Annex 1 to the Interim Report



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Consequences


Since methoxychlor has not been notified under the "Plant Protection Produts Directive" 91/414/EEC (i.e., there is no stakeholder which will produce a dossier for the substance), any plant protection products containing this substance must be withdrawn from the EU market by July 2003. This suggests that the economical consequences of inclusion in the Stockholm Convention will be insignificant within the EU.
The global use of methoxychlor is unknown and it is therefore to early to predict the global consequences for restrictions. Due to the fact that the demand for methoxychlor within the EU seems not to exist anymore, and with the knowledge that there are other insecticides on the market, it is reasonable to assume that acceptable alternatives exist, at least for some areas of use.
The substance is a ”priority chemical” in the work of OSPAR and has been selected through the DYNAMEC-process. It appears in the ”selection box” group A which means that that the substance probably has POP-like properties and there are some indication on production, use or occurrence in the environment.

References


  1. Aquire (2001), ecotoxicological database on the internet, established by USEPA

  2. Cummings, A. M. (1997) Methoxychlor as a model for environmental estrogens. Critical Reviews in Toxicology 27 (4): 367 – 379.

  3. Draft OSPAR Background Document on Methoxychlor, Presented by Finland, Meeting of the Working Group on Priority Substances (SPS) in Arona 15-19 October 2001.

  4. Howard, P. H., (1991) Handbook of Environmental Fate and Exposure data for Organic Chemicals, vol 3, p 502 – 507.

  5. Keith L. H., (1998) Environmental Endocrine Disruptors, A handbook of property data. p 802 – 830.

  6. Metabolic Pathways of Agrochemicals (1999) Insecticides and Fungicides, part two, p 181 – 185

  7. Toxicological profile for Methoxychlor, Atlanta (1994), GA, Agency for Toxic Substances and Disease Registry.


Hexabromocyclododecane (HBCD)

CAS No. 25637-99-4


HBCD is a brominated flame retardant with its main use in insulation material of polystyren, e.g., for buildings. There is also some use in textiles. HBCD is a high production volume chemical both in the EU and in the US, and there is production in Japan as well. HBCD is currently being risk assessed in the EU.
Persistence

Based on acceptable laboratory studies, HBCD is not readily biodegradable. One study may indicate some biodegradation (1). Simulation half life studies are in progress in the EU ESR program to allow a conclusion whether the criterion is met or not. The presence of HBCD in different environmental samples (sewage treatment plants, soil, fish, birds, and seals) supports a relatively high persistence.


Bioacumulation

Two studies in fish have given BCF-values well above the criteria cut-off (9000-18 000) (1). The presence of HBCD in fish (e.g. Baltic herring), birds (guillemot and peregrine falcon egg), Baltic seals (100 ng/g fat) human food stuff (e.g. meat) supports that bioaccumulation may exist (2,3).


Toxicity

At water-soluble concentrations of HBCD (a few µg/l), HBCD affects the growth of algea (Skeletonema costatum, EC50 (72 h) 11 µg/l) and growth, reproduction, and survival of Daphnia magna (1). The NOEC for daphnia magna is 3 µg HBCD/litre. The toxicity to fish is low (1).


In mammals, the liver and thyroid system is affected after repeated exposure, but no conclusive NOAEL can be set. Based on the ecotoxicity, the criterion for adverse effects is met.
Potential for long-range transport

HBCD is not very volatile, but there is data indicating its presence in air of Scandinavian background areas (0.002-0.28 ng/m3) and deposition to soil (1.6 - 13 ng/m2 and day) (1,3). Potential for long-range transport is supported by QSAR-modeling (hydroxyl-mediated degradation in air), giving a half-life of 1.8 days. The criterion is 2 days, but considering the uncertainties in the modelling, 1.8 days is close enough to support a potential for long-range transport.


Consequences

According to Industry, there are no alternative flame retardants that can be used in polystyrene. The incorporation of flame retardants into polystyrene is mandatory in many countries due to strict fire safety standards. A potential regulation of HBCD may thus be preceeded by development of other flame retardants or changes in the fire safety standards.


References

  1. EU Risk Assessment Report on Hexabromocyclododecane, CAS-No. 25637-94-4, draft of 2002.

  2. Abstracts from The Second International Workshop on Brominated Flame Retardants – BFR 2001 Stockholm May 14-16, 2001.

  3. IVL (2001) HBCD i Sverige - screening av ett bromerat flamskyddsmedel. Sternbeck J et al. IVL rapport B1434. Stockholm, IVL Svenska Miljöinstitutet AB, november 2001.



Hexachloro-1,3-butadiene

CAS No. 87-68-3


This short summary is mainly based on an IPCS EHC document from 1994 (1) and on a “Preliminary Risk Profile” document prepared in the Netherlands containing pertinent data on hexachlorobutadiene as a possible candidate for the POP-protocol in UN ECE LRTAP (2).
Hexachlorobutadiene is formed mainly as a by-product during the manufacture of certain chlorinated hydrocarbons. The global annual production was estimated to be 10 000 tonnes in 1982 (1). The use is, inter alia, as a chemical intermediate in the manufacture of rubber compounds, and in lesser amounts as a solvent, heat transfer liquid, and hydraulic fluid. Hexachlorobutadiene has also been used as a fumigant and may still be used as a fumigant in some countries (2). The substance is today not registered in any products in the Swedish product register.

Persistence


Test data regarding degradability is scarce and the estimations reported in the “Preliminary Risk Profile” document cannot clarify the picture. Accordingly, that document reaches the conclusion that insufficient evidence is available on the persistence of hexachlorobutadiene but that the substance probably is recalcitrant to biodegradation under aerobic conditions (2). This assumption could also be supported by the relative abundance of monitoring data as regards hexachlorobutadiene. The substance can be found in different compartments of the environment including biota, primarily in industrial regions but has also been detected in biota in northern Canada (2).

Bioaccumulation


The log Kow values available vary between 3.7 and 4.9 (1,2). The ”Preliminary Risk Profile” document recommends the value 4.9 to be used, which indicates a high potential for bioaccumulation although just below the limit of the screening criterion of the Stockholm Convention (2). Several bioaccumulation studies confirm a high level of bioaccumulation of hexachlorobutadiene, showing BCF values of up to 19 000, clearly fulfilling the bioaccumulation criterion (2).

Toxicity


Aquatic toxicity has been tested on species representing different groups of organisms and has been shown to be very high. The lowest acute LC50 value available is 0.032 mg/l for crustaceans and the lowest NOEC value is 0.0065 mg/l for fish.(1,2)
One reliable study with birds as test animal is available. In this 90 day toxicity test with Japanese quail a NOAEL of 3 mg/kg was found.(2)
In short-term and long-term diet studies with rats and mice the kidney has shown to be the major target organ. The NOAEL for renal toxicity in rats in a 2-year study was 0.2 mg/kg body weight per day. Based on this 2-year diet study the International Agency for Research on Cancer (IARC) has found limited evidence for carcinogenicity in animals and insufficient evidence in humans. IARC has placed hexachlorobutadiene in Group 3 (not classifiable as to human carcinogenicity).(1,2)
The ”Preliminary Risk Profile” document concludes that the criterion for toxicity in UN ECE LRTAP is met (2).

Potential for long-range transport


Hexachlorobutadiene is expected to degrade very slowly in air, with half-lives hundreds of days in different estimations (1,2). Vapour pressure is about 20 Pa at 20 ºC and Henry`s Law Constant is about 1000 Pa m3/mol (1,2). This indicates that hexachlorobutadiene possess a potential for long-range transport. This is also supported by the findings of hexachlorobutadiene in biota in northern Canada.
Hexachlorobutadiene is included in the list of priority substances in the field of water policy, established under Directive 2000/60/EC of the European Parliament and of the Council, establishing a framework for Community action in the field of water policy (3). In the context of the Water Framework Directive, 0.0093 µg/l have been reported as the mean concentration for European surface waters based on 1391 samples (1154 positive samples) from 68 stations (4). These monitoring data, though low concentrations, support the persistency as well as the potential for long-range transport of the substance.
Consequences

The available information on production and use is old and probably does not reflect the situation today. Possible use is probably limited and impact on society of restrictive measures aimed at direct production will be very small. However, measures intended for the cessation of the emissions of, and the formation of, hexachlorobutadiene as a by-product during the manufacture of other chlorinated hydrocarbons may have a larger economic impact. Provided that future use is prevented and sources of emissions are identified and eliminated, concentrations in the environment should also decrease in the long run. The substance is a ”priority chemical” in the work of OSPAR and has been selected through the DYNAMEC-process. It is assigned to ”selection box” group E; substances with PBT properties but which are heavily regulated or withdrawn from the market.



References

  1. WHO-IPCS (1994) Environmental health Criteria 156 Hexachlorobutadiene. Geneva, World Health Organization.

  2. Risk profile polychlorinated hexachlorobutadiene, Preliminary risk profile prepared for Ministry of Housing, Physical Planning and the Environment (VROM, the Netherlands) in the framework of the project Risk Profiles III, October 2001.

  3. 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. Official Journal of the European Communities L331/1, 15.12.2001.

  4. Fraunhofer-Institut (1999) Revised Proposal for a List of Priority Substances in the Context of the Water Framework Directive (COMMPS Procedure). Draft Final Report. Declaration ref.: 98/788/3040/DEB/E1. Schmallenberg, Fraunhofer Institut Umweltchemie und Ökotoxikologie.


Polycyclic aromatic hydrocarbon (PAH)
PAH is a large group of substances, which consist of molecules with 2 to 3 or more aggregated benzene rings. Most of them are generated in connection with different thermal processes and are emitted to the environment via both point and diffuse sources. Some of them have, as individual substances, a commercial use. Some PAH-substances are further toxic, some bioconcentrate in invertebrates in the aquatic environment, in fact to some extent they exhibit properties which are POP-like. PAH metabolise in vertebrates, but the metabolites are reactive and some are known to be carcinogenic.
In order to take a closer look on PAH-substances, six substances were selected, the so called Borneff 6: benzo[a]pyrene (CAS No. 50-32-8), benzo[ghi]perylene (CAS No. 191-24-2), indeno[1,2,3-cd]pyrene (CAS No. 193-39-5), benzo[b]floranthene (CAS No. 205-99-2), benzo[k]fluoranthene (CAS No. 207-08-9) och fluoranthene (CAS No. 206-44-0) (1).

Persistence

All selected PAH-substances fulfil the criteria for peristence, that is half-lifes in water exceeding 60 days, and in soil 180 days. This is not a fact for all PAH-susbstances (1,2). It is, thereby, doubtful if PAH-substances fulfil the criterion for persistence.


Bioaccumulation

All selected PAH-substances have log Kow exceeding 5 and most of them have BCF-values exceeding 5 000. The BCF values are related to organisms at lower tropic-levels. Higher organisms do metabolise PAH. However, many metabolites are toxic (1,2). PAH-substances, thereby, bioconcentrate in lower organisms, but not in higher organisms.


It is doubtful if PAH-substances fulfil the criterion for bioaccumulation.
Toxicity

All selected PAH-substances are genotoxic, which is known also for many other PAH-substances. All, except benzo(ghi)perylene, have been proven to be carcinogenic, which is also known for other individual PAH-substances. Indivual PAH-substances are classified in IARC-groups 2A (probably carcinogenic to humans) and 2B (possibly carcinogenic to humans), but none in group 1 (carcinogenic to humans). Complex mixtures containing different PAH, such as tar, soot, smoke from aluminum production and tobacco smoke, are classified in group 1.

Low molecular PAH are toxic towards several aquatic organisms with EC50-values below 0.001 mg/l. Reproduction disturbances and mutagenicity/carcinogenicity in aquatic organisms have been observed even for some high-molecular substances (1,2). PAH-substances are expected to fulfil the criterion for adverse effects.
Potential for long-range transport

Most PAH-substances, with the exception for some low molecular substances, have low volatility and water solubility. In the atmosphere they are primarily adsorbed on particles and can by that be transported long-range. Transport in this way has been reported to the Artic region, but it may be problematic to define the origin of the substances. Most of the risks related to PAH in the environment are, however, more associated to the local levels than the levels in remote areas (3).


PAH-substances are already included in the LRTAP POP-protocol, targeted for a reduction of the total discharges mainly through the application of best available technology (BAT) at some large point sources, such as the production of coke, anode and aluminium (3).
The PAH-group is treated within the Water Framework Directive 2000/60/EC, where polycyclic aromatic hydrocarbons, and some individual substances within the group, are included in the list of priority substances (4). For some PAHs1 levels of 0.0091-0.036 µg/l have been reported in European surface waters. For sediments, levels of 381-742 µg/kg for the same substances have been reported (5).

Consequences

A decision for a total cessation of discharges of PAH-substances would end all thermal processes, as would the use of automobiles and energy production from fossil fuels. The costs would be enormous. Even phasing out the use of creosote should be in the order of 220 million Euro/year, only through shorter intervals in exchanging electricity distribution- and telephone poles, depending on the lower efficiency of the substitutes. In developing countries such a decision would further forbid processes like house-warming and cooking with the aid of wood combustion (6).


The eventual inclusion of PAH in the Stocholm Convention can be discussed considering:

  • their possibilities to fulfil the criteria

  • the possibility that conventions can be weakened if substances are included, where there is little or no possibility for elimination

  • effects of PAH-substances are more considered as a local or a regional problem, not a problem caused by long-range transported PAH


References

1. PAH as a POP, Sara Edlund, Thesis, Internationella miljöinstitutet, Lund, September 2001.

2. OSPAR Draft Background Document on Polycyclic Hydrocarbons, OSPAR 2001

3. 1979 Convention on Long-Range Transboundary Air Pollution, 1998 Protocol on Persistent Organic Pollutants, United Nations, ECE/EB.Air/66, 1999

4. 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.

5. Fraunhofer-Institut (1999) Revised Proposal for a List of Priority Substances in the Context of the Water Framework Directive (COMMPS Procedure). Draft Final Report. Declaration ref.: 98/788/3040/DEB/E1. Schmallenberg, Fraunhofer Institut Umweltchemie und Ökotoxikologie.



6. 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


1 benzo-a-anthracene, benzo-a-pyrene, benzo-b-fluoroanthene, benzo-g,h,i-perylene, benzo-k-fluoranthene, samt indeno(1,2,3-cd)pyrene.





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