Transcript UNIVERSITE DE METZ Use of a battery of bioassays to classify hazardous wastes and evaluate their impact int the aquatic environment Benoit Ferrari1 and.

UNIVERSITE DE METZ
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
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Topics
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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
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Hazardous waste regulatory aspects
Framework Directive on Waste
(Council Directive 91/156/EEC)
European Waste
Catalogue EWC
including the Hazardous
Waste List HWL
•Definition of waste
•Management of waste
Hazardous Waste Directive
(Decision 2000/532/EC)
(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)
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The 14 defined hazardous properties
H1
Explosive
H2
Oxidizing
H3A
Highly flammable
 H4 to H12 = hazard
for human health
H3B
Flammable
H4
Irritant
 H13 = hazard
following elimination of
waste
H5
Harmful
H6
Toxic
H7
Carcinogenic
 H14 = environmental
hazard
H8
Corrosive
H9
Infectious
H10
Teratogenic/toxic for reproduction
H11
Mutagenic
H12
Substances and preparations which release toxic or very toxic
gases in contact with water, air or an acid
H13
Substances and preparations capable by means, after disposal,
of yielding another substance, e.g. leachate, which
possesses any of the characteristics listed above
H14
Ecotoxic
 H1 to H3 = physical
hazard
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Assessment of the H14 criterion “Ecotoxic”
WASTE
Chemical characterization
of :  Raw waste
 Leachate
The French proposal
(French Ministry of
Environment, 1998)
C > Limit
Values?
NO
•C = Concentration
•EC = Effective Concentration
YES
OR
Ecotoxicological characterization
of: Raw waste
Leachate
EC < Limit
Values?
NO
YES
HAZARDOUS WASTE
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NON–
ECOTOXIC
WASTE
Example of two solid wastes
Municipal solid waste
incinerator bottom ash (BA)
Slag from a second
smelting of lead (2SL)
EWC/HWL code 19 01 01
EWC/HWL code 10 04 01
Granular (> 4 mm)
Granular (< 4 mm)
Crushing procedure – particle
size lower than 4 mm
Evaluation of moisture content (drying at
1055°C until constant weight)
and
Sub–sampling of BA and 2SL for ecotoxicity
tests on solid–phase and on eluates
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Batch leaching procedure: Eluates
European standard EN 12457–2 (2002)
Deionized Water
100rpm – 24 hours
 Settling (15 min)
Liquid/Solid ratio =10
(on dry weight basis)
 Centrifugation (10 min – 3500 rpm)
Waste (particle size < 4mm)
Roller rotating device
Eluates tested
immediately without
filtration and pH
adjustment
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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
Chronic
test
 Measurement endpoint = EC20 + EC50
 Measurement of reproduction inhibition of the cladoceran
Ceriodaphnia dubia after 7 d (EPA 600/4_91/002, 1994) = Cd
 Measurement endpoint = EC20 + EC50
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Direct ecotoxicity testing: Solid–phase
Procedure for testing BA or 2SL
Acute test
 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
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Experimental data: Toxicity of BA (1)
INDIRECT
100
EC50 limit value
% Eluate
10
(Acute test)
1
EC20 limit value
0.1
(Chronic test)
0.01
MTX
Dm
Ps
EC50
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EC20
Cd
Most
sensitive test
Experimental data: Toxicity of BA (2)
% dry waste equivalent
DIRECT
100
EC50 limit value
10
1
0.1
0.01
Ls ger
Ls fb
EC50
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Ls db
Experimental data: Toxicity of 2SL (1)
INDIRECT
100
EC50 limit value
% Eluate
10
(Acute test)
1
EC20 limit value
0.1
(Chronic test)
0.01
MTX
Most
sensitive test
Dm
Ps
EC50
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EC20
Cd
Experimental data: Toxicity of 2SL (2)
% dry waste equivalent
DIRECT
100
EC50 limit value
10
1
0.1
0.01
Ls ger
Ls fb
EC50
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Ls db
Classification according to H14
BA
2SL
At least 1 bioassay shows a
toxicity value inferior to the
fixed limit
HAZARDOUS
3 of the 5 bioassays show
toxicity values inferior to
the fixed limits
HAZARDOUS
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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
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Field monitoring: Waste deposits
Adapted from Perrodin et al. (2002)
BA
•
2SL
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
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Field data: Waste deposits (1)
BA
2SL
100
EC50 (% of percolate)
EC50 (% of percolate)
100
10
1
0.1
0.01
10
1
0.1
0.01
MTX
Dm
Ps
P0.5
P1
Cd
P2
MTX
Dm
P2.5
Existence of a residual
ecotoxicity in the last fraction
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Ps
P5
Cd
P7.5
Field data: Waste deposits (2)
BA
Percolates 10–fold diluted
by water before supplying
the artificial river
2SL
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)
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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
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References
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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 Control January,
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.
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