Draft Version: Final Draft (Previous Version: 3.3)

Fact sheets on production, use and release of priority substances in the WFD,Royal Haskoning

Pentachlorophenol, Final draft

For official use only

Draft version: final draft (previous version: 3.3)

Status date: 15 October 2002

Comments:

- Changed format

- Remarks of EU letter ENV B.1/PMM/JD’E/ipD (2002) 310893 (30-702) incorporated

- Measures added

SUBSTANCE: Pentachlorophenol
I Chemical identity
CAS number:87-86-5
Chemical group:Chlorinated aromatic hydrocarbons
Homologues:not relevant
Synonyms:PCP, penta, 2,3,4,5,6-pentachlorophenol, chlorophen, penchlorol
Technical mixtures:NaPCP (Sodium pentachlorophenol), PCPL (Pentachlorophenyl laurate)
II Physical properties
Water solubility:14 mg/l [IPCS, 1987]
Vapour pressure:0.0147 Pa [EaSI-View v8.0][IPCS, 1987]
Log Kow3.32 (pH = 7.2) [IPCS, 1987][/ICPS]
III Production and use in 15 EU member states and accession states

Way of production/Process description:

PCP is produced by one of two methods: direct chlorination of phenols and hydrolysis of hexachlorobenzene. [IPCS, 1987]
The direct chlorination is carried out in two steps. First, liquid phenol, chlorophenol, or a polychlorophenol is bubbled with chlorine gas at 30 – 40 C to produce 2,4,6-trichlorophenol, which is then converted to PCP by further chlorination at progressively higher temperatures in the presence of catalysts (aluminium, antimony, their chlorides, and others). [IPCS, 1987]
The second method involves an alkaline hydrolysis of hexachlorobenzene (HCB) in methanol and dihydric alcohols, in water and mixtures of different solvents in an autoclave at 130 – 170 C [IPCS, 1987]
[IPPC 1987].

Fields of application:

Brown et al. [2000] OSPAR background document (1999) shows the main uses of this compound as being:
-The treatment of wood as a sap stain control agent for freshly cut timber
-As a wood preservative
-For remedial treatment of timber and as a surface biocide for masonry
-The preservation of textiles including heavy duty fibres
PCP, NaPCP and PCPL may be used in the remedial treatment of timber and as a surface biocide for masonry. According to the 9th Amendment on the EC Directive 96/769/EEC the dry and cubic rot treatment is possible to carry out after 1 July 1992 only for buildings of cultural, artistic and historic interest or in emergencies. In addition treatment must be carried out be specialised professionals authorised by the Member States and each individual treatment require authorisation. There is no data available of the number nor the extent of treatments carried out in the EU after 1 July 1992. [OSPAR, 1999]. In Sweden the use of PCP as biocide is forbidden since 1978. [Swedish EPA, 2001]
PCPL is used in the preservation of textiles. These textiles are used for transport, lorries, public market (army), tents, awnings, ropes, sails and marine fabrics. Main use of textiles treated in Europe is the UK’s army force, but also import of treated textiles. Currently PCPL has not been found in wool carpets [Bettens (2000) in OSPAR 1999]. PCPL (PCP or NaPCP) has not been used for leather preservation for at least the last ten years according to the US Pentachlorophenol Task Force (2000). PCPL is used presumably for the treatment of heavy-duted textiles in France and for textiles for transport and tents in Belgium [Bettens (2000) in OSPAR, 1999].

Production volume:

European Union
In 1992 the production of PCP and NaPCP ceased in the EU. After that, these chemicals have been imported from the USA and some from South-East Asia (OSPAR 1999). Production of PCPL from PCP by one plant in the UK [ERM, 1998]ceased in 2000 since, according to Commission Directive 1999/51/EC, placing on the market and use of PCP is not permitted as a synthesising and/or processing agent in industrial processes from 1st September 2000. [OSPAR, 1999]
Austria
BGBI.Nr. 58/1991 ST0025
The production, distribution and consuming of Pentachlorophenol (PCP) and of Pentachlorophenol-Natrium as well as other PCP-salts and –compounds are forbidden. [Anonymous, 2001]
Accession States
No information is available on the Accession States.

Number of production sites and locations of production:

There are no production sites for PCP in Europe anymore. [Balk et al., 2000]

Use volume:

In 1996 a total of 378 tonnes of NaPCP and 30 tonnes of PCP were imported in the EU. From 378 tonnes NaPCP imported, 26 tonnes were imported to France, 108 tonnes to Portugal and 144 tonnes to Spain. From the 30 tonnes of PCP imported, 28 tonnes were synthesised to 46 tonnes of PCPL in the UK. Of the 46 tonnes PCPL produced, 5-10 tonnes were exported to France and a similar quantity was used in the UK. The rest was exported to countries outside the EU. The 2 tonnes of PCP not used to convert to PCPL was sold onto the distributors, who each received 1 ton. Of these 2 tonnes, three companies used 1 tonne of PCP for wood preservation in Ireland. However, the largest of these companies is switching to Copper, Chromium and Arsenic (CCA) with the objective to increase their market share. As a consequence, it is expected that PCP consumption for wood preservation in EU will fall to 0.5 tonne in 1998. More recent data from the US Pentachlorophenol task force indicate that PCP is no longer used in the EU as a wood preservative [ERM, 1998 in OSPAR, 1999].]
According to a PCP importer, all PCP is sold to customers in the UK. In addition, all of the material is converted to PCPL and which is used solely for the preservation of industrial textiles. However, there are indications that substances are imported from Asia [ERM, 1998 in OSPAR, 1999OSPAR, 1999].
According to the only producer of PCPL in Europe they have purchased no more than 20 tonnes of PCP in 1999 for conversion to PCPL and their expected production of PCPL for 2000 was less than 30 tonnes [BrownAEA et al., Technology, 2000].
According to EuroChlor (1999) usage levels of PCP dropped to about 100 metric tonnes in 1996. Usage levels of NaPCP have been relatively stable since about 1987 and were about 1,000 metric tonnes in 1996. Usage level are approximately 20-30 metric tonnes per year in the EU [ERM, 1997 in Eurochlor, 1999].

Relative use volumes in various applications:

In 1996 almost 90% of the total EU consumption of PCP, NaPCP and PCPL was through the use of NaPCP for sapstain control in France, Portugal and Spain. In Portugal three product types are treated with NaPCP, namely pallet boards, construction timber and fencing panels. [Brown et al., 2000].
[DGIII/ERM 1998 in OSPAR Background document 1999].

Existing regulation in member states or associated member states:

In the EU, pentachlorophenol is controlled by the Council Directive 91/173/EC and 1999/51/EC, which amended Directive 76/769/EEC on restrictions on the marketing and use of certain dangerous substances and preparations. This directive states that pentachlorophenol, its salts or esters shall not be used in a concentrations equal to or greater than 0.1% by mass in substances or preparations placed on the market. By way of exception, this provision does not apply to [Brown et al., 2000]:

The treatment of wood (but the wood cannot be used for internal purposes);
The impregnation of fibres and heavy-duty textiles not intended for clothing or for decorative furnishings;

• As a synthesising and/or processing agent in industrial processes;
• For the in-situ treatment of buildings of cultural interest.
In addition to this legislation, several Member States have stricter requirements: [Brown et al., 2000].

Austria introduced a ban on the marketing of products containing pentachlorophenol and its salts and compounds at concentrations above 0.0005% (Verbot von Pentachlorphenol, BGBI. No. 58/1991);
The Commission Decision 94/783/EC of 14th September 1994 endorses the prohibition of PCP notified by the Federal Republic of Germany by the Regulation of 12 December 1989 (Pentachlorophenolverbotsverordnung). This regulation prohibits the manufacture, marketing and use of pentachlorophenol, its salts and compounds, preparations containing more than 0.01% of such substances and products which, following treatment with preparations, contain the said substances in a concentration of more than 5mg/kg;
The Commission Decision 96/211/EC of 26th February 1996 is concerned with the prohibition of PCP notified by Denmark which has stricter requirements for the concentration of dioxins in PCP introduced through Environment Ministry Orders No 582 of 28 November 1977; No 454 of 16 June 1991; and No 446 of 7 June 1992;
The Commission Decision 1999/831/EC of 26thOctober 1999 is concerned with the prohibition of PCP notified by the Netherlands which prohibits the placing on the market and use of substances containing PCP for the treatment of wood and the impregnation of fibres which are allowed by the Community directive.

Black List, pentachlorophenol, Listed:
EC (1982), List I within the framework of Directive 76/464/EEC on pollution caused by certain dangerous substances discharged into the aquatic environment of the community. Official Journal C 176, 14.7.1982 p 7-10. With the aim of eliminating pollution of the various parts of the aquatic environment which could be affected by discharges of PCP, limit values were fixed by the Council Directive 86/280/EEC of 12thJune 1986.
Pentachlorophenol has been identified as a priority substance in the proposed water framework directive (COM(2000)47), and is expected to be included in the European Pollutant Emission Register (EPER) which is a key element of Council Directive 96/61/EC - the IPPC Directive. [Brown et al., 2000].
Pentachlorophenol is subject to the Prior Informed Consent procedures (Council Regulation 3136/94). [Brown et al., 2000]
The United Nations (1994) lists a number of bans and restrictions for pentachlorophenol in both individual EU Member States and Accession States: [Brown et al., 2000]
OSPAR countries
OSPAR (1998) OSPAR 1998 List of Candidate Substances OSPAR Strategy with regard
To Hazardous Substances (Ref. nr. 1998-16), Annex 3. Sintra 22-23 July 1998. Details on list Class 1A.

Industrial associations to be addressed:

Eurochlor
IV Releases to environment

General way of entrance and schematic picture:

Relevant main routes of release to the environment are given in appendix 1 and summarised as follows:
Emission to air:
Production/Formulation/Industrial Use: A4/A5
(Volatilisation to air during dripping and drying process and evaporation during storage of treated wood)
Emissions to water:
Production/Formulation/Industrial Use: S9.1 or S9.2.2  S8.4
Waste disposal in landfills:  S10.1 (leachates).
Contaminated sites:  S11.1 (leachates).
Deposition: A4 and A5  S2, S3.2, S3.3, S4.2 and S4.3

Atmospheric cycle

Industrial point sources to air:

Formulation of PCPL (NOSE 105.09.41):
From formulation it was estimated that PCPL releases to air could have been 950 kg in 1996. [OSPAR, 1999]

Municipal collective sources to the air

No data available in project database.

Diffuse sources to air and deposition

No data available in project database.
Natural emissions (NOSE 301):
There are few indications that PCP emissions may also come from naturally occurring combustion processes like forest fire of from burning of wood. It is unclear, whether natural sources of burning processes form a significant part of PCP releases. [OSPAR, 1999]
3. Aquatic releases
a. Industrial Point sources to the aquatic environment:
Possible emission routes to the aquatic environment are:
1)During transport from dipping to drying (when process takes place in the open air) through runoff from wood surface to soils,
2)If treated (and dried) wood is stored in the open air it is difficult to prevent rainwater washing over it and then running into the soil or into surface water.
In the OSPAR Background Document (1999) calculations are made according to the EC Technical Guidance Document (TGD) on Risk Assessment of New and Existing Substances (1996). Based on these calculations the PCPL releases to water is estimated at 900 kg and PCP releases at 600 kg in 1996. From formulation it is estimated that PCPL releases to water could have been 7,600 kg. [OSPAR, 1999]
Formulation of PCPL (NOSE 105.09.41):
According to the one manufacturer of PCPL in the EU discharge of PCP to water from production do not exceed 10 g/l in their trade effluent. The manufacturer also states that this level of discharges applies also to the companies processing the textile fabrics. [OSPAR, 1999]
Industrial effluent discharge (NOSE 109.02.41):
The trade effluent from industrial production and processing is discharged to sewer from where it goes to a sewage treatment plant. [OSPAR, 1999]
PCPL released to STP (NOSE 105.09.41)
In the OSPAR Background Document (1999) a calculation is made to estimate the PCPL release to the sewage treatment plant. This calculation is based on the information of the PCPL producer of 0.5 kg of remaining PCPL per batch of 500 kg yarn (0.1% emission). [OSPAR, 1999]
Wood treatment plants(NOSE 107.04.06)::
Measured emission data or sufficient initial data for the estimation of emissions is not available. Release as a solid waste may occur during sawing (sawdust) and processing (wood chips) of wood. Also sludge, consisting of sawdust and active substance, accumulated in the dipping tank may cause emissions if it is not treated properly. According to a Finnish study at the beginning of the 1980s PCP containing solid waste of about 0.3 l/m treated wood was collected [Viitasaari 1988 in OSPAR, 1999].
b. Municipal sources to the aquatic environment:
Leeching from Waste Disposal (release route: S10)

Landfills (NOSE 109)

In a 5-year field study in Finland for 43 landfills in late 1980s concentrations of PCP were measured. The median concentration was 0.08 g/l and the maximum 3.0 g/l. Higher concentrations have been measured in other studies. [OSPAR, 1999]

Diffuse sources to water

Use of treated wood: Rain may wash from the surface of treated pallets and other treated wood, leading to high local levels in soils where the treated wood is stored and used in the open. From the soils the PCP can possibly reach surface water.
Textile industry (NOSE 107.03.13)
Textiles are treated for outdoor use, where they may be in contact with rain, surface water or seawater. According to OSPAR due to lack of information no estimation of the extent of emissions or discharges through the use of treated textiles is possible. [OSPAR, 1999]
4. Overall Releases and Summary:
No current overall data on releases to environment.
Available national release data:
Based on the flux rate from Marchall’s thesis (see under Environmental fate of substance) emissions to air in Portugal are 5,160 kg/a, in France 3,440 kg/a in the UK 2,294 kg/a and in Spain 1,147 kg/a.
This corresponds to an emission factor of 1,1% per year, which is much less than the estimation made by the WHO: Depending on the solvent, temperature, pH and the type of wood 30-80% of PCP may evaporate within 12 months from dip-brush-treated wood [IPCS, 1987].
V Environmental fate of releases to environment

Adsorption to solids (sediment, sludge, soil):

The pH seems to be the major factor controlling the magnitude of PCP adsorption. Adsorption is maximal in strongly acidic soils, relatively minor in moderately acidic soils, and absent in weak acidic or neutral soils [IPCS, 1987 EHC 71].

Volatilisation:

OSPAR (1999) calculates a steady-state flux rate of 1.2273 g/m2/hour (based on a doctoral thesis by Marchal (1996)), together with the representative loading rate of 0.33 m2/m3 (based on a study of Ozanne, 1997).
Vapour pressure: 0.0147 Pa [EaSI-View v8.0]
Henry’s Constant: 0.279825 pa.m3/mol calculated

Degradation [Blok et al.,. 1997]:

Biodegradation:Photodegradation:
Ultimate Survey Model: 1.634Fraction to air: 0.00
Linear Model: -0.1755OH half-life rate: 19.43 days

Partition to compartments:

Partition of PCP into different environmental compartments according to Mackay level I calculation [Mackay et al., 1992 in Euro chlor, 1999]
Water:74.2%
Soil:12.3%
Sediment:11.5%
Air: 2.1%.

Behaviour:

No data available in project database.
VI Evaluation
1. Relevant NOSE-codes of point sources
NOSE-codeSourcesIPPC-code
104.04/105.04Characteristic processes in the manufacture of textiles and textile 6.2
products
104.06/105.06Characteristic processes in the manufacture of wood and wooden
products
104.16/105.16Characteristic processes in construction
105.09.41Halogenated hydrocarbons production4.1/4.4
107.03.13Textile finishing6.7
107.04.06Preservation of wood6.7
107.06Use of pesticides (other than agriculture and forestry)
109.02.42Waste water treatment in industry
109.06.11Land filling
301Processes in nature
2. Evaluation of emission data:

Emission to water

Due to lack of quantitative data it will be not possible to show a pie-chart.
Release from use in wood will be mainly to soil where it is absorbed so leeching to water is low. Release from use in textiles will be to the water and partially to sewage sludge. No proper EU quantification of release to surface water.

Emission to air

No quantitative data available but fraction in air will be very low (2,1%).

Deposition

There is no data on deposition, however as the emission to the air is low deposition can be assumed to be low also.

Gaps and questions

Production and use are greatly reduced. Some residual use of imported PCP may exist but is not quantified.
VII Measures

Measures at production level:

Contribution to water at production level

No data available in project database.

Relevant IPPC sector, documents and available emission criteria

The following IPPC sectors are/ were relevant:
-4.1 Chemical installations for the production of basic organic chemicals;
-4.4 chemical installations for the production of basic health products and of biocides;
-6.2 Plants for the pre-treatment or dyeing of fibres or textiles;
-6.7 Installations for the surface treatment of substances, objects or products using organic solvents.
No specific BAT for pentachlorophenol are mentioned in IPPC BREF documents.

Voluntary agreements

Not relevant.

Substitution

Substitutes for NaPCP in wood treatment: quaternary ammonium compounds, dichlofluanide, propiconazole, 3-iodine-2-proynyl-butylcarbamate.
Substitutes for PCP in textile preservation: waterborne mixtures, usually copper, chromium and arsenic compounds, referred as CCA. For the impregnation of textile substances used instead of PCPL can be zink-2-pyridinthiol-N-oxide, 2,2’-dihydroxy-5,5’-dichloro-diphenylmethane-ester, tributyltinoxide- ester, etc. [OSPAR, 1999]

Process control, modifications

A modification of a production process is the preservation of wood by drying process.

Effluent treatment

Most appropriate process for treatment *:

phase separation (solvent extraction, stripper)
adsorption (resins, act. Carbon, biol. sludge)
precipitation (lime, iron-chloride, polymers)
oxidation (biologic, UV/catalytic, thermal)

*) BAT, BEP and EMAS related actions may include one or more of the above mentions measures.

Measures at use level:

Contribution to water at use level

No data available in project database.

Use by IPPC sectors

Application of BAT and BEP on existing processes: disposal of technical PCP and associated waste should preferably involve high-temperature combustion or, where this is possible, the use of secure land fill sites.

Use by SME groups

See VII.1.f and VII.2.b.

Use by consumers

Not relevant.

Use in agriculture

No data available in project database

Measures at community level:

Sewage treatment

General BAT for sewage treatment.

Waste disposal

Disposal of technical PCP and associated waste should preferably involve high-temperature combustion or, where this is possible, the use of secure landfills. See also VII.2.b.

Incineration

Relevant EC Directives cover BAT for municipal waste incinerators and hazardous waste incinerators. [OSPAR, 2000]

Recycling

Not relevant.

Measures at regulatory level:

EU level: IPPC emission control

Pentachlorophenol has been identified as a priority substance in the proposed water framework directive (COM(2000)47), and is expected to be included in the European Pollutant Emission Register (EPER) which is a key element of Council Directive 96/61/EC - the IPPC Directive. [Brown et al., 2000].
Pentachlorophenol is subject to the Prior Informed Consent procedures (Council Regulation 3136/94). [Brown et al., 2000]

EU level: Substitution or phase-out

EU level: Limitations of use in certain applications

See VII.4.a and b.

Other regulatory and/or national policy measures

Germany prohibited its use as a plant protectant in 1986 (the former Germany Democratic Republic also did not permit its use in agricultural chemicals, from an unspecified date). [Brown et al., 2000]
Denmark has not registered it as a pesticide. Classified as a toxic chemical and as such severely restricted. [Brown et al., 2000]
The Netherlands.
Priority Chemicals, Chloorfenolen, Listed:
Min. VROM (1986) Dutch black-listed substances. Indicative Environmental Multi-Year Programme 1986 – 1990.
Black List, Pentachloorfenol, Applies to: Water:
Min. VROM (1986) List of Dutch priority substances Indicative Environmental Multi-Year Programme 1986 – 1990.
The Netherlands prohibited selling, stock, store or use pentachlorophenol as an agricultural pesticide (1978); however use and application in wood preservatives is authorised. Pesticides containing pentachlorophenol are prohibited because of (a) the high concentration of the active substance, metabolites and contaminants in the environment; (b) its high toxicity for aquatic organisms. [Brown et al., 2000]
Sweden banned pentachlorophenol and other chlorophenols in 1978 because of highly toxic impurities in commercial products. [Brown et al., 2000]
Switzerland prohibited the manufacture, supply, import and use of 1,2,3,4,5-pentachlorophenol, its salts and pentachlorophenoxy compounds in 1986. Reasons for the control action: long persistency, high toxicity for aquatic organisms, highly toxic impurities, formation of highly toxic substances on thermolysis. [Brown et al., 2000]
Sweden has forbidden the use of PCP as biocide since 1978. [Swedish EPA, 2001]
Yugoslavia reported that the technical product is [date undefined] imported and used for the formulation of a preparation containing 4% of pentachlorophenol and 1.5% or 2.4% of lindane. The preparations are exclusively used to treat timber logs at collection points in forests where wood is felled. The technical product may not contain over 0.1 ppm of dioxin/TCDD. [Brown et al., 2000]

LITERATURE

Anonymous, 2001. Austrian legislation on Priority Chemicals of the Water Framework Directive.

Blok J., P.C. Okkerman, F. Balk, E.P. van der Zande-Guinée, 1997 Selection of Toxic, Persistent and Bioaccumulative Substances, based on ecotoxicity data. BKH Report no. 5593O. Project under the authority of the Dutch Ministry of Housing, Spacial Planning and Environment.
Brown K.A., P. Coleman, K. King, et al., 2000. Exploration of possible future POP control areas. AEA Technology.
ERM (Environmental Resources Management), 1997. Assessments of the Risks posed by pentachlorophenol (PCP) through the exposure of man and the environment to dioxins. European Commission – DG III.
ERM (Environmental Resources Management), 1998. Analysis of the advantages and drawbacks of further restrictions on the marketing and use of pentachlorophenol. European Commission – DG III. Draft final.
Eurochlor, 1999. EuroChlor Risk Assessment for the Marine Environment. Pentachlorophenol. OSPARCOM Region: North Sea, Pentachlorophenol. Draft.
ICPS (International Programme on Chemical Safety), 1987. Pentachlorophenol. Environmental Health Criteria 71. WHO. Geneva.
OSPAR, 1999. Background document on pentachlorphenol.Draft, presented by Finland.

Swedish EPA (Environmental Protection Agency), 2001. Information on emission sources for priority substances. Swedish EPA. Sweden. Plassche, E. van de, 2001. Preliminary Risk Profile Pentachlorobenzene. Prepared for Ministry of Housing, Physical Planning and the Environment (VROM) in the framework of the Project Risk Profiles II. HASKONING, March 2001.