sou · GOB353d4 · 2001-01-01 00:00:00 — In: Metal Toxicology. . och Röndell, E. (1997) Nickel i handverktyg. 7/97. , G. och , K. (2000) Förekomst och gradering av 55 olika grundelement i den svenska miljön. (1996) Metaller – Materialflöden i samhället. (1998) Gruvavfall – Miljöeffekter och behov av åtgärder. H. och Menné, T. (1992) Allergic Contact Sensitization in an Unselected Danish Population. Acta Derm Venereol (Stockh) 1992; 72:456-460. Nriagu, J. (1990) Global metal pollution. 32, nr 7. (2000) , . , V., Bergbäck, B. och , P. (1995) Chromium and nickel in . 14/95. , R. och , F. (1997) Småbarns exponering för koppar via dricksvatten och risken för diarréer. I: Naturvårdsverkets- rapport 4734. . och , F. (1999) intake of copper from drinking water among young children in . Environ Health Perspectives 107, 441-446. SBL-analys (1998) Metallemissioner från trafiken i – Slitage av bromsbelägg. Rapporter från SBL-analys nr 2:98. SCB (1999) MiljöSverige – Metallutsläpp till vatten och luft från olika källor. Schleket, C. E. och Luoma, S. (2000) You are what you eat: incorporatingdietary metals uptake into environmental quality guidelines for aquaticecosystems. Learned discourses in SETAC GLOBE, 1:2, 38- 39. Sternbeck, J. (2000) Uppträdande och effekter av koppar i vatten och mark. Sternbeck, J. och , P. (1999) Nya metaller och metalloider i samhället. TGD (1996) Technical Guidance Document in support of the Commission Directive 93/67/EEC on risk assessment for new substances and Commission Regulation (EC) No 1488/94 on risk assessment for existing substances. ECB, Ispra, . (1999) , Ångströmlaboratoriet, . (1999) , . (1992) Critical concentrations of heavy metals in the mor horizon of swedish . (1998) Health Effects of Metals in the General . I: The Impact of Metals on the Environment. Proceedings from an IVA Symposium, 12-13,1998. (2000) Ovanliga metaller i slam. , internt PM . (1999) Krom, nickel och molybden i samhälle och miljö. Wergeman, G. (2000) , . , D. F., Brumbaugh, W. G., DeLonay, A. J., , E. E. och C. E.Smith. (1994) Effects on rainbow trout fry of metals-contaminated diet ofbenthic invertebrates from the , . 123, 51-62. Ålåker, L. (1999) , . , P., Sternbeck, J. och , E. (1998) Metaller, PAH, PCB och totalkolväten i sediment runt – flöden och halter. Exempel på metallers och metallföreningars klassificering med avseende på hälsofarlighet. Listan är på intet sätt fullständig. För fullständiga uppgifter om metallers och metallföreningars klassificering hänvisar vi till Kemikalieinspektionens föreskrifter (KIFS 1994:12) om klassificering och märkning av kemiska produkter. beryllium och berylliumföreningar utom berylliumaluminiumsilikater arsenik och flera arsenikföreningar beryllium och berylliumföreningar utom berylliumaluminiumsilikater beryllium och berylliumföreningar utom berylliumaluminiumsilikater zinkbis(N,N-dimetylditiokarbamat) litium och flera litiumföreningar tenntetraklorid och tenn(II)metansulfonat beryllium och berylliumföreningar utom berylliumaluminiumsilikater Metaller som har bedömts av IPCS. Bedömningarna finns publicerade i EHC-rapporter (Environmental Health Criteria). För varje metall anges nummer och utgivningsår. Aluminium, nr 194, 1997 Arsenik, nr 18, 1981 Barium, nr 107, 1990 Beryllium, nr 106, 1990 Kadmium, nr 134, 1992 Kadmium, miljöaspekter, nr 135, 1992 Krom, nr 61, 1988 Koppar, nr 200, 1998 Bly, nr 3, 1977 Bly, oorganiskt, nr 165, 1995 Bly, miljöaspekter, nr 85, 1989 Mangan, nr 17, 1981 Kvicksilver, nr 1, 1976 Kvicksilver, miljöaspekter, nr 86, 1989 Kvicksilver, oorganiskt, nr 118, 1991 Metylkvicksilver, nr 101, 1990 Nickel, nr 108, 1991 Platina, nr 125, 1991 Selen, nr 58, 1986 Tallium, nr 182, 1996 och organiska tennföreningar, nr 15, 1980 Titan, nr 24, 1982 Vanadin, nr 81, 1988 Syftet med bilaga 6 är att beskriva kunskapsläget och behovet av åtgärder för metaller och deras föreningar. För detta ändamål har metallerna grupperats på följande sätt: ·Metaller som är mycket vanliga i den för biosfären tillgängliga delen av jorden och, med undantag av aluminium och titan, förekommande i relativt stora mängder i människokroppen (jämfört med andra metaller): aluminium, järn, natrium, kalium, magnesium, kalcium, titan ·Metaller som enligt riktlinjerna ska fasas ut: bly, kadmium, kvicksilver - med stor användning : koppar, zink, krom, nickel - alla andra (ordnade efter atomvikt, lantanoiderna och aktinoiderna utbrutna): litium, beryllium, skandium, vanadin, mangan, kobolt, gallium, germanium, arsenik, rubidium, strontium, yttrium, zirkonium, niob, molybden, teknetium, rutenium, rodium, , silver, indium, tenn, antimon, tellur, cesium, barium, lutetium, hafnium, tantal, , rhenium, osmium, iridium, platina, guld, tallium, vismut, polonium, francium, radium, lawrenciu, lantanoiderna: lantan, cerium, praseodym, neodym, prometium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, tulium, ytterbium, lutetium, aktinoiderna: aktinium, torium, protaktinium, uran, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium. Halter av metaller. Sorterad efter fallande halter i mår (minerogent material) från norra . Uppgifterna om halter i mår är framtagna vid (och , 2000). Halter i global berggrund är hämtade från (1979). : ingen uppgift. Totalhalt i mår, norra Global berggrund (mg/g TS) (mg/g TS) Totalhalt i mår, norra Global berggrund (mg/g TS) (mg/g TS) Halter av element i mark i mg/kg, uppdelat på percentiler (icke-metaller kursiva). Uppgifterna kommer från SGU:s markgeokemiska kartering och avser de delar av landet som karterats fram (m.fl., 1997). 1Avser inte riket utan ett område i inland. Halten av vissa metaller i torkad jord. Beräknad halt i jord, Beräknad halt i jord, intervall, (µg/g) medelvärde, (µg/g) 7 000 – 550 000 14 000 – 28 200 100 – 4 000 100 – 3 000 50 – 1 000 5 – 3 000 10 – 1 000 Uppgifterna baseras på svenska mineraljordar. ²Uppgifterna baseras på internationell litteratur och är att betrakta som teoretiska medelvärden för jordklotet som helhet. (Kemikalieinspektionen,1994b) Exempel på användningsområden internationellt för några nya metaller (i huvudsak baserat på uppgifter från Sternbeck och , 1999). Silver: Industriella katalysatorer, batterier (t.ex. klockor och kameror), ytbehandlat stål, elektronik (kontakter, ledare, säkringar, strömbrytare m.m.), baktericid vid vattenrening, värmereflekterande skikt på vindrutor, samt smycken. Vismut: Medicin, kosmetika, områden inom petroleumindustrin och den metallurgiska sektorn. Vismut har ibland förts fram som ett möjligt alternativ till bly i t.ex. ammunition och glasyr. Vismutproduktionen baseras till stor del på det vismut som fås som biprodukt vid brytning av bly. Indium: Tunna ytskikt i LCD-displayer, bildskärmar och på vindrutor. Legeringar och lödmetaller med låg smältpunkt t. ex. inom elektronikindustrin. Korrosionsskydd i bilar och korrosionsskydd för marint bruk. Legering i tandguld. : Katalytiska avgasrenare, elektronik, tandguld, medicin och inom kemiindustrin. Platina: Katalytisk avgasrening, katalysator inom kemi- och petroleumindustri, beläggning på hårddiskar och i glaset på bildskärmar, avfettningsmedel, smycken. Bränsleceller till elbilar kan vara ett kommande användningsområdet. Antimon: Flamskyddsmedel i t.ex. plast, textilier och elektronik, blylegeringar till t.ex. batterier, lager och kabelmantling, bildskärmsglas, katalysator inom kemiindustrin Selen: Glas, kopiatorer, elektronik t.ex. laserskrivare, IR-detektorer, solceller, röntgenutrustning, i kombination med kadmium som pigment, legeringsämne till stål och koppar, kosttillskott. Selen produceras som biprodukt till koppar. Tellur: Stål- och kopparlegeringar för att förbättra bearbetbarheten, accelerator vid gummitillverkning, pigment i glas och keramik, elektronik t.ex. termoelektronik, kopiatorer, detektorer för gamma- och röntgenstrålning och solceller. Summary Report from Round-Table Discussion on Criteria for Phasing Out Persistent and Bioaccumulating Organic The Task of the Committee............................................. The Conditions of the Discussion..................................... Summary of the Discussions .................................................. Persistence and Bioaccumulation..................................... Toxicity and other factors ............................................... On the future process ..................................................... ·in order to phase out a chemical which is highly persistent and bioaccumulative it would not be necessary to consider toxicity information, nor to perform risk assessment. ·criteria to select persistent and bioaccumulative chemicals should be held as simple as possible. ·new and existing chemicals should eventually be subject to the same regulation, but more stringent criteria could be applied to new chemicals at an earlier point in time. ·the lack of information about the properties of many anthropogenic chemicals is a major obstacle, impeding hazard assessment. 2.1The Task of the Committee The Swedish Government has proposed fifteen overarching environmental quality targets for the future environmental management (Ministry of the Environment, 1998). One of the targets concerns the achievement of an environment free from toxic chemicals. To realise this, the Government has decided on New , and our Committee has been assigned the task of concretising the Governments New Policy Guidelines on Chemicals (Ministry of the Environment, 1999). The Government intends to work to ensure the implementation of its guidelines within 10-15 years. A general approach, focusing on chemical substances with documented health-endangering properties, and on organic, man-made substances which are bioaccumulative and persistent, should be adopted, to supplement present-day risk assessment methods. Among the tasks of the Committee is to propose more exact definitions of when an anthropogenic substance is so persistent and bioaccumulative as to be affected by the phase-out requirements of the guidelines. The proposal of the Committee should be scientifically based on internationally accepted definitions, if such exist. 2.2The Conditions of the Discussion The purpose of the discussion was to obtain scientific views on a draft proposal on general definitions, and on a criteria model for selecting which persistent and bioaccumulative substances are not to be used in future, manufactured products and goods, nor in production processes unless the producer can show that the use is of no risk to human health or the environment. The form of the meeting is given by the program (1), which includes a list of participants. The summary below adheres to the program, as far as applicable, and covers solely the discussion sessions. For clarity, some definitions have been added from the draft proposal (as the Committees starting point), opening sections 3.1 and 3.2. 3 Summary of the Discussions ·persistence more weight than bioaccumulation, because persistent substances give rise to a risk of prolonged exposure and exposure far from the source. ·degradation half-life is an adequate expression of persistence. ·simple, general criteria of persistence, with the starting point in results from standardised tests, are preferrable, although any additional, relevant information should also be considered. The Committee´s starting point Persistence implies that a substance will be stable in the environment resisting chemical, physical and biological transformation reactions leading to degradation. Inert, or truly persistent, compounds have a chemical structure impeding the chemical reactions necessary for degradation. Degradation processes may be biotic, such as microbial degradation in water and sediments, and abiotic, such as photolysis in air and hydrolysis in water. The degradation of a substance should not be considered as complete until ultimate degradation to harmless products is proven to be the case. Persistence is a key property The view held by the Committee, that persistence can be regarded as a key criterion, carrying more weight than bioaccumulation potential, received substantial support by the group of participants. The reason for this view is that persistence implies an extended risk of exposure, over a long period of time, which may cause undesirable, adverse effects already at a moderate degree of bioaccumulation potential, if the substance is capable of producing such effects. Persistence also implies that a substance may be transported long distances, causing exposure far from the source. It was concluded, however, that persistence, defined as resistance to degradation, is not merely an intrinsic property of a chemical, but may to a large extent depend on environmental conditions, and also on which degradation mechanisms are in progress. Furthermore, degradation kinetics may vary, and degradation may take place in several consecutive time-phases. Half-lives should be determined in standardised tests Degradation half-lives were agreed to be an adequate expression of persistence. Half-lives should reflect the persistence in the relevant environmental compartment, and take into account mobility between compartments. However, experimentally determined half-lives can be expected to vary considerably depending on under which conditions they are determined. To try to account for many possible conditions of degradation would add back a substantial complexity to the model, the aim of which is to provide simple, general criteria. Therefore, preferably, data from standardised laboratory determinations should be used, honoring adequate safety , to keep criteria as simple (non- complex) as possible. In e.g. OECDs tests it is possible to distinguish between easily degradable and potentially persistent compounds. But chemicals with degradation characteristics in between are problematic to distinguish. It was asked what is the best acceptable evidence for degradability, and there was agreement that data from ready biodegradability tests could be used. However, available methods to determine half-lives, using todays simulation tests, should be considered in addition. It was emphasised that if favouring a simple model for the determination of persistence it is still necessary to be aware of which aspects are lacking. Not only half-lives (DT50) may be of interest, but also DT90 (the time after which of a compound has been degraded), in particular for very bioaccumulating compounds. Also, it was pointed out, besides results from tests employed to provide information to match certain criteria, all other information available on the degradability of a chemical under relevant environmental conditions should be considered. Half-lives in water and air It was generally agreed that it is justified to apply demands of shorter half-lives to the aquatic environment than to the terrestrial (soil) environment, with regard to persistent compounds distributing to these compartments. Regarding persistence in air, the view was expressed that a limitation set at a half-life longer than two days is only applicable to semi-volatile compounds that are prone to redistribute to the terrestrial and aquatic environment. Highly volatile compounds, which are not likely to be deposited after volatilisation, could be considered to be of concern if their atmospheric half-lives exceed two weeks. It was also pointed out that it is possible today to calculate overall half- lives for chemicals by multi-media models, taking into account compartment specific degradability and distribution coefficients. ·BCF values measured according to the methodology are a good indicator of the potential for a substance to bioaccumulate, but for non-ionic molecules, logKow may be a surrogate up to values of about 6-7. ·bioaccumulation caused by other intrinsic properties than lipid solubility, e.g. protein-binding, should also be considered. ·the presence of significant amounts of a substance in biota can in certain cases be used as an indicator of bioaccumulation. The Committee´s starting point Bioaccumulation potential is understood as the tendency for a substance to be enriched in organisms by uptake from the surrounding medium and from the food. Commonly, bioaccumulation is approximated using bioconcentration, which in a fish reflects primarily the uptake from water via the gills. Bioconcentration applies mainly to fat-soluble, neutral substances of relatively low molecular weight (LMW). The bioconcentration factor (BCF) is determined as the ratio between the concentrations of a substance in the organism and in the surrounding medium at equilibrium. In order for a substance to bioaccumulate or bioconcentrate it must be bioavailable, that is available for passive or uptake by organisms. The bioaccumulation potential of most LMW organic compounds is closely linked to their lipid solubility, and for such compounds the BCF is often related to the partitioning of the substance between octanol and water, expressed as the Kow. Bioaccumulating substances may be biomagnifying, that is, the concentration increases from one trophic level to the next, moving up in the food web. Bioaccumulation is not fully covered by BCF values It was regarded as being of importance to consider not only bioconcentration by uptake from surrounding water, sediment and soil, but also bioaccumulation via uptake from food, and in the atmospheric compartment, bioconcentration in vegetation by air exposure. Bioconcentration factors (BCF), measured in standardised tests using fish, it was further pointed out, may miss compounds that accumulate by binding for example to plasma proteins, that is compounds such as pentachlorophenol. Unlike partitioning phenomena modelled by Kow, protein binding is quite organism-specific, and can not easily be determined except by experiment on different species. Are BCF values more relevant than logKow? It was stressed that biomagnification is a problem also in the terrestrial environment, while standardised BCF tests using fish will only approximate the bioaccumulation in an aquatic model system. Bioavailability can be very different in terrestrial and aquatic environments. For example, compounds with very high logKow, bound mainly to particulate matter, may be quite unavailable in an aquatic system, but highly available if deposited on vegetation and consumed by herbivores. The use of different fish in the aquatic standard test will introduce some variation in the BCF values. Variation, however, may result also from e.g. experimental artefacts. Still, many participants argued that aquatic BCF is a better measure of bioaccumulation potential than is logKow, one reason being that an experimental BCF value reflects the uptake by a living organism upon exposure. Another opinion, however, was that logKow gives a measure which is independent of variations between species. A problem, it was observed, is that BCF determinations sometimes have been performed using the compound of interest at a concentration above its solubility. The issue of which of BCF and logKow values is more appropriate to use could not be settled to full satisfaction by the participants, although the general trend of the discussion was in favour of using BCF rather than logKow. It was further pointed out that certain compounds are bioaccumulating despite the fact that, nominally, their molecular size is too large. And it was noted that elimination by excretion of a persistent compound by one organism can lead to bioaccumulation in another organism, having less capacity for excretion of the compound. The answer is in the environment, one participant stated. What chemicals are present in organisms at high trophic levels? Monitoring data was agreed to be a good source of information, but the possibility of presence of anthropogenic substances in biota because of continuous exposure also has to be taken into account. And it is important to keep in mind that only relatively few substances are being monitored. At what limit is BCF of concern? In a discussion of which BCF limits would be scientifically justified to consider to be of concern, the following, different opinions were expressed: A limit of BCF > 10,000 is enough for easily degradable compounds. A lower limit than BCF > 5,000 cannot be scientifically justified, even if the toxicity is unknown. A lower limit than BCF > 5,000 is justified for compounds that do not distribute globally by transport with air, unlike in the criteria under discussion by, for example, , where globally distributing compounds are considered. A limit of BCF > 3,000 is justified considering the risk of biomagnification at higher trophic levels. A limit of BCF > 1,000 is reasonable for the aquatic environment. A limit of BCF > 100 is justified for truly persistent compounds. ·P and B criteria are necessary, but not sufficient to address all substances of potential concern. ·the industry should be responsible for providing the needed data. ·the same policy should be applied to both new and existing chemicals. The ultimate goal is the same (no accumulation in the environment) but the timing for implementation of the criteria could be different. As a general conclusion, it was¾after some discussion¾agreed upon that it can be scientifically justified to take regulatory action against the most persistent and bioaccumulating chemicals, without considering toxicity information. Future, possible problems of persistent, bioaccumulating substances cannot be known. It was pointed out that it can be justified by the Precautionary Principle to use criteria only regarding persistence and bioaccumulation, provided that it is still understood that toxicity properties are important. Furthermore, it was stressed that criteria with regard to persistence and bioaccumulation potential do not provide a complete solution to all problems with man- made chemicals. The tiered approach suggested by the Committee received substantial support. This approach implies that immediate action can be taken based on relatively simple criteria, such as the lack of data, in which case the worst case would be presumed. With regard to persistence this approach would furter imply that not ready biodegradable compounds could be subject to regulation, when no other data on degradability is at hand, while ultimate criteria allowing for longer half-lives than those estimated to correspond to not ready degradability would demand information from simulation tests. This approach also would involve the possibility for re-evaluation when data of higher quality become available, which was favoured by most participants. So was also the basic idea that it is the responsibility of the provider to produce the necessary information. It was suggested that monitoring data could be used to check whether the criteria adress the relevant compounds. But, it was objected, only a few of compounds are regularly monitored. With this reservation in mind, however, monitoring data could be a valuable complement. And to find xenobiotics in biota is reason enough for action, several participants pointed out. The P/B matrix suggested by the Committee (Figure 1) was generally accepted as a tool, in particular for initial screening, although some participants regarded it to be too simplistic. The model was suggested to be a good starting point for identifying chemicals of concern within EU, and to bring to the attention of the industry which properties in chemicals are not wanted. It was put forward that screening criteria possibly could be set at the EU classification limits. It was generally agreed that immediate action could be taken to initiate the phase out of existing P4/B4 chemicals (Figure 1), while less stringent measures (applying lower P and B values) could be considered against new compounds.