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Use of a battery of bioassays to classify hazardous wastes and evaluate their impact int the aquatic environment Benoit Ferrari 1 and Jean–François Ferard 2 1 Institut F.-A. Forel, University of Geneva, Switzerland 2 ESE, CNRS FRE 2635, University of Metz, France.
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Use of a battery of bioassays to classify hazardous wastes and evaluate their impact int the aquatic environment Benoit Ferrari1 and Jean–François Ferard2 1 Institut F.-A. Forel, University of Geneva, Switzerland 2 ESE, CNRS FRE 2635, University of Metz, France curriculumin natural environmental science, 2005
Topics • Hazardous waste legislation – Where are we now in Europe? • Waste hazardous criteria – Summary • Focus on the H14 criterion “Ecotoxic” – The French proposal • Implementation of the methodology – Case study of two solid wastes • Ecotoxicological testing approach • Data interpretation • Waste classification • Interest of the H14 criterion assessment – Case study of two waste deposits • Ecotoxicological approach • Ecological approach curriculumin natural environmental science, 2005
Hazardous waste regulatory aspects Framework Directive on Waste (Council Directive 91/156/EEC) European Waste Catalogue EWC including the Hazardous Waste List HWL (Decision 2000/532/EC) • Definition of waste • Management of waste Hazardous Waste Directive (Council Directive 91/689/EEC) Waste displaying one or more of 14 defined hazardous properties (H1 to H14) listed in Annex III Waste containing any constituents listed in Annex II (C1 to C51) and having one or more hazardous properties (e.g. C25 = asbestos) curriculumin natural environmental science, 2005
The 14 defined hazardous properties • H1 to H3 = physical hazard • H4 to H12 = hazard for human health • H13 = hazard following elimination of waste • H14 = environmental hazard curriculumin natural environmental science, 2005
Assessment of the H14 criterion “Ecotoxic” WASTE Chemicalcharacterization of : Raw waste · OR Leachate · The French proposal (French Ministry of Environment, 1998) NO Ecotoxicological characterization of: C > Limit Values? Raw waste Leachate • C = Concentration • EC = Effective Concentration NON – NO EC < Limit Values? ECOTOXIC WASTE YES YES HAZARDOUS WASTE curriculumin natural environmental science, 2005
Example of two solid wastes Municipal solid waste incinerator bottom ash (BA) EWC/HWL code 19 01 01 Granular (> 4 mm) Slag from a second smelting of lead (2SL) EWC/HWL code 10 04 01 Granular (< 4 mm) Crushing procedure – particle size lower than 4 mm Evaluation of moisture content (drying at 1055°C until constant weight) and Sub–sampling of BA and 2SL for ecotoxicity tests on solid–phase and on eluates curriculumin natural environmental science, 2005
Batch leaching procedure: Eluates European standard EN 12457–2 (2002) Deionized Water 100rpm – 24 hours Liquid/Solid ratio =10 (on dry weight basis) • Settling (15 min) • Centrifugation (10 min – 3500 rpm) Waste (particle size < 4mm) Eluates tested immediately without filtration and pH adjustment curriculumin natural environmental science, 2005
Indirect ecotoxicity testing: Eluates Procedure for testing BA or 2SL eluates • Measurement of light output inhibition of the bioluminescent bacterium Vibrio fischeri (Microtox™)after 30 min (AFNOR T90–320, 1999) = MTX • Measurement endpoint = EC50 Acute tests • Measurement of mobility inhibition of the cladoceran Daphnia magna after 2 d (AFNOR T90–301, 1996) = Dm • Measurement endpoint = EC50 • Measurement of growth inhibition of the algae Pseudokirchneriella subcapitata after 72 h (AFNOR T90–375, 1998) = Ps • Measurement endpoint = EC20 + EC50 Chronic test • Measurement of reproduction inhibition of the cladoceran Ceriodaphnia dubia after 7 d (EPA 600/4_91/002, 1994) = Cd • Measurement endpoint = EC20 +EC50 curriculumin natural environmental science, 2005
Direct ecotoxicity testing: Solid–phase Procedure for testing BA or 2SL • Measurement of growth inhibition of lettuce (Lactuca sativa L.) after 14 d (OECD 208, 1984) = Ls ger (germination), Ls fb (fresh biomass), Ls db (dry biomass) • Measurement endpoint = EC50 Acute test curriculumin natural environmental science, 2005
Experimental data: Toxicity of BA (1) INDIRECT EC50 limit value (Acute test) EC20 limit value (Chronic test) Most sensitive test curriculumin natural environmental science, 2005
Experimental data: Toxicity of BA (2) DIRECT EC50 limit value curriculumin natural environmental science, 2005
Experimental data: Toxicity of 2SL (1) INDIRECT EC50 limit value (Acute test) EC20 limit value (Chronic test) Most sensitive test curriculumin natural environmental science, 2005
Experimental data: Toxicity of 2SL (2) DIRECT EC50 limit value curriculumin natural environmental science, 2005
Classification according to H14 At least 1 bioassay shows a toxicity value inferior to the fixed limit BA HAZARDOUS 3 of the 5 bioassays show toxicity values inferior to the fixed limits 2SL HAZARDOUS curriculumin natural environmental science, 2005
Interest of H14 criterion Prerequisite step… • To select the most suitable way for managing waste in the environment • To warn about the ecotoxicological potential hazard of waste leachates for the aquatic ecosystem • To ensure that unacceptable adverse effects would not arise from storage, treatment, re–use or disposal of waste curriculumin natural environmental science, 2005
Field monitoring: Waste deposits Adapted from Perrodin et al. (2002) • 3 fractions: • P0.5, P1, P2 for BA = cumulated quantities of percolates according to L/S rations of 0.5, 1, 2 • P2.5, P5, P7.5 for 2SL = cumulated quantities of percolates according to L/S rations of 2.5, 5, 7.5 • Tested using bioassays: MTX, Dm, Ps and Cd • And supplying outdoor artificial streams (5 m, 440 L, 3 concentrations + control) colonized by aquatic invertebrate communities after having percolated through permeable subsoil BA 2SL curriculumin natural environmental science, 2005
Field data: Waste deposits (1) BA 2SL Existence of a residual ecotoxicity in the last fraction curriculumin natural environmental science, 2005
Field data: Waste deposits (2) BA 2SL Percolates 10–fold diluted by water before supplying the artificial river Percolates 100–fold diluted by water before supplying the artificial river Significant effects on abundance, richness and emergence of the aquatic invertebrates Perrodin et al. (2002) curriculumin natural environmental science, 2005
Field data: Waste deposits (3) BA 2SL Ecotoxicological approach + Ecological approach Long–term ecotoxic potential hazard of leachates for the aquatic ecosystem if no storage management curriculumin natural environmental science, 2005
References • AFNOR 1996 Water quality – Determination of the inhibition of the mobility of Daphnia magna Straus (Cladocera, Crustacea) – Acute toxicity test. N°T90-301, Association Française de Normalisation, Paris. • AFNOR 1998 Water quality – Determination of water chronic toxicity by growth inhibition of the fresh water algae Pseudokirchneriella subcapitata (Selenastrum capricornutum). N°T90-375, Association Française de Normalisation, Paris. • AFNOR 1999 Water quality – Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) – Part 3: Method using freeze-dried bacteria. N°T90-320-3, Association Française de Normalisation, Paris. • Council Directive 91/156/EEC of 18 March 1991 amending Directive 75/442/EEC on waste. Official Journal L 078, 26/03/1991, Brussels, 32–7. • Council Directive 91/689/EEC of 12 December 1991 on hazardous waste. Official Journal L 377, 31/12/1991, Brussels, 20–7. • EN 12457-2 2002 Characterization of waste – Leaching – Compliance test for leaching of granular waste materials and sludges – Part 2: One-stage batch test at a liquid to solids ratio of 10 l/kg for materials with a particle size below 4 mm (with or without size reduction), CEN/TC292/WG2, European Committee for Standardization, Brussels. • EPA 1994 Short-term methods for estimating the chronic toxicity of effluents and receiving waters to freshwater organisms. EPA 600/4_91/002, Environmental Systems Laboratory, Cincinnati, OH. • French Ministry of Environment 1998 Criteria and methods for the assessment of the ecotoxicity of wastes. French Ministry of Environment/Directorate for Prevention Pollution and Risk ControlJanuary, Paris. • OECD 1984 Guidelines for testing of chemicals: Terrestrial plants, growth test. Document 208, Oragnisation for Economic Co–ordination and Development, Paris. • Perrodin, Y., Gobbey, A., Grelier-Volatier, L., Canivet, V., Fruget, J.F., Gibert, J., Texier, C., Cluzeau, D., Gros, R., Poly, F. and Jocteur–Monrozier, L.2002 Waste ecocompatibility in storage and reuse scenarios: global methodology and detailed presentation of the impact study on the recipient environments. Waste Management, 22, 215-228. curriculumin natural environmental science, 2005