ECOSAR model performance with a large test set of industrial chemicals.

The widely used ECOSAR computer programme for QSAR prediction of chemical toxicity towards aquatic organisms was evaluated by using large data sets of industrial chemicals with varying molecular structures. Experimentally derived toxicity data covering acute effects on fish, Daphnia and green algae growth inhibition of in total more than 1,000 randomly selected substances were compared to the prediction results of the ECOSAR programme in order (1) to assess the capability of ECOSAR to correctly classify the chemicals into defined classes of aquatic toxicity according to rules of EU regulation and (2) to determine the number of correct predictions within tolerance factors from 2 to 1,000. Regarding ecotoxicity classification, 65% (fish), 52% (Daphnia) and 49% (algae) of the substances were correctly predicted into the classes "not harmful", "harmful", "toxic" and "very toxic". At all trophic levels about 20% of the chemicals were underestimated in their toxicity. The class of "not harmful" substances (experimental LC/EC(50)>100 mg l(-1)) represents nearly half of the whole data set. The percentages for correct predictions of toxic effects on fish, Daphnia and algae growth inhibition were 69%, 64% and 60%, respectively, when a tolerance factor of 10 was allowed. Focussing on those experimental results which were verified by analytically measured concentrations, the predictability for Daphnia and algae toxicity was improved by approximately three percentage points, whereas for fish no improvement was determined. The calculated correlation coefficients demonstrated poor correlation when the complete data set was taken, but showed good results for some of the ECOSAR chemical classes. The results are discussed in the context of literature data on the performance of ECOSAR and other QSAR models.

Development and evaluation of an online CO(2) evolution test and a multicomponent biodegradation test system.

Well-established biodegradation tests use biogenously evolved carbon dioxide (CO(2)) as an analytical parameter to determine the ultimate biodegradability of substances. A newly developed analytical technique based on the continuous online measurement of conductivity showed its suitability over other techniques. It could be demonstrated that the method met all criteria of established biodegradation tests, gave continuous biodegradation curves, and was more reliable than other tests. In parallel experiments, only small variations in the biodegradation pattern occurred. When comparing the new online CO(2) method with existing CO(2) evolution tests, growth rates and lag periods were similar and only the final degree of biodegradation of aniline was slightly lower. A further test development was the unification and parallel measurement of all three important summary parameters for biodegradation--i.e., CO(2) evolution, determination of the biochemical oxygen demand (BOD), and removal of dissolved organic carbon (DOC)--in a multicomponent biodegradation test system (MCBTS). The practicability of this test method was demonstrated with aniline. This test system had advantages for poorly water-soluble and highly volatile compounds and allowed the determination of the carbon fraction integrated into biomass (heterotrophic yield). The integrated online measurements of CO(2) and BOD systems produced continuous degradation curves, which better met the stringent criteria of ready biodegradability (60% biodegradation in a 10-day window). Furthermore the data could be used to calculate maximal growth rates for the modeling of biodegradation processes.

A critical comparison of respirometric biodegradation tests based on OECD 301 and related test methods.

Biodegradation studies of organic compounds in the aquatic environment gain important information for the final fate of chemicals in the environment. A decisive role play tests for ready biodegradability (OECD 301) and in this context, the respirometric test (OECD 301F). Two different respirometric systems (Oxitop and Sapromat) were compared and in two of ten cases (diethylene glycol and 2-ethylhexylacrylate) differences were observed indicating that the test systems are not always equivalent. For 2-ethylhexylacrylate and cyclohexanone we could not state differences in the extent of biodegradation with a municipal and industrial inoculum whereas for cyclohexanone the degradation rate was faster with a municipal inoculum. Allylthiourea (ATU) proved to be an effective inhibitor of nitrification processes and did not affect the heterotrophic biodegradation activity. Modelling of biodegradation processes could be successfully performed with a first-order and a modified logistic plot.

Laboratory shake flask batch tests can predict field biodegradation of aniline in the Rhine.

The aim of this study was to compare degradation rates of aniline in laboratory shake flask simulation tests with field rates in the river Rhine. The combined events of a low flow situation in the Rhine and residual aniline concentrations in the effluent from the BASF treatment plant in Ludwigshafen temporarily higher than normal, made it possible to monitor aniline at trace concentrations in the river water downstream the wastewater outlet by means of a sensitive GC headspace analytical method. Aniline was analyzed along a downstream gradient and the dilution along the gradient was calculated from measurements of conductivity, sulfate and a non-readily biodegradable substance, 1,4-dioxane. Compensating dilution, field first-order degradation rate constants downstream the discharge of BASF were estimated at 1.8 day(-1) for two different dates with water temperatures of 21.9 and 14.7 degrees C, respectively. This field rate estimate was compared with results from 38 laboratory shake flask batch tests with Rhine water which averaged 1.5 day(-1) at 15 degrees C and 2.0 day(-1) at 20 degrees C. These results indicate that laboratory shake flask batch tests with low concentrations of test substance can be good predictors of degradation rates in natural water bodies--at least as ascertained here for short duration tests with readily degradable compounds among which aniline is a commonly used reference.