Technical Guidelines for Environmentally Sound Management Ofwastes Consisting Of, Containing

DRAFT

Technical Guidelines for Environmentally Sound Management ofWastes consisting of, containing or contaminated with the pesticides Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene, Mirex or Toxaphene

7 February 2005

December 2004

[Document Number!]

Table of Contents

I. Introduction

A.Scope

B.Description, production, use and wastes

1.Aldrin

(a)Descriription

(b)Production

(c)Use

2. Chlordane

(a)Description

(b)Production

(c)Use

3. Dieldrin

(a)Description

(b)Production

(c)Use (see also Aldrin)

4. Endrin

(a)Description

(b)Production...... 7

(c)Use

5 HCB

(a)Description

(b)Production

(c)Use

6 Heptachlor

(a)Description

(b)Production

(c)Use

7 Mirex

(a)Description

(b)Production

(c)Use

8. Toxaphene

(a)Description

(b)Production

(c)Use

9Wastes

II.Relevant provisions of the Basel and Stockholm Conventions

A.Basel Convention

B.Stockholm Convention

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

A.Low POP content

B.Levels of destruction and irreversible transformation

C.Methods that constitute environmentally sound disposal

IV.Guidance on environmentally sound management (ESM)

A.General considerations

1.Basel Convention

2.Stockholm Convention

3.Organization for Economic Cooperation and Development

B. Legislative and regulatory framework

C.Waste prevention and minimization

D.Identification and inventories

1. Identification

2.Inventories

E.Sampling, analysis and monitoring

1.Sampling

2.Analysis

(a)Field tests

(b)Laboratory analysis

3.Monitoring

F.Handling, collection, packaging, labelling, transportation and storage

1.Handling

2.Collection

3.Packaging

4Labelling

5.Transportation

6.Storage

G.Environmentally sound disposal...... 20

1. Pretreatment...... 20

2.Destruction and irreversible transformation methods...... 20

3.Other disposal methods when destruction or irreversible transformation does not represent the environmentally preferable option 20

4.Other disposal methods when the POP content is low...... 21

H.Remediation of contaminated sites...... 21

I.Health and safety...... 21

1. High-volume, high-concentration or high-risk situations...... 21

2.Low-volume, low-concentration sites or low-risk situations...... 22

J. Emergency response...... 23

K. Public participation...... 23

Annex I:

Synonyms and trade names for POPs pesticides………………………………………………………….24

Annex II: Bibliography………………………………………………………………………………………………30

Abbreviations and Acronyms

ADREuropean Agreement of Road Transport Hazardous Waste Materials

ATSDRAgency for Toxic Substances and Disease Registry

BATBest Available Techniques

BEPBest Environmental Practices

COPConference of the Parties

DDT Dichloro-diphenyl-trichloroethane

ESMEnvironmentally sound management

EUEuropean Union

FAOFood and Agriculture Organisation

GCGas chromatography

GCMSGas chromatography mass spectrometry

HEOD1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro- endo-1,4- exo-5,8,-dimethanonaphthalene

HHDN1,2,3,4,1910-hexachloro, 1,4,4a,5,8,8a-hexachydro-exo-1,4-endo-5,8-dimethanonaphtalene

HCBHexachlorobenzene

HASPHealth and Safety Plan

HPLCHigh-pressure liquid chromatograph

IATAInternational Air Transport Association

ICAO International Civil Aviation Organisation

IMDG CodeInternational Maritime Dangerous Goods Code

IMOInternational Maritime Organisation

INCIntergovernmental Negotiating Committee

IPCSInternational Programme on Chemical Safety

MSMass spectrometry

OECD Organization for Economic Cooperation and Development

OEWGOpen Ended Working Group

OSHAOccupational Safety and Health Administration

PICsPacific Island Countries

PCBPolychlorinated biphenyl

PCCPolychlorinated camphenes

PCDDPolychlorinated dibenzo-p-dioxins

PCDFPolychlorinated dibenzofurans

POPPersistent organic pollutant

Pesticide POPsGroup of pesticides being: Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene (HCB),

Mirex or Toxaphene except DDT

PPEPersonal protective equipment

PVCPolyvinylchloride

SDSSafety Data Sheets

TEQ Toxic equivalent(s)

UNECEUnited Nations Economic Commission for Europe

UNEPUnited Nations Environment Programme

US EPAUnited States Environmental Protection Agency

WHOWorld Health Organization

Units of measurement

mg/kg Milligram(s) per kilogram. Corresponds to parts per million (ppm) by mass.

μg/kg Microgram(s) per kilogram. Corresponds to parts per billion (ppb) by mass.

ng/kgNanogram(s) per kilogram. Corresponds to parts per trillion (ppt) by mass.

ppbParts per billion

ppmParts per million

pptParts per trillion

tonstons in SI units

1December, 2004

[Document Number]

I. Introduction

A.Scope

These technical guidelines provide guidance for the environmentally sound management (ESM) of wastes consisting of, containing or contaminated with the pesticides aldrin, chlordane, dieldrin, endrin, heptachlor, hexachlorobenzene (HCB), mirex or toxaphene (abbreviated as “Pesticide POPs”) in accordance with decisions V/8, VI/23 and VII/13 of the Conference of the Parties to the Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and Their Disposal, decisions OEWG-I/4, OEWG-II/10 and OEWG-III/8 of the Open-ended Working Group of the Basel Convention, and taking into account Resolution 5 of the Conference of Plenipotentiaries on the Stockholm Convention on Persistent Organic Pollutants and decisions INC-6/5 and INC-7/6 of the Intergovernmental Negotiating Committee for an International Legally Binding Instrument for Implementing International Action on Certain Persistent Organic Pollutants. The Conference of the Parties to the Stockholm Convention on Persistent Organic Pollutants may consider these guidelines in accordance with article 6.2 of that convention.
In these technical guidelines all pesticides listed as Persistent Organic Pollutants (POPs) in Annex A of the Stockholm Convention are addressed. Dichloro-diphenyl-trichloroethane (DDT) is addressed in separate technical guidelines owing to its importance for malaria vector control in many tropical countries. Due to its importance for malaria vector control, DDT has been addressed separately in Annex B of the Stockholm Convention...
HCB as an unintentionally produced POP and as an industrial chemical is not covered by these guidelines. HCB as an unintentionally produced POP will be addressed in technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with PCDDs, PCDFs or unintentionally produced PCBs or HCB. HCB as an industrial chemical will be addressed in technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with HCB as an industrial chemical.

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 pesticide POPs (except DDT) for purposes of their identification and management.

B.Description, production, use and wastes

1.Aldrin

(a)Description

Aldrin are white, odourless crystals, when they are pure. Technical grades are tan to dark brown with a mild chemical odour (Ritter, year). Aldrin contains no less than 95% 1,2,3,4,10,10-hexachloro, 1,4,4a,5,8,8a-hexahydro-exo-1,4-endo-5,8-dimethanonaphtalene (HHDN). HHDN is a white, crystalline, odourless solid with a melting point of 104 to 104.5 °C. Technical aldrin is a tan to dark brown solid with a melting range from 49 to 60 °C. It is practically insoluble in water, moderately soluble in petroleum oil and stable to heat alkali and mild acids (ATSDR, 2002; IPCS, no date; WHO-FAO, 1979). Pure aldrin is stable at < 200 °C and between a pH-range from 4 to 8, however, oxidizing agents and concentrated acids attack the unchlorinated ring under any conditions. Aldrin is non-corrosive or slightly corrosive to metals because of the slow formation of hydrogen chloride on storage. Aldrin and Dieldrin are the common names of two insecticides, which are chemically closely related. Aldrin is readily converted to dieldrin in the environment (Global Pesticides Release Database, Environment Canada, no date). See annex I for examples of trade names.

(b)Production

Aldrin was first synthesized as a pesticide in the United States in 1948. Aldrin was manufactured by the Diels-Alder reaction of hexachlorocyclopentadiene with bicyclo[2.2.1]-2,5-heptadiene. The final condensation was usually performed at approximately 120 °C and at atmospheric pressure. Excess bicycloheptadiene was removed by distillation. The final product was usually further purified by recrystallization. Aldrin has been manufactured commercially since the 1950, and used throughout the world up to the early 1970s (ATSDR 2002, UNEP 2003 d).

(c)Use

Aldrin has been manufactured commercially since 1950 and used throughout the world up to the early 1970s to control soil pests such as corn rootworm, wireworms, rice water weevil, and grasshoppers. It has also been used to protect wooden structures, plastic and rubber coverings of electrical and telecommunication cables (ATSDR, 2002; UNEP, 2002a). In 1966, aldrin use in the United States peaked at 8,550,000 kg, but by 1970, use had decreased to 4,720,000 kg.
In 1970, the U.S. Department of Agriculture cancelled all uses of aldrin and dieldrin due to the concern that these chemicals could cause a severe environmental damage to aquatic ecosystems and their potentially carcinogenic properties. In early 1971, US EPA initiated the cancellation proceedings for aldrin and dieldrin, but did not order the suspension of aldrin and dieldrin use. In 1972, under the authority of the Federal Insecticide, Fungicide and Rodenticide Act as amended by the Federal Pesticide Control Act of 1972, an EPA order lifted the cancellation of aldrin and dieldrin use in three cases:
subsurface ground insertion for termite control;
dipping of nonfood plant roots and tops; and
moth-proofing in manufacturing processes using completely closed systems.

Most of the information on aldrin is also applicable for dieldrin.

2. Chlordane

(d)Description

Technical chlordane is a viscous mixture of at least 23 different components, including chlordane isomers, other chlorinated hydrocarbons, and by-products. The main constituents of technical chlordanes are trans-chlordane (gamma-chlordane) (share of about 25 %), cis-chlordane (alpha-chlordane) (share of about 70%), heptachlor, trans-nonachlor, and cis-nonachlor (share less than 1 %). Heptachlor is one of the most active components of technical chlordane. Chlordane is a viscous, colourless or amber-coloured liquid with a chlorine-like odour. Pure chlordane has a melting point of 104 °C, is not soluble in water and stable in most organic solvents, including petroleum oils. It is unstable in the presence of weak alkalis. (ATSDR, 1994; EXTOXNET, Holoubek, 2004; IPCS,no date;UNEP, 2002a; WHO-FAO, 1979). See annex I for examples of trade names.

(e)Production

Chlordane is produced by chlorinating cyclopentadiene to form hexachlorocyclopentadiene and condensing the latter with cyclopentadiene to form chlordene. The chlordene is further chlorinated at high temperature and pressure to chlordane (ATSDR, 2002; UNEP, 2003d).
The raw materials for the manufacturing process are cyclopentadiene, hexachloro- cyclopentadiene and chlorine, or some chlorinating agent. Chlordane is manufactured in a two-step reaction. In the first step, hexachlorocyclopentadiene reacts with cyclopentadiene in a Diels-Alder reaction. The reaction is exothermic and proceeds readily at a temperature up to about 100°C. The intermediate is called “chlordane”. In the next step, chlorine is added to the unsubstituted double bond. Various chlorinated agents e.g. sulphuryl chloride, and catalysts, such as ferrochloride have been described to make addition dominant over substitution, but it is believed that only chlorine is used in actual practice (De Bruin, 1979).

(f)Use

Chlordane, which was introduced on the market for the first time in 1945,is a broad-spectrum contact insecticide that had been employed on agricultural crops, on lawns and gardens.It has also extensively been used in the control of termites, cockroaches, ants and other household pests (Fiedler, 2000; UNEP, 2002a). In China, chlordane is still used as a termicide in buildings and dams. China has requested a specific exemption for the use as a termicide according to Art.4 and Annex A of the Stockholm Convention (UNEP, 2002b).
In 1988, the commercial use of chlordane was cancelled in the United States. Between 1983 and 1988 the sole/core use for chlordane was to control subterranean termites. For this purpose, chlordane was applied primarily as a liquid that was poured or injected around the foundation of a building. Chlordane, in conjunction with heptachlor, was at one time widely used as a pesticide for the control of insects on various types of agricultural crops and vegetation. The use pattern for chlordane in the mid 1970s was as follows: 35 % used by pest control operators, mostly on termites; 28 % on agricultural crops, including corn and citrus; 30 % for home lawn and garden use; and 7 % on turf and ornamentals. In 1978, a final cancellation notice was issued which called for the suspension of the use of chlordane except for subsurface injection to control termites and for dipping roots and tops of nonfood plants. Minor use of chlordane for treating nonfood plants was cancelled by 1983. The use of chlordane decreased drastically in the 1970s when EPA cancelled all uses other than subterranean termite control (ATSDR, 2002).

3. Dieldrin

(a)Description

Dieldrin is a technical product containing 85 % of the chemical known as 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro- endo-1,4- exo-5,8,-dimethanonaphthalene (HEOD). Dieldrin is closely related to its metabolic precursor aldrin. The pure major ingredient HEOD is a white crystalline solid with a melting point of 176/177 °C. Technical dieldrin is a light tan flaky solid with a melting point of 150 °C. In water, it is practically insoluble and slightly soluble in alcohol. Pure HEOD is stable in alkali and diluted acids, but reacts with strong acids (ATSDR, 2002; IPCS, year; WHO-FAO, 1975). See annex I for examples of trade names.

(b)Production

Dieldrin was manufactured by epoxidation of aldrin. The epoxidation of aldrin was obtained by reaction with a peracid (producing dieldrinand an acid byproduct) or withhydrogen 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).

(c)Use (see also Aldrin)

Dieldrin was mainly used for the control of soil insects such as corn rootworms, wireworms and catworms (UNEP, 2002a). Besides, dieldrin was and is still used in public health protection to control several insect vectors (ATSDR, 2002; Fiedler, 2000).In India, its manufacture and import are banned, but marketing and restricted use (locust control) is permitted for a period of 2 years of the date of expiry, which date is earlier. Restricted use of dieldrin is reported from Bangladesh, Myanmar and Nepal (UNEP, 2002c)

4. Endrin

(a)Description

Endrin, when pure, is a white crystalline solid and has a melting point of 200 °C. It is decomposed

at temperatures above 245 °C (Boiling point). The technical product is a light tan powder with a characteristic odour. It is practically insoluble in water and slightly soluble in alcohol. It is stable in alkali and acids, but it rearranges to less insecticidally active substances in the presence of strong acids, on the exposure to sunlight or on heating above 200 °C (ATSDR, 1996; IPCS, year; WHO-FAO, 1975)

(b)Production

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).
It is estimated that 2,345,000 kg of endrin were sold in the United States in 1962, while less than 450,000 kg were produced in 1971. More recent estimates of domestic production of endrin could not be found. As with many toxic chemicals, information on production or use of pesticides is often proprietary, and quantitative estimates of production of endrin are virtually impossible to obtain. No information on the production of endrin was available from the Toxic Release Inventory (TRI), because endrin is not one of the chemicals that producers are required to report on. Endrin aldehyde and endrin ketone never were commercial products, but occurred as impurities of endrin or as degradation products. While commercial preparations of solid endrin were typically 95-98 % pure, the following chemicals (in addition to endrin aldehyde and endrin ketone) have been found as trace impurities in commercial endrin products: aldrin, dieldrin, isodrin, heptachloronorbornadiene, and heptachloronorborene (HSDB, 1995). The active ingredient would often be mixed with one or more organic solvents for application in a liquid form. Carriers included xylene, hexane, and cyclohexane (ATSDR, 2002; UNEP, 2003d). See annex I for examples of trade names.

(c) Use

Beginning in 1951, endrin was first used as an insecticide, rodenticide, and avicide to control cutworms, mice, voles, grasshoppers, borers, and other pests on cotton, sugarcane, tobacco, apple orchards, and grain. It was also used as an insecticide agent on bird perches, but has never been extensively used for termite-proofing or other applications in urban areas, even if it has many chemical similarities with aldrin and dieldrin.. Endrin’s toxicity to nontarget populations of raptors and migratory birds was a major reason for its cancellation as a pesticide agent. Except for use as a toxicant on bird perches, which was cancelled in 1991, the manufacturer voluntarily canceled all other uses of endrin in the United States in 1986. It has been estimated that 6,250 kg of endrin were used annually in the United States prior to 1983. Both the EPA and FDA revoked all food tolerances for endrin in 1993 (ATSDR 2002, Fiedler 2000).

5 HCB

(a)Description

Hexachlorobenzene (HCB) consists of a colourless white powder or needles with a melting range of 229 to 326 °C. Products in technical or agricultural grade contain 98 % HCB and up to 2 % impurities (1.8 % pentachlorobenzene and 0.2 % 1,2,4,5-tetrachlorobenzene including higher chlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls). Its melting point is over 200 °C. HCB is practically insoluble in water, slightly soluble in cold alcohol. It is stable in strong acids and its decomposition in alkalis continues very slowly (ATSDR, 2002; IPCS, year; WHO-FAO, 1977; Holoubek et al, 2004). See annex I for examples of trade names.

(b)Production

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 production process of several pesticides, including pentachloronitrobenzene (PCNB), tetrachloroisophthalonitrile (chlorothalonil), 4-amino-3,5,6-trichloropicolinic acid (picloram), pentachlorophenol (PCP) (only in Europe) and dimethyltetrachloroterephthalate (DCPA or Dacthal®) and was also produced as a by-product during the production of atrazine, propazine, simazine, and mirex (De Bruin, 1979; ATSDR, 2002).

Hexachlorobenzene (HCB) was used world-wide as a fungicide for agricultural purposes from 1915 on. HCB was widely used as a pesticide, mainly as a seed dressing to prevent fungal disease on grain and field crops such as wheat and rye. Its use in industry is not described here (Holoubek, 2004). HCB has been extensively applied in the Russian Federation and is therefore a pesticide of serious environmental concern in that area. (ATSDR, 2002; Fiedler, 2000; UNEP, 2002b).

6 Heptachlor

(a)Description

Pure heptachlor is a white crystalline solid with a melting point of 95/96 °C. Technical heptachlor is a soft waxy solid with a melting range between 46 and 74 °C. It is practically insoluble in water and slightly soluble in alcohol. It is stable up to temperatures between 150 and 160 °C as well as towards light, air moisture, alkalies and acids. It is not readily dechlorinated, but is susceptible to epoxidation (ATSDR 1993; IPCS, no year; WHO-FAO, 1975). See annex I for examples of trade names.

(b)Production