Persistence
PFOS does not hydrolyse, photolyse or biodegrade under environmental conditions. This stability is typical for perflourinated compounds and the reason for that is that the carbon chain, which is the backbone of the molecule, is totally surrounded by fluorine atoms with strong bindings to all positions of the carbon chain. These C – F bindings are probably the strongest bindings in nature. PFOS is therefore assessed to be very persistent in the environment, and to fulfil the criterion for persistence. The occurrences of PFOS in the environment confirm this statement through findings in blood plasma (up to 1 047 ppb) in birds (eagles, albatross) and fish. PFOS has also been detected in polar bears and seals in the arctic, dolphins in the Mediterranean Sea and Ganges and turtles in Mississippi.
Bioaccumulation
Due to the fact that PFOS is an extreme surface-active agent, it is impossible to measure log Kow since the test ends up with three phases. Reported Bioconcentration Factor (BCF) in fish is 980, but it is possible that the physical/chemical properties of PFOS may influence the validity of this test. Experiment on rats indicates that PFOS do not accumulate in adipose tissue but on blood proteins. PFOS is well-absorbed following ingestion. The half-life for elimination from plasma after single oral dose in male rats was 7.5 days. A study on humans which were exposed over a long time, retirees who worked in a factory producing PFOS, shows a very long half-life for elimination: between 1 and 4 years. The occurrences of PFOS in birds of prey, fish and polar bears are also an indication on accumulation in these organisms and this bioaccumulation is not connected to adipose tissue.
Toxicity
During chronic toxicity studies on fish (Pimephales promelas) adverse effects has been observed such as growth inhibition and decreased survival at 0.3 mg/L of the potassium salt of PFOS after 42 days. At almost the same level (0.25 mg/L) there are also growth inhibition and impact on the reproduction to the saltwater species Mysidopsis bahia (Mysid shrimp) at a 35-day test with the potassium salt of PFOS.
Postnatal deaths and other developmental effects were reported at low doses in offspring in a 2-generation reproductive toxicity study in rats. The NOAEL and LOAEL for the second-generation offspring (F2 pups) were 0.1 mg/kg/day and 0.4 mg/kg/day, respectively, based on reduction in pup body weight. In a 6 month study of cynomolgus monkeys, deaths were observed at doses as low as 0.75 mg/kg/day. Thus, the criterion for adverse effects is considered to be met.
Potential for long-range transport
PFOS is not a volatile compound and PFOS is likely to resist in the atmosphere due to the persistency of PFOS. Findings in polar bears and seals in the Arctic indicate long-range transport of PFOS.
The largest producer of PFOS, 3M, is going to phase out PFOS due to voluntarily agreements. This is a result of negotiations between 3M and USEPA. Obviously there are alternative to PFOS and these alternatives are soon going to be put on the market. USEPA has during spring 2002 declared new regulations which regulates new uses of PFOS. Within the EU, a risk management program is currently initiated in the EU, with UK as a lead country.
References -
Renner, R.,(2001) Environmental Science and Technology, vol 35, p. 155 – 160.
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Sulfonated Perfluorochemicals in the Environment, Sources, Dispersion, Fate and Effects, 3M, (2000)
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Draft OECD report
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Federal Register, USEPA, Monday, March 11, 2002, part 3, 40 CFR part 721, Perfluoroalkyl Sulfonates; Significant New use Rule; Final Rule and Supplemental Proposed Rule.
Short-chained chlorinated paraffins (Alkanes, C10-13, chloro, SCCP)
CAS No 85535-84-8
Short-chained chlorinated paraffins (SCCP) is the group of chlorinated paraffins (short-, medium- and long-chained) which exhibit properties, that qualify the group as POP. Two producer exist within EU, according to the EU RAR under the Council Regulation (EEC) No 793/93 of 23 March 1993 on the evaluation and control of the risks of existing substances. The main uses are in metal working fluids, as plasticiser in paints, coatings and sealants, as flame retardant in rubbers and textiles, and in leather processing (fat liquoring) (1).
Persistence
SCCP is recognized as very persistent. SCCP does not hydrolyse in water and is neither readily biodegradable nor inherently biodegradable (1). SCCP is expected to fulfil the criterion for persistence.
Bioaccumulation
The log Kow for SCCP is 4.4-8.7. High bioaccumulation factors between 1000 and up to 50 000 have been noted i fresh- and seawater organisms. In “pure water”, the elimination half time is between 9 and 20 days (1). SCCP is expected to fulfil the criterion for bioaccumulation.
Toxicity
SCCP exhibits a high toxicity towards aquatic organisms: NOEC for fish is in the order of 0,04 mg/l, for Daphnia magna 0.005 mg/l and for algae 0.012 mg/l. Reproduction test with mallard exhibits a NOAEL of 166 mg/kg. SCCP is further classified as to IARC group 3 (not classifiable as to human carcinogenicity) (1). SCCP is expected to fulfil the criterion for toxicity.
Potential for long-range transport
Emissions of SCCP to the atmosphere are likely to be very low. Estimated levels exhibit a small but measurable volatility. Vapour pressure at 40°C is 0.0123 Pa. The half life time in air has been estimated to 1.9-7.2 days. Recently performed investigations exhibit high levels of SCCP in biota from the Artic region, up to 1.4 mg/kg blubber in white whales (Beluga). This may indicate that these substances are transported over long distances (1). Some uncertainties still remain if SCCP can fulfil the criterion for long-range transportation.
Consequences
In 1994 ca. 15 000 tonnes of SCCP were produced within EU. Different voluntary actions within EU resulted in a drastically reduced use, and EuroChlor estimated the use for 1998 to ca. 4 000 tonnes (1). In the context of a possible long-range transportation, SCCP is discussed as a possible candidate for inclusion in the LRTAP POP-protocol. On 25 June 2002 the EC agreed on Directive 2002/45/EC, as 20th amendment to Directive 76/769/EC, banning the use of SCCPs in metal working fluids and leather fattening liquors (2). SCCP is further selected for priority action within OSPAR (3), and classified as a priority hazardous substance within the Water Framework Directive (2000/60/EC) (4).
The consequence of a regulation within EU is expected to be moderate (5). Medium- (MCCP) and long- (LCCP) chained chlorinated paraffins are used as substitutes. These substances are, however, presently investigated according to their human and environmental effects. Since SCCP also is produced and used globally, the total global consequence is difficult to judge.
References
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OJ of the European Communities, Commission Recommendation of 12 October 1999 for:
Alkanes, C10-13, chloro, CAS#: 85535-84-8, EINECS#: 287-476-5.
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Directive 2002/45/EC of the European Parliament and of the Council of 25 June 2002 amending for the twentieth time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (short-chain chlorinated paraffins)
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OSPAR Background Document on Short Chain Chlorinated Paraffins, OSPAR 01/4/8, 2001
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DECISION No 2455/2001/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 20 November 2001 establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC.
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Socio-Economic Impacts of the Identification of Priority Hazardous Substances under the Water Framework Directive, Final Report prepared for European Commission Directorate-General Environment, RPA, December 2000.
Chlordecone (Kepone)
1,1a,3,3a,4,5,5,5a,5b,6-decachlorooctahydro-1,3,4-metheno-2H-cyclobuta(cd)pentalen-2-one.
CAS No. 143-50-0
Chlordecone is a pesticide (insecticide and fungicide) that has been used mainly in the US, Africa, and South America. It has not been produced after 1976 in the EU or North America. There was an approved, but very limited, use of chlordecone in Sweden 1973-1978. It has also been used as a starting material in the production of the pesticide Kelevan. There is no information indicating use or production of chlordecone for, at least, the last 10 years (1). All information below is extracted from IPCS Environmental Health Criteria 43, Chlordecone, 1984 (2).
Persistence
We have not found any degradation studies. However, a high persistence is indicated by widespread occurence of chlordecone in soil and birds in areas where chlordecone has been used, and by an estimated half-life of 2-5 months in humans. thus, the criterion for persistence seems to be met.
Bioaccumulation
Chlordecone has a relatively high lipophilicity (log Kow 4.5). A fish study from 1982 has generated a BCF-value of 16 600 in fathead minnow. Studies in marine fish species have given BCF-values between 1800 and 7100. The presence in birds (<13 mg/kg) and human breast milk supports that the criterion for bioaccumulation is met.
Toxicity
The acute toxicity of chlordecone is high in algea (7-days EC50 <1 µg/l in four species) and fishes (96 h LC50 70 µg/l in four species). The acute toxicity is also relatively high in mammals, with LD50 values just below 100 mg/kg in rats and rabbits. Repeated exposure to 1-25 mg/kg food may cause neurotoxicity, liver toxicity, and morphological changes in endocrine organs, such as the adrenal, the thyroid, and the testis. Hormonal effects may underlie the reproductive toxicity observed at exposure to >1 mg/kg body weight/day. Liver tumours are observed both in mice and rats, and the substance is classified as a possible (2B) carcinogen by IARC. The criteriron for adverse effect is met.
Potential for long-distance transport
Chlordecone is not expected to be degraded by sunlight. Half-lives > 10 days has been measured in the presence of ethylendiamin. The criteria for long-distance transport is probably met, but there is no clear evidence.
Consequences
Chlordecone is included in the ECE-LRTAP treaty. If there is production of chlordecone, for which there is no indications today, it is relevant to include it in the SC. Numerous alternative pesticides are available today. Possible economic consequences depends on whether there is still any production and use of chlordecone.
References
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Pesticide manual
2. WHO-IPCS (1984) Environmental Health Criteria 43 Chlordecone. Geneva, World Health Organization.
Pentachlorobenzene
CAS No. 608-93-5
This short summary is mainly based on an IPCS EHC document from 1991 (1) and on a “Preliminary Risk Profile” document prepared in the Netherlands containing pertinent data on pentachlorobenzene as a possible candidate for the POP-protocol in UN ECE LRTAP (2).
Pentachlorobenzene was formerly used as a fungicide and as a flame retardant. If these uses still can be found somewhere in the world is unknown. Probably there is no production any longer. Pentachlorobenzene is an impurity of up to 2% in hexachlorobenzene and has previously been an impurity in the pesticide quintozene. The substance is today not registered in any products in the Swedish product register.(2)
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