Geperfluoreerde verbindingen in Nederlands oppervlaktewater: Een screening in 2003 van PFOS en PFOA

Geperfluoreerde (volledig gefluoreerde) verbindingen worden sinds 1950 veelvuldig gebruikt om vloerbedekking en textiel water- en vuilafstotend te maken. Ze worden ook gebruikt om papier voor het verpakken van etenswaren vetvrij te maken. Een heel andere toepassing van deze stoffen is de toevoeging aan brandblusmiddelen. Sinds het begin van de negentiger jaren bestaat er in Canada en de Verenigde Staten aandacht voor deze geperfluoreerde verbindingen in het milieu en de laatste jaren is er ook in Europa aandacht voor deze stoffen. Dat er pas recent in het milieu gemeten wordt, heeft voor een groot deel te maken met het feit dat analysetechnieken voor deze stoffen pas sinds kort beschikbaar zijn. Geperfluoreerde verbindingen zijn zeer persistent en sterk bioaccumulerend. Het grootste risico van deze stoffen voor het milieu is de ophoping in de voedselketen (doorvergiftiging). Over de manier waarop de verspreiding van de stoffen in het milieu plaatsvindt is nog veel onduidelijkheid. Wel duidelijk is dat geperfluoreerde verbindingen wereldwijd, tot in ijsberen uit het Noordpoolgebied, worden aangetroffen. In 2003 heeft Rijkswaterstaat een screening naar het voorkomen van geperfluoreerde verbindingen in zoet en zout oppervlaktewater gedaan, om een beeld voor de Nederlandse situatie te krijgen. Hiervoor zijn twee geperfluoreerde verbindingen, PFOS en PFOA, in sediment, zwevend stof en verschillende soorten biota gemeten. Opgemerkt moet worden dat de analysemethodes voor deze stoffen nog niet volledig uitontwikkeld zijn, zodat de resultaten als globale indicatie van de concentraties in het Nederlandse aquatische milieu gezien moeten worden. Analyses in het water zelf waren ten tijde van het onderzoek nog niet goed uitvoerbaar. De resultaten van deze screening laten zien dat PFOS in Nederland overal aangetroffen worden, zowel in de zoete binnenwateren als in zee. PFOA wordt in zwevend stof slechts in enkele monsters aangetroffen, in sediment daarentegen relatief veel vaker. De aangetroffen concentraties zijn voor beide stoffen vergelijkbaar. In zwevend stof worden concentraties tot enkele tientallen nanogrammen per gram gevonden, terwijl in het sediment de concentraties over het algemeen lager liggen. In sedimentmonsters afkomstig uit een gebied waar perfluorhoudende brandblusmiddelen zijn gebruikt, zijn verhoogde concentraties van PFOS (factor 2 tot 5 hoger) aangetroffen. In vis wordt alleen PFOS aangetroffen, met de hoogste concentraties in aal tot meer dan 100 nanogram per gram vis. PFOA was in geen enkel biotamonster boven de detectiegrens aanwezig. De PFOS gehalten in aal zijn van dezelfde ordegrootte als polychloorbifenylen, bijv. PCB153, en gebromeerde brandvertragers zoals BDE47 en HBCD. Ook voor zwevend stof en sediment gaat het om vergelijkbare concentraties als die van PCB153 en bijvoorbeeld de veel voorkomende gebromeerde brandvertrager BDE 209. De resultaten van deze Nederlandse studie geven aan dat geperfluoreerde verbindingen ook in het Nederlandse milieu alom aanwezig zijn. Dit ondersteunt het belang van de beleidsmatige aandacht die er binnen de EU, ook vanuit Nederland, voor deze stoffen is

Chemical study on Bisphenol A

General Bisphenol A is used as an intermediate (binding, plasticizing, hardening) in plastics, paints/lacquers, binding materials and filling-in materials. The substrate is mainly used for the production of polycarbonate resins (71%) and epoxy resins (27%). Furthermore bisphenol A is used as an additive for flame-retardants, brake fluids and thermal papers. The current (1999) world-wide production of bisphenol A is approx. 2,000 ktonnes/year. Over the next 5 years, overall production is believed to grow to around 3,500 ktonnes/year in 2005. Sources and emissions The production of bisphenol A in the Netherlands in 1999 was around 280 ktonnes/year, which is approx. 35% of the total production in Europe and around 14% of the total world production. A review of all produced, used amounts and emissions is given in Table 1. Over the years bisphenol A consumption has more than doubled. From 1993 to 1996, total consumption for polycarbonates grew with 11.6% per year and is expected to continue to grow at an average annual rate of 7.6% during the period 1996-2001. Bisphenol A consumption for the production of epoxy resins will also grow but more moderately. In 1999 annual bisphenol A consumption in Europe is estimated at 680 ktonnes. Total polycarbonate consumption in the Netherlands is 14 ktonnes/year while other consumption of bisphenol A based products is 11 ktonnes. Emissions of bisphenol A may occur during bisphenol A production, production of products using bisphenol A and from products in-use. Emission during bisphenol A production is around 2 tonnes/year to surface waters and 1 tonne to air. The most important emissions during bisphenol A product processing occur during production of phenoplast cast resins (43 tonnes to water in Europe), thermal paper production (151 tonnes to water in Europe) and the use of bisphenol A as inhibitor during PVC production (25 tonnes to water in Europe). Total emissions are 2.1 tonnes to air, 199 tonnes to water and 30 tonnes to soil in Europe. The specific emissions for the Netherlands are unknown. Emissions from products in-use are estimated at 160 kg from polycarbonates and <1 kg of epoxy resins used in can lining. Furthermore losses from PVC articles inuse are 20 tonnes to air and 30 tonnes to water. Concerning emissions are the leaches of bisphenol A from baby bottles, cans and flasks to food. In baby bottles in a study an average of 56 ppm is found to leach and in another study a maximum of 20 mg BADGE/kg plastic leached from cans. Concentrations in food are not available. Environmental characteristics and toxicity in aquatic systems Bisphenol A has a moderately high water solubility (120 mg/l) and a low vapour pressure (5.32 10-5 Pa). The log Kow value varies from 2.2 to 3.4. As a result of these characteristics bisphenol A has a tendency to partition into water and the rate of evaporation from soil and water will be low. The log Kow indicates a low bioaccumulative potential. Based on experimental data the BCF varies from 1 to 196, which also indicates a low potential to bioaccumulate in aquatic species. Bisphenol A is not susceptible to hydrolysis but has a potential to photolyse in water if not bound to organic matters (particulate phase) in water. From biodegradation tests bisphenol A is found to be not readily biodegradable, but to be inherently biodegradable. However measured levels of bisphenol A before and after wastewater treatment suggest a high level of removal. After a short period of adaptation, bisphenol A seems to be readily biodegradable. The same goes for the biodegradation in natural waters after acclimatisation. Bisphenol A is acutely moderately toxic to freshwater and marine algae, fish and crustaceans. Based on chronic tests bisphenol A is very slightly to slightly toxic in freswater and moderately toxic in marine water. Based on 1 chronic study with endocrine effects (skewed sex-ratio) with an amphibian, bisphenol A is very toxic. Occurrence and behaviour in aquatic systems In the Netherlands concentrations of 21 to 40 ng/l have been found in fresh waters and of 3.5 to 23 ng/l in marine waters. The concentrations in industrial and urban wastewater are in the range of 300 to 700 ng/l but for two locations, where the concentration reached the 2 mg/l. Bisphenol A concentration in sewerage and wastewater sludge ranged from <116 to 7000 ng/l (15-270 ng/g dry matter). In sediments concentrations were below the detection limit of 0.05 - 0.25 ?g/kg dry matter. There are no data on concentrations in other environmental compartments. In Japan concentrations of 60 to 1900 ng/l have been measured in surface water in 1974-1978. All measured concentrations are considerable lower than the calculated HTBA value of 247 mg/kg and lower than the calculated iMPCs of 0.064 mg/l and 22.9 mg/kg for resp. surface water and sediment. Policy No specific quality standards are derived for bisphenol A. Bisphenol A is not regulated. However there are some regulations with regard to the maximum limits of bisphenol A in food and migration from materials that come into contact with food. Conclusions and recommendations From the results of this study can be concluded that bisphenol is widely used and therefore also widely spread in the environment. Current data on the release and distribution of bisphenol A are limited, but suggest that the substance will primarily be available in the aquatic phase in surface waters and probably will hardly bioaccumulate in organisms. Estimates of emissions to the environment demonstrate that significant amounts may be released to surface water by discharge of treated wastewater. For evaluation of the aquatic toxicity of bisphenol A, a limited amount of data was available. Considering the large emission estimates to surface water, their high tendency to spread in aquatic systems and the fact that bisphenol A is moderately toxic to aquatic organisms, it is recommended to perform an additional study on these compounds with emphasis on collection and verification of emission factors and furthermore to generate new toxicity data. Especially in the area of endocrine disrupting effects more research should be done because these effects concentration may be a factor 100-1000 lower. Further research into concentrations in food are also considered important in relation to the leaching of bisphenol A from baby bottles, flasks and cans

Chemical study on estrogens

General Natural estrogens are mainly formed in the ovary, during pregnancy in the placenta and in smaller quantities in the adrenal glands and testicles. Natural estrogens control the development of secondary female sex characteristics and together with the gestagens control almost all of the reproductive processes in women. Synthetic estrogens are used as a pharmaceutical product as an oral contraceptive and hormonal replacement therapy. In the USA synthetic estrogens are also used in veterinary the induce growth of animals. The most commonly used synthetic estrogen is 17a-ethinyloestradiol. A synthetic estrogen is in principle a more stable compound in order to fullfill a wanted effect, before the substance is degraded and metabolised. Sources and emissions Primary production of natural estrogens occurs in female mammalian animals and in female humans. Synthetic estrogens as 17ß-oestradiol and 17a-ethinyloestradiol are produced in the Netherlands, Germany and the USA but production volumes are largely unknown. The total emissions of endogenous estrogens by human beings and animals in the Netherlands can be estimated at approximately 50 kilograms per day. This figure is possibly an underestimate, since neither, other livestock - such as rabbits, ducks, sheep, goats, horses, etc - nor companion animals, were included. Emissions of ethinyl oestradiol ('the pill') are estimated at 43 grams per day. This may be an underestimate, in view of the fact that the progestagens that are also in the anticonception pill, may also be metabolised to steroid metabolites. In any case, this contribution is insignificant compared with the estimated total emissions of natural estrogens (50 kg/day). It should be noted that emissions from countries surrounding the Netherlands have not been taken into consideration. Assuming a leaching of 3% from applied manure to surface water and an average rainfall of 60 mm/month, the concentration in surface water, will be 1.3 ?g/l after application of the maximum allowed amount of manure of sows in 1 month and 0.43 ?g/l in 3 months in local waters. After application of manure of cows in the maximum allowed amount in 1 month, the concentration in surface water is 0.9 ?/l and in 3 months 0.3 ?g/l in local waters. Estimated concentrations in regional waters range from 19-76 ng/l for the river Rhine and from 35-140 ng/l for the river Meuse. Environmental characteristics and toxicity in aquatic systems All oestradiols, oestrone and ethinyloestradiol have a low vapour pressure and a low water solubility. The log Kow varies from 3.13 for oestrone to 4.01 for both oestradiols. This indicates a moderate potential to bioaccumulate. There are no data on bioaccumulation. Occurrence and behaviour in aquatic systems There is no information on hydrolysis or photolysis. There are some differing results for biodegradation in STP in Germany and Brazil. The differences are probably due to the difference in temperature. Based on the limited data it can be concluded that oestradiols and oestrone are fairly rapidly degraded. Ethinyloestradiol seems to be more persistent. Under anaerobic conditions degradation is considerably lower. Concentrations in the Netherlands have only been measured in one study in 1997. Highest concentrations were measured in Lobith and Eijsden (upto 5.5 ng/l). In large surface waters and marine waters, dilution occurs and concentrations are hardly detectable. Concentrations in sewerage in The Netherlands are lower than in the surrounding countries (UK, Germany) There are very limited data on concentrations in food: milk of carying cows contains about 1 ?g estrogen/l. Toxicity Estrogens are (de)oxidated, hydrolysed and methylised in liver and conjugated with glucuronic acid or sulfate. 17ß-oestradiol is easily oxidised to oestrone, which is further metabolised to oestriol or 2-methoxy-oestrone. Ethinyloestradiol is metabolised to hydroxy-ethinyloestradiol and further metabolised to methoxyethinyloestradiol or deethinylated to oestrone. Estrogens are excreted in faeces and urine. All estrogens are suspected carcinogens. Data on acute toxicity indicate that estrogens are very toxic to mammalians. Toxicity data are scarce. Based on endocrine disrupting effects all estrogens are very toxic. Based on acute effects on survival and reproduction 17aethinyloestradiol is also very toxic to freshwater algae and crustaceans. Based on chronic effects on survival and reproduction 17ß-oestradiol, oestrone and 17a-ethinyloestradiol are only slightly toxic to marine crustaceans. There are no limit values derived for the estrogens. There is a iMPC derived for 17a-ethinylopestradiol of 1 ?g/l. Concentrations in surface water in the Netherlands do not exceed this iMPC. Policy There is hardly any policy on estrogens in relation to the environment. 17ß-Oestradiol, oestrone and 17-ethinyloestradiol are on the OSPAR list VI. However there are no actions to this group of substances, yet. There is, however, a ban on the use of estrogens as growth inducers in farm animals in Europe (88/146/EEC). In Canada and the USA estrogens are still used for this purpose. This ban on meat from farm animals treated with estrogens, has led to an discussion with Canada and the USA. Furthermore there is a regulation that estrogen may not be part of cosmetic products (76/768/EEC). There are also plans for a directive on assessing the risk of environmental exposure of veterinary products and a similar directive on medicines is launched as a draft. Conclusions and recommendations In general data on estrogens are very scarce. Data should be produced on behaviour, distribution, production and emission. Also, more data on acute and chronic toxicity should be produced. Furthermore there should be a guideline on how to treat effects on the endocrine system. Especially interesting is, how these endocrine effects influence the populations. Recommended is to conduct a study into the production volumes of estrogens and the concentrations of estrogens in groundwater, drinking water and food

Chemical study on alkylphenols

General Alkylphenols are mainly used as raw material in the production of a variety of industrial products such as surfactants, detergents, phenolic resins, polymer additives and lubricants. Private and commercial use of alkylphenols does not occur. Current world demand is estimated at approximately 400,000 tonnes/y, with nonylphenol as the most widely used compound (market share: 80- 90%). Octyl-, dibutyl-, decyl- and dodecylphenols are produced in total quantities of 60,000 tonnes/year. Nonylphenol production in Western Europe amounts to 75,000- 80,000 tonnes/year. Octylphenol production is estimated at approx. 7,000 tonnes/year. In the Netherlands, there are no production sites for alkylphenols. Nonylphenol demand in The Netherlands is estimated at 1300- 1400 tonnes/year. For the next few years, world demand will grow 1-2 % per year. Alkylphenol ethoxylates are primarily used as surfactants, detergents and emulsifiers in a wide range of applications in the industry (auxiliaries) and as commercial product (cleaning agents, wetting agents, dispersants, lubricants, etc) in many end use sectors. Current world demand is estimated at 600,000 tonnes/y, with nonylphenol (85%) and octylphenol ethoxylates (15%) as most widely used compounds. World demand growth is estimated at 2-3 %/year. In the EU, due to voluntary and regulatory initiatives, the use of these substances is to be limited in order to minimise alkylphenol emissions to the environment. In Western Europe, nonylphenol ethoxylates production is about 120,000 tonnes/year. Demand in the EU varies from 65,000 to 80,000 tonnes, while export amounts to 35,000- 45,000 tonnes/year. In the Netherlands, there is no production of alkylphenol ethoxylates. Annual nonylphenol ethoxylates demand in 1997 was estimated at approx. 1,500 tonnes, coming down from 4,900 tonnes/year in 1986. Sources and emissions Nonylphenol emissions due to use in the chemical and polymer industry in the Netherlands (10), are very soluble in water, making these compounds potentially mobile. However, once released in water, they are easily hydrolysed to compounds with few ethoxylate groups (n10) are easily hydrolysed to short chained ethoxylate compounds (n nonylphenol > nonylphenol ethoxylate. Octylphenol and nonylphenol ethoxylates are metabolized to octyl- and nonylphenol. Numerous ecotoxicity data are available on nonylphenol. There are no data on the ecotoxicity of octylphenol ethoxylates. From the available data on octylphenol is appears that octylphenol is extremely toxic to aquatic organisms but seems to be less toxic to algae and bacteria. Nonylphenol is also very toxic to most aquatic organisms. Nonylphenol ethoxylate is moderately to very toxic to aquatic organisms. The iMPCs are derived for octylphenol (0.122 ?g/l and 16.08 ?g/kg ds), nonylphenol (0.35 ?g/l and 1186 ?g/kg ds) and nonylphenol ethoxylate (0.044 ? g/l and 5.67 - 11.31 ?g/kg ds). Comparing the iMPC with the actual measured concentrations the iMPCs for nonylphenol and nonylphenol ethoxylate are exceeded in the Netherlands. The iMPCs for octylphenol is not exceeded in the Netherlands but concentrations in other countries in Europe do exceed the iMPC. Occurrence and behaviour in aquatic systems Significantly increased levels of alkylphenols and alkylphenol ethoxylates are found in sediments near wastewater treatment plants and specific user sites, with highest levels for nonylphenol and its ethoxylates. Levels in water are significantly lower. In the middle and late 1980\u92s, sediment/water concentration ratios for nonylphenol ranged from 300- 5,000, at concentrations of 500- 15,000 ?g/kg (dw) in sediment and 1- 10 ?g/l in water. Concentrations for short chained nonylphenol ethoxylates (NP1EO and NP2EO) varied from 3,000- 12,000 ?g/kg (dw) in sediment and 10- 100 ?g/l in water. Comparison of 1984 and 1996 nonylphenol concentrations in Swiss river waters revealed that levels in water have decreased by roughly a factor 10. Similar data for comparison of sediment concentrations were not available. In the Netherlands, 1997 values for nonylphenol in fresh waters were below detection (< 0.07 ?g/l), whereas concentrations of nonylphenol ethoxylates were only a little higher (0.14 ?g/l). Nonylphenol levels in fresh water sediments (1,500- 1,700 ?g/kg dw) were lower than for nonylphenol ethoxylates (3,000- 8,000 ? g/kg dw). Concentrations of nonylphenol and nonylphenol ethoxylates were < 0.07 ?g/l in Dutch estuarine surfacewaters. For both nonylphenol and nonylphenol ethoxylates, levels in Dutch estuarine sediments were approximately 2-3 times lower than in fresh water sediments. Policy In several countries policy has been made on octylphenol and nonylphenol ethoxylates. Virtually all domestic uses of nonylphenol ethoxylates as cleaning agents have been phased out. In the Netherlands the use of nonylphenol ethoxylates as cleaning agents for industrial uses is reported as terminated. Prognosis Further to voluntary industry initiatives to minimise the use of nonylphenol ethoxylates as much as possible, the nonylphenol ethoxylates demand in the EU is expected to decline in the coming years. Quantitative data for future reduction targets are not available, however. Within the framework of PARCOM, national authorities in various Western European countries will shortly review the progress of current voluntary initiatives, in order to assess the necessity of further regulatory use restrictions. Conclusions and recommendations From the study results can be assessed that due to wide spread use of nonylphenol ethoxylates in industrial and non-industrial applications, selected compounds are abundantly present in fresh water environments, mainly due to biodegradation of nonylphenol ethoxylates in municipal wastewater. Major emissions to surfacewater are coming from end-use applications where used products are integrally discharged with wastewater. Physico-chemical data of selected compounds indicate that, due to sorption onto sediments, mobility in aquatic environments will be low. Environmental data for release verification and distribution in marine sediments and biota are however scarce. In the Netherlands, due to restricted use in non-industrial applications, many nonylphenol ethoxylates have been replaced in the last decade and their use has decreased by approx. 70%. National data for historical evaluation of emissions are not available, but from foreign figures it is expected that lower use will have lead to lower nonylphenol and nonylphenol ethoxylates levels in environments. Further it is assessed that alkylphenols are moderately to very toxic to aquatic organisms. Alkylphenols also exert endocrine disrupting effects and are widely observed in the environment at concentrations exceeding the derived iMPCs. Although degradation in the environment occurs (inherently biodegradable) the substances present a considerable risk to the environment. Based on the fact that alkylphenols are carcinogenic and exert endocrine disrupting effects, it is recommended to derive an ADI or TDI in order to facilitate a comparison between human exposure and the concentrations in the environment. From comparison of iMPC values with concentrations in the environment it follows that the iMPC are exceeded in most cases. It is therefore advised to derive an official MPC. There are for the moment no data available on octylphenol ethoxylate. Although octylphenol ethoxylate use is minor and their occurrence is scarcely monitored in the environment, it is recommended to gather more information on these substances because it is closely related to nonylphenol ethoxylates

Perfluoroalkylated substances: Aquatic environmental assessment

GENERAL Perfluoroalkylated substances (PFAS) is the collective name for a group of fluorinated chemicals, including oligomers and polymers. There are two major production routes for PFAS: Electrochemical fluorination and telomerisation. The products from the first process contain a sulfonyl group (the so-called ECFproducts). The products from the second production process contain an ethylene group (telomers). POSF (C8F17SO2F) is the most important production intermediate for electrochemical fluorination. 8:2 FTOH (C8F17C2H4OH) is the pivotal substance for telomer production. The most important difference between the two production processes is that ECF yields even and odd numbered, branched and straight perfluoroalkyl chains, whereas telomerisation only yields even, linear chains. Both ECF-products and telomers have four major forms of appearance, namely monomeric, homo-polymeric, co-polymeric, and phosphate esters. Co-polymers, based on acrylates or methacrylates, are the most common form of appearance. Until the 3M company decided to phase out their PFAS production line, they were the major producer of PFAS. Other important suppliers of PFAS chemistry are DuPont, Asahiglass, Clariant, Daikin and Ciba. For the present study 15 perfluoroalkylated substances have been selected. These substances are used in commercial products, monomers for polymers, important production intermediates or important degradation products. PFAS have special physical and chemical properties, including chemical inertness, high thermal stability, low surface energy, hydrophobicity and oleophobicity. These properties make PFAS valuable compounds for a wide variety of applications, including carpet, textile, leather and paper and board protection, fire-fighting foams, and specialty surfactants. SOURCES AND EMISSIONS Several applications may lead to emissions of PFAS. The most important is the emission due to wear of PFAS treated tissue (carpet, textile, leather). These emissions are polymeric substances; whether this may lead to monomeric PFAS is not known. The use of fire-fighting foams for calamities or training leads to emissions of monomeric PFAS to the environment. Furthermore, emissions from fluorochemical production sites may be a route of introduction of PFAS into the environment. The use and associated emissions from these applications were assessed in the current report. The most important application of PFAS in the Netherlands is in paper and paper board treatment, but all this paper is imported. The carpet, leather and presumably the textile industry are the biggest users of PFAS based products in the Netherlands. BEHAVIOUR IN THE AQUATIC ENVIRONMENT For a proper assessment of the behaviour of PFAS in the environment many data are lacking. The available data show that the standard concepts of environmental modelling are not applicable. PFAS distribution is not solely based on hydrophobic and hydrophilic interactions, but most likely also on electrostatic interactions. The most important accumulation positions in (aqiatic) biota are expected to be blood and liver. n-EtFOSE, n-MeFOSE and n-EtFOSA (ECF-products) and 6:2 FTOH, 8:2 FTOH and 10:2 FTOH can readily escape from the water phase to air, considering their relatively high Henry\u92s Law constants (HLC). Some of these chemicals have been detected in air recently. This may be an important factor in the global distribution of the PFAS. Other fluorinated chemicals have lower HLC and are expected to remain in the water phase. PFOS and 8:2 FTOH exhibit a high sorption potential and desorption is difficult. Test results show that the perfluoroalkyl chain of ECF-products is not affected by biodegradation, hydrolysis or photolysis. The non-fluorinated part of ECF-products is expected to degrade to sulfonate or carboxylate. The degradation products of telomers are not known, but it is expected that the perfluorinated chain is not affected by degradation, hydrolysis or direct photolysis. Indirect photolysis by OH radicals in air may lead to the decomposition of fluorinated chemicals. 8:2 FTOH was shown to be transformed to some extent in rats to PFOA. For fluorinated organic polymers no degradation data are available. PFOS is highly bioaccumulative, considering its bioaccumulation factor of 6300-125000. PFOA hardly bioconcentrates (BCF = 1.8) and 8:2 FTOH has a bioconcentration factor of 87-1100. OCCURENCE PFOS and to a much lesser extent PFOA have been detected in the environment on a global scale. No validated sampling or analytical method for PFAS exist as yet. Point sources may lead to elevated levels of PFAS in biota and the abiotic environment. Concentrations of PFAS are higher in more urbanised or industrialised areas, in biota and in the abiotic environment. Concentrations in biota from North America were highest, followed by biota from Europe. Concentrations in biota from remote locations such as the Arctic were much lower. All PFAS that have been detected in biota were present in blood, liver, kidney, muscle or brain. PFOS concentrations ranged from below limited of quantification to 907 ng/g wet weight. No data are available for the occurrence of telomers in the environment. In humans, PFOS and PFOA has been detected in occupationally exposed workers and in the general public. Levels in fluorochemical production workers were 0.135-2.44 mg/L (PFOS) and 0.106-6.8 mg/L (PFOA); concentrations in the general public were 17-53 ?g/L (PFOS) and 3-17 ?g/L (PFOA). TOXICITY Toxicity tests for PFOS and PFOA have been performed, although many of them with limited reliability. Therefore the assessment of toxicity of PFAS should be considered as a first estimation. The results show that PFOS has moderate acute toxicity to freshwater fish and slight acute toxicicity to invertebrates. Toxicity to algae is practically nihil. The chronic toxicity of PFOS to freshwater fish is low and practically nihil to invertebrates. PFOS has moderate acute and slight chronic toxicity to marine invertebrates. Due to the relative data richness an assessment factor of 50 can be applied to the lowest chronic toxicity data to derive the proposed value for the Dutch quality objectives (iMPC) for PFOS of 5 ?g/L. PFOS concentrations in fresh water were shown to exceed the iMPC, in case of point sources. In other freshwaters, the iMPC was approached. PFOA has slight acute toxicity to freshwater invertebrates and algae, while being practically non-toxic to freshwater fish. Due to the limited number of studies currently available, an assessment factor of 1000 has to be applied to the lowest acute toxicity data to derive the iMPC for PFOA of 3.8 ?g/L. This iMPC may be approached close to point sources. For telomers no conclusions regarding their toxicity can be drawn. Both PFOS and PFOA have long half-lives (8.67 and 1-3.5 years, respectively) in the human body. Both chemicals are distributed to liver, plasma and kidney. To rodents PFOS and PFOA exhibit low acute toxicity, but they are eye irritating. In chronic feeding tests with rodents and primates the primary target was the liver for PFOS and PFOA. PFOA was found to be weakly carcinogenic. Mutagenicity testing of PFOS did not show any mutagenic effects. PFOA did induce chromosomal aberrations and polyploidy in Chinese hamster ovary cells, but did not show mutagenic effects in most mutagenicity test, including an in vivo micronucleus test. In a developmental effect study with PFOS the no observed adverse effect level (NOAEL) and the lowest observed adverse effect level (LOAEL) for the second generation of rodents were determined to be 0.1 mg/kg/day and 0.4 mg/kg/day, respectively. POLICY In the Netherlands, no specific policy concerning PFAS exists. In the USA the production and import of some ECF-products is regulated and a hazard assessment on PFOA has been performed. The governments from Canada, the United Kingdom and Denmark have programmed studies on the potential risks of PFAS. Furthermore, the OECD has performed a hazard assessment on PFOS. The 3M corporation has performed various studies on the toxicology, pharmacokinetics and environmental fate and effects of ECF-products, notably PFOS. The Association of Plastic Manufacturers in Europe, APME, has set up a research program on the toxicology, pharmaco-kinetics and environmental fate and effects of PFOA. The manufacturers of telomers, gathered in the Telomer Research Program (TRP), have set up a research program on the toxicology, pharmacokinetics and environmental fate and effects of 8:2 FTOH

Stoffen in de Noordzee en de Nederlandse Kustzone in 2003: Ftalaten, vlamvertragers, organotin- en geperfluoreerde verbindingen en effectgerichte metingen

Om de toestand van watersystemen te kunnen beschrijven en zo nodig maatregelen te kunnen nemen, is inzicht nodig in concentraties van prioritaire stoffen. Op de prioritaire stoffenlijst van de OSPAR en de Europese Kaderrichtlijn Water staan echter stoffen waarvan niet of slechts ten dele bekend is of ze een mogelijk probleem vormen in de Nederlandse mariene wateren. Deze onzekerheid was de voornaamste aanleiding voor de in dit rapport beschreven survey. Het hoofddoel van de survey was een beeld te krijgen van: - de concentraties van stoffen; - de respons van een aantal effectgerichte metingen met bioassays; in sediment en zwevend stof monsters uit mariene en estuariene watersystemen. De subdoelen van de survey waren: \u95 Een verkenning naar de aanwezigheid van ftalaten, gebromeerde vlamvertragers, organotinverbindingen en geperfluoreerde verbindingen in de Noordzee, Waddenzee en Eems-Dollard, en deze in kaart te brengen volgens de begrenzingen van de deelstroomgebieden uit de Kaderrichtlijn Water; \u95 Toetsing van stoffen aan nationale en Europese normen. \u95 Een risico-evaluatie van potentiële (onbekende) probleemstoffen aan de hand van biologische effectmetingen met monsters uit mariene en estuariene watersystemen; waarbij in een later stadium stofidentificaties kunnen worden uitgevoerd; \u95 Het vaststellen van de invloed van stoffen vanuit kustrivieren (via de Noordzee) op het Waddengebied; \u95 Het lokaliseren van mogelijke vervuilingsgradiënten vanuit havens (Delfzijl, Harlingen, Rijnmond en Antwerpen); Geconcludeerd kan worden dat met deze survey een goed beeld gekregen is van de aanwezigheid van ftalaten, gebromeerde vlamvertragers en organotinverbindingen in sediment en zwevend stof in de Nederlandse mariene en estuariene wateren. Verder is een eerste stap genomen om het voorkomen van geperfluoreerde verbindingen te beschrijven. De respons van de sediment- en zwevend stofmonsters in een aantal effectgerichte toetsen met bioassays tonen met name dioxine-achtige toxiciteit en oestrogene activiteit aan. De overige bioassays die toetsen op acute toxiciteit en genotoxiciteit vertonen, met uitzondering van één locatie, geen toxische respons. Voor exacte conclusies per stof wordt er verwezen naar tabellen in het rapport