/ ).

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