Results from a round robin test for the ecotoxicological evaluation of construction products using two leaching tests and an aquatic test battery.

A European round robin test according to ISO 5725-2 was conceptually prepared, realised, and evaluated. The aim was to determine the inter-laboratory variability of the overall process for the ecotoxicological characterization of construction products in eluates and bioassays. To this end, two construction products BAM-G1 (granulate) and HSR-2 (roof sealing sheet), both made of EPDM polymers (rubber), were selected. The granular construction product was eluted in a one stage batch test, the planar product in the Dynamic Surface Leaching test (DSLT). A total of 17 laboratories from 5 countries participated in the round robin test: Germany (12), Austria (2), Belgium (1), Czech Republic (1) and France (1). A test battery of four standardised ecotoxicity tests with algae, daphnia, luminescent bacteria and zebrafish eggs was used. As toxicity measures, EC50 and LID values were calculated. All tests, except the fish egg test, were basically able to demonstrate toxic effects and the level of toxicity. The reproducibility of test results depended on the test specimens and the test organisms. Generally, the variability of the EC50 or LID values increased with the overall level of toxicity. For the very toxic BAM-G1 eluate a relative high variability of CV = 73%-110% was observed for EC50 in all biotests, while for the less toxic HSR-2 eluate the reproducibility of EC50 varied with sensitivity: it was very good (CV = 9.3%) for the daphnia test with the lowest sensitivity, followed by the algae test (CV = 36.4%). The luminescent bacteria test, being the most sensitive bioassay for HSR-2 Eluate, showed the highest variability (CV = 74.8%). When considering the complex overall process the reproducibility of bioassays with eluates from construction products was acceptable.

Hazard property classification of waste according to the recent propositions of the EC using different methods.

Hazard classification of waste is a necessity, but the hazard properties (named "H" and soon "HP") are still not all defined in a practical and operational manner at EU level. Following discussion of subsequent draft proposals from the Commission there is still no final decision. Methods to implement the proposals have recently been proposed: tests methods for physical risks, test batteries for aquatic and terrestrial ecotoxicity, an analytical package for exhaustive determination of organic substances and mineral elements, surrogate methods for the speciation of mineral elements in mineral substances in waste, and calculation methods for human toxicity and ecotoxicity with M factors. In this paper the different proposed methods have been applied to a large assortment of solid and liquid wastes (>100). Data for 45 wastes - documented with extensive chemical analysis and flammability test - were assessed in terms of the different HP criteria and results were compared to LoW for lack of an independent classification. For most waste streams the classification matches with the designation provided in the LoW. This indicates that the criteria used by LoW are similar to the HP limit values. This data set showed HP 14 'Ecotoxic chronic' is the most discriminating HP. All wastes classified as acute ecotoxic are also chronic ecotoxic and the assessment of acute ecotoxicity separately is therefore not needed. The high number of HP 14 classified wastes is due to the very low limit values when stringent M factors are applied to total concentrations (worst case method). With M factor set to 1 the classification method is not sufficiently discriminating between hazardous and non-hazardous materials. The second most frequent hazard is HP 7 'Carcinogenic'. The third most frequent hazard is HP 10 'Toxic for reproduction' and the fourth most frequent hazard is HP 4 "Irritant - skin irritation and eye damage". In a stepwise approach, it seems relevant to assess HP 14 first, then, if the waste is not classified as hazardous, to assess subsequently HP 7, HP 10 and HP 4, and then if still not classified as hazardous, to assess the remaining properties. The elements triggering the HP 14 classification in order of importance are Zn, Cu, Pb, Cr, Cd and Hg. Progress in the speciation of Zn and Cu is essential for HP 14. Organics were quantified by the proposed method (AFNOR XP X30-489) and need no speciation. Organics can contribute significantly to intrinsic toxicity in many waste materials, but they are only of minor importance for the assessment of HP 14 as the metal concentrations are the main HP 14 classifiers. Organic compounds are however responsible for other toxicological characteristics (hormone disturbance, genotoxicity, reprotoxicity…) and shall be taken into account when the waste is not HP 14 classified.

The relevance of physicochemical and biological parameters for setting emission limit values for plants treating complex industrial wastewaters.

The influents of plants treating complex industrial wastewaters from third parties may contain a large variety of often unknown or unidentified potentially harmful substances. The conventional approach of assessing and regulating the effluents of these plants is to set emission limit values for a limited set of physicochemical parameters, such as heavy metals, biological oxygen demand, chemical oxygen demand and adsorbable organic halogen compounds. The objective of this study was to evaluate the relevance of physicochemical parameters for setting emission limit values for such plants based on a comparison of effluent analyses by physicochemical and biological assessment tools. The results show that physicochemical parameters alone are not sufficient to evaluate the effectiveness of the water treatment plants for removing hazardous compounds and to protect the environment. The introduction of toxicity limits and limits for the total bioaccumulation potential should be considered to supplement generic parameters such as chemical oxygen demand and adsorbable organic halogens. A recommendation is made to include toxicity screening as a technique to consider in the determination of best available techniques (BAT) during the upcoming revision of the BAT reference document for the waste treatment industries to provide a more rational basis in decisions on additional treatment steps.

Combining HPLC-GCXGC, GCXGC/ToF-MS, and selected ecotoxicity assays for detailed monitoring of petroleum hydrocarbon degradation in soil and leaching water.

HPLC-GCXGC/FID (high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography with flame-ionization detection) and GCXGC/ToF-MS (comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry) were used to study the biodegradation of petroleum hydrocarbons in soil microcosms during 20 weeks. Two soils were studied: one spiked with fresh diesel and one field sample containing weathered diesel-like oil. Nutrient amended and unamended samples were included. Total petroleum hydrocarbon (TPH) levels in spiked soil decreased from 15,000 to 7,500 mg/kg d.m. and from 12,0O0 to 4,000 mg/kg d.m. in the field soil. Linear alkanes and aromatic hydrocarbons were better biodegradable (>60% degraded) than iso-alkanes; cycloalkanes were least degradable (<40%). Aromatic hydrocarbons up to three rings showed better degradability than n-alkanes. GCXGC/ToF-MS analysis of leaching water showed that initially various oxygenated hydrocarbons were produced. Compound peaks seemed to move up and rightward in the GCXGC chromatograms, indicating that more polar and heavier compounds were formed as biodegradation proceeded. Nutrient amendment can increase TPH removal rates, but had adverse effects on ecotoxicity and leaching potential in our experiment This was explained by observed shifts in the soil microbial community. Ecotoxicity assays showed that residual TPH still inhibited cress (Lepidium sativum) seed germination, but the leaching water was no longer toxic toward luminescent bacteria (Vibrio fischeri).

Estimation of ecotoxicity of petroleum hydrocarbon mixtures in soil based on HPLC-GCXGC analysis.

Detailed HPLC-GCXGC/FID (high performance liquid chromatography followed by comprehensive two-dimensional gas chromatography with flame-ionization detection) analysis of oil-contaminated soils was performed to interpret results of selected acute ecotoxicity assays. For the five ecotoxicity assays tested, plant seed germination and Microtox were selected as most sensitive for evaluating ecotoxicity of the oil in the soil phase and in the leaching water, respectively. The measured toxicity for cress when testing the soil samples did not correspond to TPH concentration in the soil. A detailed chemical composition analysis of the oil contamination using HPLC-GCXGC/FID allows to better predict the ecotoxicological risk and leaching potential of petroleum hydrocarbons in soil. Cress biomass production per plant was well correlated to the total aromatic hydrocarbon concentration (R2=0.79, n=6), while cress seed germination was correlated (R2=0.82, n=6) with total concentration of "highly water-soluble aromatic hydrocarbons" (HSaromatics). The observed ecotoxicity of the leaching water for Microtox-bacteria related well to calculated (based on the HPLC-GCXGC/FID results) petroleum hydrocarbon equilibrium concentrations in water.