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ENVIRONMENTAL EXPOSURE ASSESSMENT 2.3.6.2 Photolysis in water In the vast majority of surface water bodies dissolved organic matter is responsible for intensive light attenuation. Thus photolysis processes are normally restricted to the upper zones of water bodies. Indirect processes like photo-sensitisation or reaction with oxygen transients ( 1 O2, OHradicals, ROO-radicals) may significantly contribute to the overall breakdown rate. Photochemical degradation processes in water may only become an important fate process for substances, which are persistent to other degradation processes (e.g. biodegradation and hydrolysis). The experimental determination of the quantum yield (OECD, 1992c) and the UVabsorption spectrum of the substance are prerequisites for estimating the rate of photodegradation in surface water. Due to high seasonal variation in light flux, photochemical degradation should only be based on average EU conditions. Methods to derive average degradation rates which can be used in the model calculation of PECregional are described in Zepp and Cline (1977) and Frank and Klöppfer (1989). The following aspects have to be considered when estimating the photochemical transformation in natural water bodies: • the intensity of the incident light depends on seasonal and geographic conditions and varies within wide ranges. For long-term considerations average values can be used while for short-term exposure an unfavourable solar irradiance (winter season) should be chosen; • in most natural water bodies, the rate of photoreaction is affected by dissolved and suspended matter. Since the concentration of the substance under consideration is normally low compared to the concentration of e.g. dissolved humic acids, the natural constituents absorb by far the larger portion of the sunlight penetrating the water bodies. Using the standard parameters of the regional model (i.e. a water depth of 3 m and a concentration of suspended matter of 15 mg/l), the reduction in light intensity is higher than 98% through the water column. Indirect (sensitised) photochemical reactions should only be included in the overall breakdown rate of water bodies if there is clear evidence that this pathway is not of minor importance compared to other processes and its effectiveness can be quantified. For facilitating the complex calculation of phototransformation processes in natural waters computer programmes have been developed (e.g. ABIWAS by Frank and Klöppfer, 1989; GC-SOLAR by Zepp and Cline, 1977). In practice it will not be possible to easily demonstrate that photodegradation in water is significant in the environment. A value for the half-life for photolysis in water (if known) can be converted to a pseudo firstorder rate constant: Explanation of symbols 50 ln 2 kphoto water = DT50 photowater DT50photowater half-lifetime for photolysis in surface water [d] data set kphotowater first order rate constant for photolysis in surface water [d -1 ] (27)
2.3.6.3 Photochemical reactions in the atmosphere ENVIRONMENTAL EXPOSURE ASSESSMENT Although for some substances direct photolysis may be an important breakdown process, the most effective elimination process in the troposphere for most substances results from reactions with photochemically generated species like OH radicals, ozone and nitrate radicals. The specific first order degradation rate constant of a substance with OH-radicals (kOH in cm 3 .molecule -1 .s -1 ) can either be determined experimentally (OECD, 1992c) or estimated by (Q)SAR-methods and other methods described in Chapter 4 (US EPA, 2002). By relating kOH to the average OH-radical concentration in the atmosphere, the pseudo-first order rate constant in air is determined: Explanation of symbols kdegair = kOH • OHCONCair • 24 • 3600 (28) kOH specific degradation rate constant with OH-radicals [cm 3. molec -1. s -1 ] data set/Ch.4 OHCONCair concentration of OH-radicals in atmosphere [molec . cm -3 ] 5 . 10 5 * kdegair pseudo first order rate constant for degradation in air [d -1 ] *The global annual average OH-radical concentration can be assumed to be 5.10 5 molecules.cm -3 (BUA, 1992). Degradation in the atmosphere is an important process and it is essential to consider whether it can affect the outcome, particularly for high tonnage substances when the regional concentration may be significant. Photodegradation data in the atmosphere must be evaluated with some care. Highly persistent substances may be reported as rapidly degraded in air under environmental conditions where the chemical could be in large amounts in the gas phase. In the real environment, most of the substance may be associated to particles or aerosol and the real atmospheric half-life could be orders of magnitude higher. 2.3.6.4 Biodegradation in a sewage treatment plant The assessment of biodegradability and/or removal in sewage treatment plants should preferably be based on results from tests simulating the conditions in treatment plants. Such a test may be the OECD 303 test (2001b) or equivalent. For further guidance on use of STP simulation test results, see Section 2.3.7. The ready biodegradability tests that are used at the moment are aimed at measuring the ultimate biodegradability of a substance. They do not give a quantitative estimate of the removal percentage in a wastewater treatment plant. Therefore, in order to make use of the biodegradation test results that are available and requested in the present chemical legislation, it is necessary to assign rate constants to the results of the standard tests for use in STP-models. These constants are based on a relatively limited number of empirical data. However, since direct measurements of degradation rates at environmentally relevant concentrations are often not available, a pragmatic solution to this problem has been found. For the purpose of modelling a sewage treatment plant (STP), the rate constants of Table 6 were derived from the biodegradation screening tests. All constants in Table 6 have the following prerequisites: 51
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Institute for Health and Consumer P
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LEGAL NOTICE Neither the European C
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Page 101 and 102: 3 EFFECTS ASSESSMENT 3.1 INTRODUCTI
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Table 16 Assessment factors to deri
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Input data EFFECTS ASSESSMENT The m
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Estimation of the PNEC The PNEC is
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EFFECTS ASSESSMENT biodegradability
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Table 17 Test systems for derivatio
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EFFECTS ASSESSMENT representative o
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In the partitioning method, it is a
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EFFECTS ASSESSMENT As mentioned in
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3.6.2.1 Calculation of PNEC using t
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3.7 EFFECTS ASSESSMENT FOR THE AIR
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EFFECTS ASSESSMENT procedure availa
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EFFECTS ASSESSMENT bioaccumulation
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EFFECTS ASSESSMENT For some chemica
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EFFECTS ASSESSMENT i.e. without enh
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Conversion factors for laboratory a
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EFFECTS ASSESSMENT • relative sen
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EFFECTS ASSESSMENT Earthworms are a
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MARINE RISK ASSESSMENT environment
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MARINE RISK ASSESSMENT of equal rel
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4.2.3.3 Marine biodegradation simul
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MARINE RISK ASSESSMENT In addition
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Explanation of symbols MARINE RISK
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MARINE RISK ASSESSMENT evaluate the
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MARINE RISK ASSESSMENT marine water
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MARINE RISK ASSESSMENT The addition
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MARINE RISK ASSESSMENT Statistical
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MARINE RISK ASSESSMENT sediment, fo
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Table 27 Assessment factors for der
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Table 28 continued Acute and chroni
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MARINE RISK ASSESSMENT of different
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MARINE RISK ASSESSMENT • a measur
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MARINE RISK ASSESSMENT b. the conce
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MARINE RISK ASSESSMENT mechanisms s
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MARINE RISK ASSESSMENT The use of t
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4.4.4.2 Assessment of measured BCF
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MARINE RISK ASSESSMENT required to
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Table 33 Overview of PEC/PNEC ratio
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RISK CHARACTERISATION If a refineme
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Classified dangerous to the Environ
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RISK CHARACTERISATION eaters. This
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6 TESTING STRATEGIES 6.1 INTRODUCTI
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TESTING STRATEGIES Performance of a
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TESTING STRATEGIES Care must be tak
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Algal testing Algae toxicity test (
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TESTING STRATEGIES • long-term te
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Microbial assays TESTING STRATEGIES
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TESTING STRATEGIES A soil bioassay
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REFERENCES Brandes LJ, den Hollande
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REFERENCES IPCS (2000). Framework f
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REFERENCES OECD (1984f). Activated
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REFERENCES Pack S. (1993). A review
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REFERENCES US EPA (1996). Whole Sed
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APPENDIX I volume imported in the E
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APPENDIX I MC IV “Wide dispersive
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APPENDIX I 210 Stage Main category
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APPENDIX I the number of days over
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APPENDIX I Stage Main category Ia I
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APPENDIX I manufacturing of motor c
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APPENDIX I 1. extension of the tabl
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APPENDIX I 220 A-tables Estimates f
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APPENDIX I PRIVATE USE Not applicab
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APPENDIX I IC = 3: CHEMICAL INDUSTR
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APPENDIX I IC = 5: PERSONAL /DOMEST
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APPENDIX I Table A4.1 continued Com
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APPENDIX I IC = 7: LEATHER PROCESSI
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APPENDIX I IC = 9: MINERAL OIL AND
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APPENDIX I WASTE TREATMENT Table A5
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APPENDIX I For the emission factors
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APPENDIX I INDUSTRIAL USE Table A3.
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APPENDIX I INDUSTRIAL USE Table A3.
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APPENDIX I PRIVATE USE Table A4.5 C
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APPENDIX I PRIVATE USE Table A3.16
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APPENDIX I 246 B-tables Estimates f
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APPENDIX I FORMULATION Table B2.2 f
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APPENDIX I IC = 3: CHEMICAL INDUSTR
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APPENDIX I IC = 5: PERSONAL/DOMESTI
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APPENDIX I IC = 7: LEATHER PROCESSI
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APPENDIX I IC = 9: MINERAL OIL AND
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APPENDIX I IC = 11: POLYMERS INDUST
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APPENDIX I IC =13: TEXTILE PROCESSI
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APPENDIX I IC = 16: ENGINEERING IND
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APPENDIX I Appendix I-a: List of sy
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APPENDIX I No. Use Category No. Fun
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APPENDIX I Appendix I-b: List of sy
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APPENDIX I 290 Organic intermediate
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APPENDIX I Other IC/UC combinations
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APPENDIX II Appendix II Fate of che
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APPENDIX II b) Inherent biodegradab
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APPENDIX II log H % removal -4 -3 -
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APPENDIX III Appendix III Evaluatio
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APPENDIX III Field studies In gener
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APPENDIX IV together the mentioned
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290 Table 1 Selected soil test meth
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292 Table 1 continued Selected soil
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298 Table 1 Selected freshwater sed
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APPENDIX VII Appendix VII Toxicity
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APPENDIX VIII collection), and that
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APPENDIX VIII chemicals (see Sectio
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APPENDIX VIII Multimedia fate model
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APPENDIX VIII Monitoring data Metal
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APPENDIX VIII homeostatic regulatio
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APPENDIX IX based on the proportion
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APPENDIX IX Definition of “blocks
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APPENDIX IX these “blocks” will
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APPENDIX IX and PNECs for the “bl
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APPENDIX XI Appendix XI Environment
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APPENDIX XII Appendix XII Connectio
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APPENDIX XII +40% compared to 1992.
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APPENDIX XIII other substance is be
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APPENDIX XIV Taxonomic group No. of
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