Common Implementation Strategy for the Water Framework Directive. Anthracene

Transcription

1 Common Implementation Strategy for the Water Framework Directive Environmental Quality Standards (EQS) Priority Substance No. 2 Anthracene CAS-No Final version Brussels, 31 July 2005

2 Disclaimer This data sheet provides background information on the setting of the Environmental Quality Standard in accordance with Article 16 of the Water Framework Directive (2000/60/EC). The information was compiled, evaluated and used as outlined in the Manual [4] and has been discussed in a consultative process with the Expert Advisory Forum on Priority Substances and the Expert Group on Quality Standards. Furthermore, it has been peer-reviewed by the SCTEE ] [12]. The substance data sheet may, however, not necessarily represent the views of the European Commission. New upcoming information was considered and included up to the date of finalisation of this data sheet. Information becoming available after finalisation of this document will be evaluated in the review process of priority substances according to Art. 16(4) of the Water Framework Directive. If necessary, the Environmental Quality Standard substance data sheets will then be revised in the light of technical and scientific progress.

3 1 Identity of substance Priority Substance No: 2 Anthracene (synonyms: Paranaphthalene, p-naphthalene) CAS-Number: Classification WFD Priority List * : PSR * PS: priority substance; PHS: priority hazardous substance; PSR: priority substance under review according to Decision 2455/ Proposed quality standards 2.1 Overall quality standards Ecosystem Quality Standard Quality Standard rounded values AA-QS all surface waters Comment 0.11 µg/l 0.1 µg/l Overall QS refers to the protection of the pelagic community, see 8.1 & 8.6 MAC-QS (ECO) 0.36 µg/l 0.4 µg/l see section Specific quality standards Protection Objective # Quality Standard Comment Pelagic community (inland waters) Pelagic community (transitional, coastal and territorial waters) Benthic community (freshwater & saltwater sediment) Predators (secondary poisoning) 0.11 µg/l (297.4 µg/kg SPM dry wt) 0.11 µg/l (307.4 µg/kg SPM dry wt) 67.4 µg/kg wet wt ( 310 µg/kg dry wt TGD standard sediment) 33.3 mg/kg prey tissue (wet wt) (corresponding water concentration 3.6 µg/l) see section 8.1 see section 8.1 see section 8.2 see section 8.3 Food uptake by man not required see section 8.4 trigger values not met Abstraction of water intended for human consumption (AWIHC) Water intended for human consumption (WIHC) # 0.2 µg/l A-1 value for ΣPAH in CD 75/440/EEC see section Anthracene is not covered by the limit value set in CD 98/83/EC for the sum of certain PAHs; setting of a DW standard is not required, see section 8.5 If justified by substance properties or data available, QS for the different protection objectives are given independently for freshwater environments, transitional waters or coastal and territorial waters - 1 -

4 3 Classification R-Phrases and Labelling Reference This chemical substance is not classified in the Annex I of Directive 67/548/EEC [11] 4 Physical and chemical properties Property Value Ref. Comments Mol. Weight: g/mol [1] Water Solubility mg/l at 20 o C mg/l at 22 o C mg/l at 25 o C mg/l at 25.3 o C mg/l at 20 o C [8] Vapour Pressure: 8.0 * 10-4 Pa at 25 o C [8] Used in the risk assessment Saltwater, salinity 36.5 o/oo Saltwater, salinity 35 o/oo 5 Environmental fate and partitioning Property Value Ref. Comments Abiotic degradation Hydrolysis Photolysis Biodegradation Partition coefficients Octanol Water The rate constant for the vapourphase reaction of anthracene has been measured to be 1.12 x cm 3 /molecule.sec at 52 deg C. This corresponds to an atmospheric half-life of about 3.4 hours at an atmospheric concentration of 5 x 10 5 hydroxyl radicals per cm 3. Half-life for photolysis in water lies in the range 20 minutes and 4.8 hours depending on the experimental conditions in surface water: 150 days in sediment: 30,000 days in bulk soil: 3,000 days log Pow , [8] [1]: Hydrolysis of anthracene is not expected. Anthracene is photoreactive. The photolysis rate constant for a 3 x 10-7 M aqueous solution of anthracene was measured to be 5.16 x 10-4 /sec. This corresponds to a half-life of 20 min. [8] Calculated according to TGD provisions Anthracene is considered not to fulfilling the 10-day criteria for inherently biodegradable in the risk assessment. This corresponds to an estimated half-life of 150 days in surface water and 80.2 years in sediment. However, experimentally determined half-lives in sediments exhibit a wide range in reported values from days to months. Results indicate that anthracene can be regarded as inherently biodegradable (in the general sense, rather than in relation to specific inherent biodegradability tests). [1] [8]: used in the risk assessment Koc l/kg [1]: Measured values - 2 -

5 Property Value Ref. Comments Koc 71, ,000 [1]: (Jones & Tiller, 1996) Koc (used in PEC calculation) Kp susp (solid-water in SPM) Bioaccumulation Bioconcentration Factor (BCF) Fish Algae Daphnids Molluscs (Macoma baltica) Midge (Chrionomus riparius) l/kg [calculated from foc (0.1) *Koc (555.9)] BCFfish: 1,440 (calculated acc. TGD provisions based on log Pow 4.54) 162 9, , ,915 [8] [8]: Calculation of BCF from log Kow, using the equation of TGD: logbcf fish = 0.85 * logkow Effect data (aquatic environment) The draft of the anthracene RAR (part environment, file R316_0305_env.doc) was discussed at Technical Meeting for the Existing Substances Regulation 793/93 (TM II 03). According to the minutes (file mi_316_tm203_env_dr1.doc), the Rapporteur was asked to: (i) revise the section on effects assessment with the objective to clearly distinguish between the effects of anthracene alone and the combined effects of anthracene and UV irradiation (additional phototoxicity), (ii) to set up an overview-table with the available aquatic effects data, (iii) to re-calculate the PNEC for the aquatic compartment using the relevant data and the appropriate assessment factor, (iv) to include a section on "Non-compartment specific effects relevant for the food chain (secondary poisoning)" in the RAR. However, the above points are not yet or only partially realised in the most recent version of the draft RAR (February 2004 [8] ), especially the section on evaluation of the available aquatic toxicity data, does not yet provide a clear and unequivocal description of tests, exposure conditions, results and conclusions to be drawn. Therefore, the most relevant data from the draft RAR were extracted and supplementary data provided by Member States [5, 6, 7, 13] were added, where deemed appropriate. The toxicity of most PAHs can be greatly enhanced on exposure of a living organism and/or the chemicals to ultraviolet radiation 1. However, evidence exists that this enhancing effect might not be relevant under natural conditions where e.g. humic substances may alleviate the effects of UV radiation by decreasing light penetration, decreasing bioavailability, or increasing rates of photodecomposition. It was therefore agreed by the Technical Meeting on Existing Substances that for the EU risk assessment only studies are considered that were conducted without supplementary UV-exposure. 1 There are two major mechanisms involved in photoinduced toxicity of PAHs: photosensitization and photomodification. In the former, production of singled oxygen leads to cellular damage. In the later, photooxidation of PAHs results in new compounds that are often more toxic then their parent PAHs. [8] - 3 -

6 Therefore, for the purpose of quality standard setting, only those studies are considered for that it was confirmed in the RAR that they were conducted without supplementary exposure to artificial UV-sources (i.e., studies conducted under natural sunlight are not discarded). According to the RAR [8], the water solubility limit of anthracene is approx. 41 µg/l in freshwater and 32 µg/l in saltwater (both 25 C). Therefore toxicity tests with effect concentrations above 45 µg/l are not considered for the purpose of QS setting. In the recent version of the RAR [8] some toxicity studies of algae, invertebrates and vertebrates are listed in overview tables (tables 3.29, 3.30 & 3.33 of [8] ) for that no references are given, that are not described in the corresponding effects assessment sections, and not used for PNEC derivation. These studies are as well not considered for quality standard derivation in this document and therefore not listed in table Summary on endocrine disrupting potential The substance appears not to affect endocrine regulation. Effects on the endocrine system are not mentioned in references [1], [2] or [8]

7 Table 6.1: Summary of relevant anthracene toxicity data for aquatic species. Full references are listed in the RAR [8] a) Acute and chronic toxicity to aquatic plants Species Exposure duration Endpoint Effect Concentration (µg/l) Reference Freshwater alga (Chlorella pyrenoidosa) Freshwater alga (Selenastrum capricornutum) Freshwater alga (Selenastrum capricornutum) 24 hrs exposure in the dark, then 3 hrs UV-B irradiation UV-B 310nm, intensity in laboratory test was 130µW/cm 2 and in field test µW/cm 2 NOEC 22 hrs EC10 (exposed to UV) 22 hrs EC50 (exposed to UV) b) Acute and chronic toxicity to aquatic invertebrates Inhibition of growth Inhibition of growth Inhibition of growth 3 30 Oris et al., ( µw/cm² UV-A) ( µw/cm² UV-A) Gala and Giesy, 1992 Gala and Giesy, 1992 Species Exposure duration Endpoint Effect Concentration (µg/l) Reference Comments Invertebrates Waterflea (Daphnia magna) Paper pondshell (Utterbackia imbecillis) Brine shrimp (Artemia salina) Culicid mosquito larvae Waterflea (Daphnia magna) Brine shrimp (Artemia salina) Waterflea (Daphnia magna) Waterflea (Daphnia magna) Waterflea (Daphnia magna) 14 minutes EC 50 Immobilisat ion 24 hrs LC 50 Survival 1.93 Weinstein, J. E. et al hrs incubation in the dark, then 1 hr UV irradiation LC 50 Survival after 1 h UV irradiation 1.2 Oris et al (1984) exposed to natural sunlight Study not considered valid in RAR [8] 20 Kagan et al (1985) 24 hrs LC Oris, J. T. et al., hrs LC Abernethy et al., hrs LC 50 >50 Abernethy et al., 1986 Incubation in the dark for 1 hr, than 1 hr UV irradiation EC 50 Survival after 1 h UV irradiation 20 Kagan et al (1985) 21 days NOEC 2.2 Foran J.A. et al., days NOEC Foran J.A. et al., 1991 exposed to UV-A, 70 µw/cm² exposed to UV with max. intensity around 350 nm Study not considered valid for PNEC derivation exposure concentrations not measured exposed to UV intensity 5-times less than summer max. in Michigan Exposure in the dark Exposure in the dark Effect concentration above WS of substance exposed to UV with max. intsity around 350 nm Study not considered valid for PNEC derivation by MS- Rapporteur exposure concentrations not measured without UV exposure exposed to UV Valid studies not considered in RAR: Waterflea (Daphnia magna) Pacific oyster (Crassostrea gigas) Green sea urchin (Psammechinus miliaris) 21 days LOEC NOEC 48 hrs NOEC EC10 EC50 48 hrs NOEC EC10 EC50 reproductio n Larval development Larval development 2.1 (1.1) Holst and Giesy 1989 without UV exposure NOEC = LOEC/2 (significant 5.4% reduction in no of offspring) [13] without UV exposure [13] without UV exposure - 5 -

8 Table 6.1: (continued) Summary of relevant anthracene toxicity data for aquatic species. Full references are listed in the RAR [8] c) Acute and prolonged toxicity to fish and other aquatic vertebrates Species Exposure duration Endpoint Effect Concentration (µg/l) Reference Comments Fish Bluegill sunfish 96 hrs LC50 Survival Oris, J.T. et al., 1984 Bluegill sunfish 96 hrs LC Oris, T. & Giesy, J.P.Jr, 1985 sunlight Fathead 4 days post NOEC 6 Tilghman Hall minnow hatch and Oris, 1991 Fathead minnow Fathead minnow Amphibians 4 days post hatch 4 days post hatch LOEC NOEC Deformities, hatching success Deformities, hatching success survival of larvae 12 Tilghman Hall and Oris, Tilghman Hall and Oris, 1991 Rana pipiens 5 hrs LC Kagan et al., 1984 exposed to UV intensity corresponding to 60 cm depth in a northern temperate lake exposed to UV simulated Adult minnows exposed for 2-11 wk to anthracene but not to simulated sunlight, eggs collected daily, development of eggs observed until 4 days post hatch eggs exposed to simulated sunlight eggs exposed to simulated sunlight eggs/larvae not exposed to simulated sunlight phototoxicity 7 Effect data (human health) Summary human health [1] From repeated dose experiments in animals, a human oral NOAEL of 0.3 mg/kg/day has been calculated: Administration of anthracene to rats in the diet for up to 550 days, at a daily dose of up to 50 mg/kg, did not reveal any adverse effects. Thus the NOAEL for rats can be taken as greater than 50 mg/kg/day. Daily administration of anthracene by gavage to mice for at least 90 days, at doses up to 1000 mg/kg/day, did not result in any treatment-related effects, indicating that the NOAEL for subchronic (90 day) exposure of mice is greater than 1000 mg/kg/day. Based on this, a LOAEL cannot be directly defined. Taking 1000 mg/kg/day as a NOAEL for mice, and including a 3000 safety factor (10 for interspecies extrapolation, 10 for intraspecies variability and 30 for the use of subchronic data for chronic NOAEL derivation, and for the absence of reproductive and developmental toxicity data, a human NOAEL level of 0.3 mg/kg/day can be calculated (47). On the other hand, taking 50 mg/kg/day as a NOAEL for chronic exposure of rats and including a safety factor of 100 (10 for interspecies extrapolation and 10 for intraspecies variability) would lead to a human NOAEL of 0.5 mg/kg/day, in reasonable agreement with the above value. No data for the evaluation of reproductive or developmental toxicity are available. The limited evidence that anthracene may exert toxic effects on the developing embryo means that such lack of such information is an important hurdle in the risk assessment of anthracene. On the other hand, - 6 -

9 although human data are not available, mutagenicity and carcinogenicity seem unlikely to constitute a significant hazard in view of the lack of corresponding activity in in vitro systems and animals, respectively. Exposure of the general population via the environment may occur via inhalation of polluted air, drinking water and the diet. In addition, subgroups of workers may be exposed to anthracene in their occupational environment as a result of incomplete combustion of fossil fuels. As regards oral exposure, drinking water would be expected to contribute about 60 ng to the daily intake of anthracene, taking the typical concentrations as 30 ng/l, while, based on the available measured data on anthracene-contaminated foodstuffs, diet may contribute a few hundreds of ng. Adding to this oral intake the systemic intake arising via inhalation of contaminated air, the total human daily intake of anthracene appears likely to be well under 1 µg/day, or 14 ng/kg/day. This is more than 5 orders of magnitude lower than the NOAEL for chronic oral exposure and can be considered negligible. Table 7.1: Summary of anthracene toxicity data [1] end-point animals humans (observed or derived) repeated dose toxicity mouse (sub-chronic), NOAEL: 1,000 NOAEL, oral: 0.3 mg/kg/day mg/kg/day rat (chronic), NOAEL: 50 mg/kg/day Mutagenicity in vitro and in vivo: negative no information Carcinogenicity rat, mouse: negative no information reproductive toxicity no information no information developmental toxicity no information no information - 7 -

10 8. Calculation of quality standards 8.1 Quality standards for water Freshwater In the current draft of the RAR [8], a PNEC aqua of 0.12 µg/l is suggested based on an assessment factor of 10 on the NOEC of 1.2 µg/l for Lepomis macrochirus (Oris and Giesy, 1986 [9] ) as the lowest value. However, this NOEC is an inappropriate starting point for two reasons: 1. This NOEC is an extrapolated figure based on acute toxicity data from short term experiments investigating the combined effects of anthracene and UV-radiation. Beside the fact that this NOEC is not a real NOEC obtained in a standard long-term test, it is based on the phototoxic effects of anthracencene in the presence of UV-light. It was however decided by the Technical Meeting on Existing Substances that for the EU risk assessment only studies shall be considered that were conducted without supplementary UV-exposure because evidence exists that this enhancing effect might not be relevant under natural conditions where e.g. humic substances may alleviate the effects of UV radiation by decreasing light penetration, decreasing bioavailability, or increasing rates of photodecomposition. 2. Objective of the study was to examine rates of phototoxic damage and physiologic repair in relation to the duration of daily photoperiods at a certain UV-intensity 2. The NOEC of 1.2 µg/l was extrapolated for a 24 h light : 0 h darkness period, which has no relevance for most of the territory of the EU. Extrapolated NOECs ( LC1 values in the study) for 18:6, 12:12 and 6:12 hours light : darkness periods under these irradiation conditions are 3.2, 6.9 and 13.5 µg/l, respectively. The lowest relevant long-term NOEC in the data set of the draft RAR is the Daphnia magna 21d NOEC of 2.2 µg anthracene/l observed in the absence of UV exposure (Foran et al. 1991, see table 6.1b). However, there is another apparently valid 3 Daphnia magna 21d LOEC of 2.1 µg/l available that is not considered in the draft RAR (Holst and Giesy 1989 [10] ). Number of neonates in relation to control is 5.4% at the LOEC (p< 0.05). Hence, according to the provisions of the TGD [3], a NOEC can be derived by dividing the LOEC by 2: NOEC 1.1 µg/l 4. In addition to the long-term NOECs for invertebrates, a long-term NOEC fish for egg and larvae development after 2-11 week exposure of adult fathead minnows in the absence of supplementary UV-irradiation is available (cf. table 6.1c). But for algae, no NOEC/EC10 obtained in a test of standard duration (72h) is available (cf tab 6.1a). The available NOEC/EC10 algae values however indicate that algae are not the most sensitive species although in all studies supplementary UVradiation - known to significantly increase anthracene toxicity - was applied. Therefore, it is deemed reasonable to assume that algae toxicity tests of 72 h duration in the absence of supplementary UV-irradiation would not result in lower NOECs than those obtained for h anthracene exposure plus UV-irradiation. Consequently, an assessment factor of 10 may suffice to derive the quality standard in accordance with the TGD provisions (long-term NOEC data available for at least the 3 trophic levels algae, crustaceans and fish) µw/cm² UV-B (310 ± 34 nm) and 100 µw/cm² UV-A (365 ± 36 nm) 3 Full description of study design, exposure conditions as well as analytical and statistical methods applied available. Test conducted in the absence of UV radiation. Clear concentration effect relationship shown 4 This value is also used in [5] - 8 -

11 The QS freshwater is derived on the basis of the lowest NOEC (1.1 µg/l) and an AF of 10: QS freshwater = NOEC (1.1 µg/l) / AF (10) = 0.11 µg anthracene/l In the RAR [8] it is stated that anthracene is expected to adsorb to suspended solids and sediment in water. But the Kp susp (solid water partition coefficient in SPM [ Koc * foc SPM] ) is only calculated as l/kg based on a Koc of and the TGD standard weight fraction of organic carbon (foc) in suspended solids of 0.1 [3]. It is not explained in the RAR on which basis the Koc is derived or calculated. Measured values cited in the RAR range from 2,600 to 8,600 for soils and 71, ,000 for humic acids in aqueous soils. In a report of the Dutch RIVM dealing with the derivation of EQS for PAH [5] the experimental average log Koc of anthracene is calculated as 4.73 (finally, a calculated value of 4.45 was used in the RIVM report for assessment) and in a study conducted on behalf of the German LAWA [6] for the derivation of quality targets sediment Koc.s of 14,000 (log 4.14) and 26,000 (log 4.41) are cited. As the Koc used in the RAR [8] is apparently to low, it is proposed to use the calculated log Koc of the RIVM report (4.45), which is very close to the higher sediment log Koc (4.41) cited in the LAWA study. Log Koc 4.45 corresponds to Koc Thus, the Kp susp is calculated as follows according to the provisions of the TGD: Kp susp [l/kg] = foc (0.1) * Koc (28184) = 2818 As the log Kp susp is >3, the QS for water is additionally given as concentration in SPM of the TGD standard water (15mg/l SPM (dry weight), see section of the final report [4] ): QS freshwater [0.11 µg/l] QS SPM.freshwat = = µg/kg SPM (dry wt) C SPM [15 mg/l] * 10-6 [kg/mg] + Kp -1 [(2818 l/kg) -1 ] Transitional, coastal and territorial waters The TGD assessment factor method as proposed for the marine effects assessment is used (section 4.3 in chapter 3b of volume II of the TGD [3] ). In addition to the freshwater toxicity data, valid data for 2 additional marine taxonomic groups have been provided in a report submitted by the Netherlands in 2005 [13]. These toxicity data referring to the larval development of the echinoderm Psammechinus miliaris and the mollusc Crassostrea gigas indicate that these marine groups are not more sensitive towards anthracene than freshwater organisms. Thus, given the data available, an AF of 10 on the lowest NOEC is appropriate according to the provisions of the TGD for marine effects assessment. QS saltwater = NOEC (1.1 µg/l) / AF (10) = 0.11 µg anthracene/l As the log Kp Water-SPM is >3, the QS for water is additionally given as concentration in SPM. The SPM concentration in marine waters is significantly lower than in freshwater (discussed in the context of the marine risk assessment: approx. 3 mg/l as standard concentration). Therefore, the quality standard is, as an example, also calculated for a SPM concentration of 3 mg/l: QS wat [0.11 µg/l] QS SPM.saltwat = = µg/kg SPM dry wt C SPM [3 mg/l] * 10-6 [kg/mg] + Kp -1 [(2818 l/kg) -1 ] - 9 -

12 Quality standard accounting for transient concentration peaks (MAC-QS) In the RAR [8], there is only one acute toxicity test available that was conducted without supplementary UV-irradiation and where the resulting LEC50 is not higher than the water solubility of the substance (see table 6.1a-c). This is the Daphnia magna 48 h LC50 of 36 µg/l (Abernethy et al. 1986). The Netherlands provided two other tests with the marine species Crassostrea gigas and Psammechinus miliaris [13]. However, in both tests the results are unbounded (no effects seen at highest concentration tested, see table 6.1b) and therefore cannot be used for EQS derivation. It is suggested to derive the MAC-QS on the basis of the LC50 of 36 µg/l and the guidance given in the TGD on the effects assessment for intermittent releases (section of part II of [3] ). The standard assessment factor of 100 may be used because of the uncertainty associated with the availability of only 3 valid short-term test results. MAC-QS = LC50 (36 µg/l) / AF (100) = 0.36 µg anthracene / l 8.2 Quality standard for sediment Anthracene is expected to adsorb to suspended solids and sediment in water [8]. The log Kp susp of anthracene is >3 and thus the derivation of a QS sediment is required (see table 1a in [4] ). Toxicity data for sediment dwelling organisms are not available. Therefore, according to the TGD [3], the PNEC sediment may be calculated using the equilibrium partitioning method in the absence of ecotoxicological data for sediment-dwelling organisms. The approach only considers uptake via the water phase. However, uptake may also occur via other exposure pathways like ingestion of sediment and direct contact with sediment but for substances with a log Kow < 5 uptake via ingestion or contact with sediment is considered negligible 3]. As the log Kow of anthracene used in the risk assessment is 4.54 [8] the additional exposure routes need not to be considered in the calculation of QS sediment from the QS water. Kp SPM-water [704.6 m 3 /m 3 ] QS sed [mg.kg -1 ] = * 1000 * QS water [mg/l] bulk density SPM.wet [1150 kg/m 3 ] with: K SPM-water 5 = m 3 /m 3 bulk density SPM.wet 1150 kg.m -3 QS water (freshwater & saltwater) = mg/l 1000 = conversion factor m 3 /kg to l/kg The TGD defines wet SPM as 90% vol/vol water (density 1 kg/l) and 10% vol/vol solids (density 2.5 kg/l), thus giving a wet density of (0.9 1) + ( ) = 1.15 kg/l. The dry weight of solids is therefore 0.25 kg (per litre wet SPM) and thus the wet:dry ratio is 1.15/0.25 = 4.6. This results in the following quality standards for freshwater and marine sediments (wet and dry weight): QS sediment 67.4 µg/kg (wet wt) 310 µg/kg (dry wt) Standards derived by the EP-method should be considered as tentative for the reasons given above. In order to refine the quality standards calculated for the sediment compartment, results of tests conducted with benthic organisms using spiked sediment are required. 5 According to section of the TGD [3] : K SPM-water = Fsolid SPM (0.1 m 3 /m 3 ) * foc SPM (0.1 kg/kg) * Koc (28184 l/kg) / 1000 * RHOsolid (2500 kg/m 3 )

13 8.3 Secondary poisoning of top predators As the trigger value for the derivation of a quality standard referring to secondary poisoning of top predators is met (BCF 100), the calculation of the respective standard is required (see table 1a of the Manual [4] ). A NOAEL of 50 mg/kg bw.d referring to chronic oral toxicity in rat was identified in the risk assessment [1] (see table 7.1). From this NOAEL a PNEC oral is calculated according to the procedure described in section of the Manual [4] (based on section of the TGD [3] ). NOEC oral = NOAEL mammal.chronic (5 * 10-5 kg/kg bw.d) * CONV mammal (20 kg bw.d/kg food) PNEC oral = NOEC oral (1000 (mg/ kg food) / AF (30) = 33.3 mg/kg food with: CONF mammal : conversion factor from NOAEL to NOEC for the species (20 for rat >6 weeks) AF: assessment factor for the extrapolation to PNEC, depending on duration of test (30 for chronic study with mammals) Thus, the QS secpois.biota is: QS secpois.biota = 33.3 mg anthracene / kg food (prey tissue; wet weight) Anthracene has been shown to bioconcentrate. The highest BCF fish mentioned in the RAR [8] (9370) is used to calculate the concentration in water that corresponds to the QS biota. secpois. Bioconcentration in fish is higher than observed in crustaceans and molluscs. No information is available on observations regarding biomagnification. According to the provisions given in the TGD [3] with regard to the assessment of secondary poisoning, biomagnification factors (BMF) should be taken into account for the calculation of the PEC oral of top predators. The use of default BMFs as proposed in the TGD is recommended, if the bioconcentration factor of the substance concerned exceeds certain levels and measured BMFs are not available (see sections of the Manual [4] or sections and of the TGD [3] for details). However, relatively low levels of PAH accumulation were found for vertebrates due to mixed function oxidase (MFO) enzym systems which enable them to metabolize PAHs and excrete the metabolites. Moreover, apparently no information exists on PAH accumulation in bird and mammal species higher in the food chain [5]. In the draft RAR [2] secondary poisoning is not explicitly addressed but it is mentioned that accumulation in food is not considered to be high. Therefore, it seems not justified to use default BMF values for the calculation of the quality standard referring to secondary poisoning. The QS secpois.water is calculated as follows: QS secpois.water = QS secpois.biota (33.3 [mg/kg]) * BCF -1 ((9370 [kg/l]) -1 ) = 3.6 µg anthracene /l Thus, the protection of the pelagic community does require by far lower QS than the protection of top predators from secondary poisoning (i.e. top predators are protected by the QS for freshwater or saltwater)

14 8.4 Quality Standard referring to food uptake by humans As the trigger values according to table 1b of the Manual for the derivation of a quality standard referring to food uptake by humans are not met, the calculation of the respective standard is not required. The lowest relevant NOAEL oral identified in the risk assessment [1] is 0.3 mg/kg bw d -1 for repeated dose toxicity in humans ( 21 mg.d -1 for a person with 70 kg body weight as relevant threshold level). In the Manual (section ) [4] it is suggested that the relevant threshold level may not be exhausted for more than 10% by consumption of food originating from aquatic sources (i.e. 2.1 mg.d -1 ). The average fish consumption of an EU citizen is 115 g.d -1 (TGD [3] ). Thus, 115 g fish (or seafood) must not contain more than 2.1 mg anthracene. 2.1 mg anthracene QS hh.food = * 1000 g = mg anthracene / kg seafood 115g seafood consumption In the TGD approach for the assessment of secondary poisoning (see section of the Manual [4] ) it is foreseen to consider bioconcentration and biomagnification as relevant factors affecting body burdens and the PEC, respectively. If no information on BMF values is available, it is proposed in the TGD to use default BMFs for substances with a BCF fish >2000. The BCF fish for anthracene is [8]. Thus, normally the application of default BMFs would be required, as no information on observed BMFs is available. However, according to the RAR [1] the concentration in food is not considered as high. The reason for this might be due to the fact that fish, birds and mammals have mixed function oxidase (MFO) enzyme systems which enable them to metabolize PAHs and excrete the metabolites [5]. In derogation from the TGD approach it is therefore suggested to neglect the possibility of biomagnification and to take only the BCFfish into account for the calculation of the water concentration corresponding to the QS hh.food : [mg/kg] QS hh.food.water = = 1.9 µg anthracene / l BCF (9370 [l/kg]) Thus, the quality standard required to protect human health from adverse effects due to ingestion of food originating from aquatic environments is not as low as the respective standards required for the protection of freshwater and saltwater communities. 8.5 Quality Standard for drinking water abstraction The "A1 value" for PAHs (sum) set in the context of Council Directive 75/440/EEC is 0.2 µg/l. Anthracene is not covered by the limit value set in Council Directive 98/83/EC for the sum of certain PAHs. Therefore, a provisional drinking water quality standard is calculated based on the recommendations given in the TGD [3]. The lowest relevant NOAEL oral identified in the risk assessment [1] is 0.3 mg/kg bw d -1 for humans. The provisional quality standard for drinking water is calculated with the provision that uptake by drinking water should in any case not exceed 10% of the threshold level for human health [3]

15 0.1*TL HH * BW QS DW.provisional = = 1.05 mg anthracene /l Uptake DW with: QS DW.provisional provisional quality standard for drinking water (mg/l) TL HH threshold level for human health (0.3 mg anthracene /kg bw per day) BW body weight (70 kg) Uptake DW uptake drinking water (2 l per day) The provisional drinking water quality standard is by far higher than the proposed quality standard for the protection of the pelagic community in freshwater and as well higher than the water solubility limit of anthracene. It is therefore not necessary to set a quality standard referring to the possibility of drinking water abstraction as objective of protection. 8.6 Overall quality standard For polyaromatic hydrocarbons, the SCTEE recommended to use a group approach both for the quality standards referring to ecological protection objectives as well as to human health [12]. However, with the current scientific knowledge on environmental behaviour, fate and effects it is not possible to develop such an approach. Therefore, although the proposal of the SCTEE is in principle supported, the quality standard proposals must at present be based on information / data available for the individual PAH-compounds. Due to lack of data for sediment dwelling organisms the quality standards for sediment are only a transformation of the freshwater or saltwater standards. As anthracene is known to accumulate in the sediment, the tentative standard derived by the equilibrium partitioning method should be reviewed as soon as valid effects data for sediment dwelling organisms become available. Protection of the pelagic community is the objective of protection that requires the lowest levels of anthracene

16 9 References [1] European Union Risk Assessment Report: Anthracene (CAS No: ). Part environment draft of June 2001 (file R316_0106_env1) and part human health draft of 21 July 2000 (file R316_0007_env_hh). Actual drafts or the final report may be available at the internet site of the European Chemicals Bureau: tick ESIS button, then enter CAS or EINECS number of substance [2] COM(2001)262 final: Communication from the Commission to the Council and the European Parliament on the implementation of the Community Strategy for Endocrine Disrupters a range of substances suspected of interfering with the hormone system of humans and wildlife. (Table 2: substances with evidence of ED or evidence of potential ED which are neither restricted nor currently being addressed under existing Community legislation. Table 3: Substances with evidence of ED or evidence of potential ED, already regulated or being addressed under existing legislation. Table 4: Substances with insufficient data in the BKH Report) [3] Technical Guidance Document on Risk Assessment in Support of Commission Directive 93/67/EEC on Risk Assessment for New Notified Substances and Commission Regulation (EC) No 1488/94 on Risk Assessment for Existing Substances and Directive 98/8/EC of the European Parliament and the Council Concerning the placing of biocidal products on the market. Part II. European Commission Joint Research Centre, EUR EN/2, European Communities Available at the internet-site of the European Chemicals Bureau: [4] Manual of the Methodological Framework Used to Derive Environmental Quality Standards for Priority Substances of the Water Framework Directive. Peter Lepper, Fraunhofer-Institute Molecular Biology and Applied Ecology, 15 November Available at the internet-site of the European Commission: [5] Kalf, DF et al., 1995: Integrated Environmental Quality Objectives for Polycyclic Aromatic Hydrocarbons [PAHs). National Institute of Public Health and the Environment, Bilthoven, The Netherlands. RIVM Report no [6] Frimmel, FH et al., 2001: Ableitung von Qualitätszielen für Kandidatenstoffe der prioritären Liste für die EU-Wasserrahmenrichtlinie. Projektbericht zum Forschungsvorhaben. [7] Vindimian et al : Complément au SEQ-Eau : méthode de détermination des seuils de qualité pour les substances génotoxiques. Rapport final. Client: Agence de l eau Rhin Meuse. [8] Environmental risk assessment report. Anthracene, CAS No: , EINECS No: Rapporteur: Greece. Draft of February Actual drafts or the final report may be available at the internet site of the European Chemicals Bureau: tick ESIS button, then enter CAS or EINECS number of substance. [9] Oris, JT, JP Giesy Jr. ; 1986 : Photoinduced toxicity of anthracene to juvenile Bluegill Sunfish (Lepomis macrochirus): Photoperiod effects and predictive hazard evaluation. Environ Toxicol Chem 5(8): [10] Holst, LL and JP Giesy ; 1989 : Chronic effects of the photoenhanced toxicity of anthracene on Daphnia magna reproduction. Environ Toxicol Chemistry 8: [11] ESIS: European Chemicals Bureau ESIS (European Substances Information System), July tick ESIS button, then enter CAS or EINECS number of substance. [12] Opinion of the Scientific Committee on Toxicity, Ecotoxicity and the Environment (SCTEE) on The Setting of Environmental Quality Standards for the Priority Substances included in Annex X of Directive 2000/60/EC in Accordance with Article 16 thereof, adopted by the CSTEE during the 43 rd plenary meeting of 28 May 2004, European Commission Health & Consumer Protection Directorate General, Brussels. [13] AquaSense (2005). Toxicity tests with priority substances in the Water Framework Directive. Sponsor: Institute for Inland Water Management and Waste Water Treatment (RIZA). Report number: