Fact sheets on production, use and release of priority substances in the WFDRoyal Haskoning
Heaxachlorobenzene, Final draft
For official use only
Draft version: Final draft (previous version: 3.3)
Status date: 15 oktober 2002
Comments:
-Changed format
-Remarks of EU letter ENV B.1/PMM/JD’E/ipD (2002) 310893 (30-702) incorporated
-Measures added
SUBSTANCE: HexachlorobenzeneI Chemical identity
CAS number:118-74-1
Chemical group: Chlorinated aromatic hydrocarbons C6-C16
Homologues: not relevant
Synonyms: HCB, Amatin; Anticarie; Bunt-cure, Hexa CB; No bunt 80; Pentachlorphenylchlorid; Perchlorbenzol; Sanocide; Sniecotox
Technical mixtures: not relevant-
II Physical properties
Water solubility: 5 µg/l [BD RIVM][Slooff et al, 1991]
Vapour pressure: 0,0013 Pa
0.02 Pa at 25.0 °C [BgVV, 1999]
Log Kow: 3.03-6.92
III Production and use in 15 EU member states and accession states
- Way of production/process description:
By-product present in technical grade products. [Baily, 2001]
HCB is formed by chlorination of benzene or a lower chlorinated benzene at elevated temperature with a catalyst [Beck, 1986 in Baily, 2001]
- Fields of application:
Former use was:
- A fungicide for seed treatment especially for control of bunt in wheat and fungi in onions.
- A by-product of production of carbontetrachloride, perchloroethylene, trichloroethylene, and pentachlorobenzene.
- Impurity in formulations of pentachlorphenol and dichloram.
- Industrial chemical for making fireworks, ammunition, and synthetic rubber.
- Used in secondary aluminium processing.
- Graphite rods. [Eurochlor, 20001a].
- Production volume
Former production:
Since 1974 4,000 t/y
In 1980 5,000 t/y
In 1990 1,500 t/y as intermediate for pentachlorothiophenol (auxiliary agent for rubber) (Bayer AG, Germany)
Former production by ICI Ltd
- Number of production sites and locations of production:
HCB is not produced anymore as a product. Unintentional production in chlor-alkali industry at about 80 sites (members of Euro Chlor).
Locations of production, reported by IUCLID[2000], are presented in appendix 1. (This may be misleading in contrast to the information of Euro Chlor.)
- Use volume:
- Relative use volumes in various applications:
- Existing regulation:
Community wide limit values for discharges of wastes (88/347/EEC)
Black list, hexachlorobenzene, Listed:
EC (1982) List I within the framework of Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the community Official Journal C 176, 14/7/1982 p. 7-10. Emission limit value 1.5 g/t per and tetra production.
Voluntary limit 10 µg/l in waste water from EDC, VCM and PVC production before 2003.
Proposed WQO EEC 0.01 µg/l [Euro Chlor][Eurochlor, 2001a]
Priority substance under WFD
To be monitored under EPER [AEAT][Brown et al., 2000]
Banned in member states: Austria (1992), Belgium, Denmark, France, Germany (1988), Netherlands (1973), Sweden, (1980), Switzerland, UK, (1975)
Banned in Accession countries: Cz, Sl (1988), Hungary [AEAT][Brown et al., 2000]
Under UNECE protocol scheduled for elimination of production and use
Included in draft UNEP convention [AEAT][Brown et al., 2000]
UNECE POP & Heavy metals, hexachlorobenzene, Listed:
OSPAR 1998 List of Candidate Substances OSPAR strategy with regard to Hazardous Substances (Ref. nr. 1998-16), Annex 3, Sintra 22-23, July 1998 [EaSIView 9]
North sea Action Plan (NAP), Hexachlorobenzene, Class 1A:
North Sea Ministers Conference (1990), North Sea Action Plan, National implementation order third North Sea Ministers Conference. Lower chamber, Conference year 1990-1991, 21884 no. 1-2 [EaSIView 9]
- Industrial associations to be addressed:
IV Releases to environment
- General way of entrance into the aquatic environment:
From historical pollution sites, waste disposal and anaerobic sediments S10 and S11
Agriculture: S3.1
S2, S5, S4-S6
Atmospheric deposition:Formulation/industrial use: A5/A6 S1 S2 or S5 (low)
Waste incineration &
Volatilisation from landfill:A7
Historic pollution:A8
- Atmospheric cycle:
- Industrial Point Sources to the air
-According to an industrial survey, emissions from Euro Chlor member companies ( 80 sites) have decreased 3 kg/year to air in 1998. In 1997 this was 4 kg to air. Emissions to air have been divided by a factor 40 in 15 years (1983-1998) [Eurochlor, 2001b]
-Chlorinated chemicals (NOSE 105.09.63)
In the production of chlorinated chemicals, process water containing HCB is separated and incinerated or placed in underground disposal facilities. Small amounts are emitted to air or wastewater. The European HCB emissions inventory lists 557 kg/year for HCB emissions to the atmosphere from organic chemical manufacturing. [Berdowski, 1997 in Baily, 2001]
-Chemical processing(NOSE 105.09.63)
Emissions from chemical processes (production PER, chlorobenzenes and other chlorinated organics). In EU HCB formed is separated and incinerated with high efficiency. [Eurochlor, 2001a]
-Emissions from metalsindustries (NOSE 104.12.11)
Degassing of aluminium with hexachloroethane yields 4300 micrograms HCB/g hexachloroethane. This could lead to a global HCB emission of 15,050 kg/yr. Part of this (+-50%) will be removed by treatment. Secondary copper recovery: the high emission factor rates 3.9E-07 kg HCB/kg corresponding to a calculated global emission of 1042 kg/yr. [Baily, 2001]
-Emissions from combustionprocesses (NOSE 101)
Coal combustion: emission factors are reported ranging from 1.3x10-11 – 4.9x10-10 HCB/kg coal. [Baily, 2001]
-Cement production (NOSE104.11.02)
Hazardous wastes are used as fuel supplement because of controlled high temperature. Emissionfactor 1.7x10-10 kg/kg cement. [Cornelissen 1998 in Baily, 2001]
-Iron ore sintering (NOSE104.12.02)
Emission factor: 1.5x10-10-1.5x10-8 kg HCB/kg. Estimated global HCB emission is 70 kg/year. [Baily, 2001]
Available national release data:
-Germany
Total industrial and anthopogenic environmental emissions of HCB in Germany 200 kg/yr along with 10,000-50,000 kg/year remobilised from soil. [Franke et al. 1996 in Baily, 2001]
- Municipal Collective Sources to the Air:
-Volatilisation from landfills (NOSE109.06.11)
Volatilisation from landfills does occur. [Eurochlor, 2001a]
-Incinerators(NOSE109.03.01)
emission to air 10 kg/y
In ashes 50 kg/y [Slooff et al, 1991]
-Emissions from municipal waste incineration (NOSE 109.03.01)
Reported is a wide range of HCB yield from municipal waste incineration: 7.7x10-10 - 1.7x10-6 kg HCB/kg waste. [Baily, 2001]
-Emissions from hazardous waste incineration (NOSE 109.03.06)
Oberg and bergstrom report a wide range of emission factors: 2.1x10-10-3.6x10-8 kg HCB/kg waste. [Baily, 2001]
-Sewage sludge incineration (NOSE109.05.01)
Emission factor: 4.7x10-10-4.7x10-8 kg HCB/kg. Estimated global HCB emission is 12 kg/year. [Baily, 2001]
-Biomass burning
No experimental data on HCB emissions are available. Reported factors by Cohen et al.: 1.9x10-11-1.9x10-10 kg HCB/kg wood. [Baily, 2001]
- Diffuse sources to air and deposition
-Estimated HCB emissions for Europe from 1982-1985 (including European part of USSR): 51,132 kg/yr. The majority of this was attributed to the use of contaminated pesticides. [Axenfeld 1992 in Baily, 2001]
-Trace contaminant in certain pesticides (NOSE 110.06)
Modelling studies have shown that 6% of the HCB contained in pentachlorophenol used in wood treatment is volatilised over the 35 year service life of treated wood. [Estreicher 1999 in Baily, 2001][Eurochlor, 2001a]
-Global emission from contamination of pesticides (NOSE 110.06)
Total estimated global emission from contamination of pesticides: 6500 kg/yr. [Baily, 2001]
For Europe (38 countries), an estimated emission level of 8040 kg in 1990 is mentioned with emissions from agriculture representing 72% of the total.[Berdowski 1995 in Eurochlor, 2001a]
Release from traffic to air (release route: A2)
-Motor fuel(NOSE 201/202)
Emissions are reported to be insignificant. [Baily, 2001]
Soil to air due to revitalisation
-While production and use have been eliminated, its continued presence in the environment suggests some current releases of HCB. [Estreicher 1999 in Baily, 2001]
Available national release data:
-Germany:
Total industrial and anthopogenic environmental emissions of HCB in Germany 200 kg/yr along with 10,000-50,000 kg/year remobilised from soil. [Franke et al. 1996 in Baily, 2001]
- Aquatic releases:
- Industrial Point Sources to the aquatic environment
According to an industrial survey, emissions from Euro Chlor member companies ( 80 sites) have decreased to 90 kg/year to water in 1998. In 1997 this was 100 kg/year to water. Emissions to water have been divided by a factor 7 in 15 years (1983-1998) [Eurochlor, 2001b]
- Municipal Collective Sources to the aquatic environment:
-Leaching from landfills [Eurochlor, 2001a](NOSE 109.06.11)
In 1987 estimated emission to Dutch Surface water via STP (S9) was 0.4 kg/y = 0.027 mg/capita.y. In municipal sewage sludge 0.6Mt ds with 10 – 100 µg/kg HCB = 6 – 60 g/y = 0.2 – 2 mg/capita.y. In 1988 1.5 mg/ton municipal solid waste = 11.3 kg in the Netherlands or 11.3/15 million inhabitants = 0.75 mg/capita.y.
Together these emissions are about 2 mg/capita.y, and for EU population 0.7 ton/y [Slooff et al, 1991]
- Diffuse sources to water
- Overall Releases and Summary:
Global HCB emissions are estimated at 23,000 kg/y with a range of 12,000 – 92,000 kg/y. Divided in different categories of sources:
-pesticides application: 6,500 kg/y
-manufacturing: 9,500 kg/y
-combustion: 7,000 kg/y.
V Environmental fate of releases to water
- Adsorption to solids (sediment, sludge, soil):
90 percentile value in sediments of EU rivers: 50 µg/kg [Eurochlor, 2001a]
Based on this Kd = 6.25 * 103 l/kg
- Volatilisation:
131 Pa.m3/mol (calculated from solubility and vapour pressure) [Euro Chlor 2001][Eurochlor, 2001b]
Substantial HCB volatilisation is suggested from its application in agriculture. [Baily, 2001]
- Degradation:
Photodegradation half life > 1 year [Blok et al., 1998][PTB]
1-2 year [BD RIVM][Slooff et al, 1991]
Deposition residence time for dry deposition 0.25 – 2 year and wet deposition 0.5 – 20 years
No important contribution to chemical reactions in stratosphere.
Overall residence time in atmosphere 0.01 – 1 year
- Partition between compartments:
Strong adsorption to soil no release to groundwater, evaporation from water to air 10 – 20 days.
Partition of HCB into different environmental compartments, according to MacKay level I calculation:
Air:48.3%
Water:1.1%
Soil:26.2%
Sediment:24.4% [Euro Chlor 2001][Eurochlor, 2001b]
- Behaviour
BCF up to 100,000
VI Evaluation
- Relevant NOSE-codes of point sources
101Combustion processes (production of heat and electricity)1.1
104.09/105.09Characteristic processes in the manufacture of chemicals, chemical4
products and man-made fibres
104.10/105.10Characteristic processes in the manufacture of rubber and plastic
products
104.11.02Cement
104.12.02Sinter plants2
104.12.11Secondary aluminium production2
105.09.11Graphite4.1
105.09.63Halogenated hydrocarbons production
107.03.05Rubber processing4.1
109.02Waste water treatment
109.03.01Incineration of domestic and municipal wastes
109.03.06Incineration of hazardous waste
109.05.01Incineration of sludges from waste water treatment
109.06.11Land filling
110.06Use of pesticides
201/202Traffic
- Evaluation of emission data:
- Emission to water
Global estimations indicate that 41% of total emission were due to manufacturing, 30 % due to combustion and 29% is caused by use of pesticides.
If 1,1% of total HCB emissions is released to water, the annual amount of emissions to water in the EU can be estimated at 90 kg/y.
- Emission to air
- Deposition
- Gaps and questions
- The size and the number of cases for historical pollution and release from landfills are not known.
- No data available in project database about deposition.
- The EUROCHLOR marine risk assessment clearly shows a significant decrease of HCB concentration in water, sediment and fish over the last 15 years, indicating that the remaining emissions are not leading to an additional burden to the environment. However it isn't clear how much is actually released to the water and by which route and source.
VII Measures
- Measures at production level:
- Contribution to water at production level
- Relevant IPPC sector, documents and available emission criteria
-1.1 Combustion installations;
-2. Production and processing of metals;
-4 Chemical industry;
-4.1 Chemical installations for the production of basic organic chemicals.
HCB is mentioned in the following BREF documents of IPPC sectors:
-Common waste water treatment;
-Textiles industry;
-Non-ferrous metal industry.
- Voluntary agreements
- Substitution
- Process control, modifications
- Effluent treatment
- co-agulation.
- Measures at use level:
- Contribution to water at use level
- Use by IPPC sectors
-to encourage collaboration with upstream partners about quantity and quality of substances (like HCB) applied to fibre during up-stream processes;
-avoid emissions of dioxins and furans arising from organically bound chlorine while incinerating sludge from waste water treatment
- Use by SME groups
- Use by consumers
- Use in agriculture
- Measures at community level:
- Sewage treatment
- Waste disposal
- Incineration
- Recycling
- Measures at regulatory level:
- EU level: IPPC emission control
EC (1982) List I within the framework of Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the community Official Journal C 176, 14/7/1982 p. 7-10. Emission limit value 1.5 g/t per and tetra production.
Community wide limit values for discharges of wastes (88/347/EEC)
- EU level: Substitution or outphasing
- EU level: Limitations of use in certain applications
- Other regulatory and/or national policy measures
Priority substance under WFD
To be monitored under EPER [Brown et al., 2000]
Banned in member states: Austria (1992), Belgium, Denmark, France, Germany (1988), Netherlands (1973), Sweden, (1980), Switzerland, UK, (1975)
Banned in Accession countries: Cz, Sl (1988), Hungary [Brown et al., 2000]
Under UNECE protocol scheduled for elimination of production and use
Included in draft UNEP convention [Brown et al., 2000]
UNECE POP & Heavy metals, hexachlorobenzene, Listed:
OSPAR 1998 List of Candidate Substances OSPAR strategy with regard to Hazardous Substances (Ref. nr. 1998-16), Annex 3, Sintra 22-23, July 1998
North sea Action Plan (NAP), Hexachlorobenzene, Class 1A:
North Sea Ministers Conference (1990), North Sea Action Plan, National implementation order third North Sea Ministers Conference. Lower chamber, Conference year 1990-1991, 21884 no. 1-2
LITERATURE
- Brown, K.A. et al., 2000. Exploration of possible future POP control areas.AEA Technology. AEAT/EPSC-0070.
- Baily R. E., 2001, Global hexachlorobenzene emissions. Chemosphere, Volume 43(2001).
- BgVV (Bundesinstitut für gesundheitlichen Verbraucherschutz und Veterinärmedizin), 1999. Chemikalieninformationssystem für Verbraucherrelevante Stoffe (CIVS). Berlin, Germany.
- Blok J., P.C. Okkerman, F. Balk, E.P. van der Zande-Guinée, J.P. Kimmel, 1998. Selection of Persistent, Toxic and Bioaccumulating (PTB) Substances - phase 2. HASKONING. Project under the authority of the Dutch Ministry of Housing, Spacial Planning and Environment.
Cordon, C., 2000, Socio-Economic Impacts of the Identification of Priority Hazardous Substances under the Water Framework Directive, Risk & Policy Analists
- Eurochlor, 2001a.0Information sheet on Hexachlorobenzene (HCB).
- Eurochlor, 2001b. Euro Chlor risk assessment for the marine environment OSPARCOM Region: North Sea. Hexachlorobenzene (HCB). Final draft.
- IUCLID, 2000. IUCLID Datasheet Hexachlorobenzene. ISBN 92–828–8641–7. Ispra, Italy.
Ministerio de Medio Ambiente, 2001, Spanish comments on the 2nd meeting of Experts Advisory Forum (EAF)
- Naturvårdsverket, 2001, Information on emission sources for priority substancesSlooff W., Bremmer H.J., Hesse J.M. en Matthijsen A.J.C.M. (eds.), 1991. Basis document Chloorbenzeen, RIVM, Report No. 710401005. Bilthoven, The Netherlands.
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Fact sheets on production, use and release of priority substances in the WFDRoyal Haskoning
Heaxachlorobenzene, Final draft
For official use only
aPPENDIX 1 lOCATION OF PRODUCTION
Country / Town / Company / DCM / CHCl3 / TCE / CTC / 1,2-DE / C2Cl4 / 1,2,4-TCB / 1,2,3-TCB / HCB / SCCP / HCBDB / Antwerpen / BASF Antwerpen N.V. / H
B / Tessenderlo / Limburgse Vinyl Maatschappij / H
B / Brussels / Solvay S.A. / H / H / H / H / H / H / L1)
D / Ludwigshafen / BASF AG / H / H
D / Leverkusen / Bayer AG / H / H / L1) / H
D / Frankfurt am Main / Celanese GmbH / H / H / H / H
D / Wolfen / Chemie GmbH Bitterfeld-Wolfen / H / H / L
D / Frankfurt am Main / Clariant GmbH / H
D / Stade / DOW Deutchland Inc. / H / H / H / H / H / L1)
D / Frankfurt/Main / EVC GmbH / H
D / Frankfurt/Main / Hoechst AG / H / H / H / H / H
D / Marl / Huels AG / H / H / H / H + L / L1)
D / Solingen / Solvay Alkali GmbH / H
D / Burgkirchen / Vinnolit Monomer GmbH / H
D / Burghausen / Wacker-Chemie GmbH / H / H / H
E / Barcelona / Erkimia, S.A. / H / H / H
E / Madrid / Aragones industrrias y energöa S.A. / H / H / H
E / Madrid / Viniclor S.A. / H
F / Paris la Defence / Atochem / H / H / H / H / H / ?1) / L1)
F / Paris / ESAR S.A. / L1)
F / Rueil Malmaison / Shell / H
GR / ? / ? / H
I / Ausimont Spa / Bollate / H / H / H
I / Milan / Caffaro S.p.A. / H
I / Torviscosa / Chimica del Friuli / H
I / Venezia / EVC S.p.A. / H
I / Milan / Enichem S.p.A. / H / H / H / H
I / Pieve Emanuele / S.A.I. Societa’ Approvv.
Indutriali Spa / H
NL / Amersfoort / Akzo Chemicals b.v. / H / H / H / H
NL / Rijswijk / Eurobrom B.V. / L
S / Steenungsund / Hydro Plast AB / H
UK / Runcorn, Cheshire / EVC Limited / H
UK / Runcorn, Cheshire / ICI Chemicals & Polymers Limited / H / ? 1) / H1) / H1) / H / ? 1) / ? 1)
1) Not reported is whether this implies production or importation
Information is derived from IUCLID (2000)
H: High volume production
L: Low volume production
High production volume (HPV) chemical is defined as a chemical being produced or imported in quantity of at least 1000 tonnes per year in EU by at least one Industry.
A LPVC is a chemical which has been produced or imported in EU with a tonnage >10t/y but never more than 1000
Appendix 2. Scheme of release routes for Hexachlorobenzene
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