Reductive dechlorination of chlorofluorocarbons and hydrochlorofluorocarbons in sewage sludge and aquifer sediment microcosms

The reductive transformation of the 10 most-widely distributed fluorinated volatile compounds and of tetrachloroethene was investigated for up to 177 days under anaerobic conditions in sewage sludge and aquifer sediment slurries. Concentrations of parent compounds and of degradation products were identified by GC-MS. We observed transformation of CFC-11 to HCFC-21 and HCFC-31, of CFC-113 to HCFC-123a, chlorotrifluoroethene and trifluoroethene, of CFC-12 to HCFC-22, of HCFC-141b to HCFC-151b, and of tetrachloroethene to vinyl chloride and ethene. CFC-114, CFC-115, HCFC-142b, HFC-134a and HCFC-22 were not transformed. The results suggest that with both inocula studied here, hydrogenolysis is the primary reductive dechlorination reaction. CFC-113 was the only compound where a dichloro-elimination was observed, leading to the formation of chlorotrifluoroethene as temporal intermediate and to trifluoroethene as end product. The relative reduction rates of chlorofluoromethanes compared reasonably well with theoretical rates calculated based on thermochemical data according to the Marcus theory. Some of the accumulating HCFCs and haloethenes observed in this study are toxic and may be of practical relevance in anaerobic environments.     

Einsatz der Hasse-Diagrammtechnik zur vergleichenden Bewertung von aquatischen Wirkungstests

In eine ?kotoxikologische Bewertung von Schadstoffen müssen die Ergebnisse von Wirkungstests einflie?en. Die Qualit?t der Bewertung im ?kosystemaren Kontext steht und f?llt mit der ?kosystemaren Qualit?t der Tests. In der vorliegenden Arbeit wird eine Bestandsaufnahme aquatischer Wirkungstests (unabh?ngig von bestehenden legislativen Vorgaben) vorgenommen, und es werden die Ergebnisse in einer Tabelle zusammengestellt, die Einsatzbereiche, Anwendbarkeit für mathematische Wirkungsmodellierung und ?kosystemare Relevanz enth?lt. Die hieraus resultierende Tabelle ist schwer zu überblicken und Zusammenh?nge zwischen bestimmten Wirkungstests sind kaum überschaubar. So ist auch eine Einstufung der aquatischen Wirkungstests ohne zus?tzliche mathematische Hilfsmittel schwierig. Hier wird gezeigt, wie anhand der Technik derHasse-Diagramme die Einstufung der Wirkungstests nach ihrer Qualit?t erleichtert wird. Es zeigt sich u.a., da? es keinen Test gibt, der alle Anforderungen gleichzeitig erfüllt. Einerseits gibt es sechs Tests, die — nach ihren Einsatzbereichen und nach ihrer Umsetzbarkeit für die mathematische Modellierung beurteilt — zwar optimal sind, aber keine ?kosystemare Relevanz aufweisen. Andererseits gibt es zwei Tests, die besonders ausgezeichnet sind: Einer (Test 8), der drei Einsatzbereiche aufweist und gleichzeitig sowohl für die mathematische Modellierung geeignet, als auch ?kosystemar relevant ist, und einer, der in zwei anderen Einsatzbereichen positiv beurteilt wurde und noch ?kosystemar interessant ist (Test 54). Es zeigt sich, da? zwischen Tests mit breitem Einsatzbereich und solchen, die ?kosystemar relevant sind, eine Lücke klafft. An evaluation of pollutants depends on the ecotoxicological quality of the effect tests carried out. In this paper a compilation of aquatic tests is given independently on administration needs. The results are summarized in a table listing fields of application, importance for mathematical modelling and ecological relevance. The table includes 55 tests and 8 attributes characterizing each tests The interpretation of the results listed in this table is hardly feasible. An appropriate tool to rank the tests is the technique ofHasse-diagrams. Using this tool it can be deduced that no test fulfills all demands. There are six tests which are optimal with respect to applicability and mathematical modelling. However, they have no relevance for ecosystems. Only two tests are optimal with respect to ecotoxicology, There is still a gap between tests with a wide field of applications and those tests which are relevant with respect to ecotoxicology.     

Aquatic microcosm assessment of the effects of tylosin on Lemna gibba and Myriophyllum spicatum

Tylosin is a macrolide antibiotic commonly used for therapeutic treatment and prophylaxis in livestock. As part of a larger ecotoxicological study, the potential phytotoxic effects of tylosin on the rooted macrophyte Myriophyllum spicatum and the floating macrophyte Lemna gibba were assessed under semi-field conditions using 15 12 000-L microcosms. Concentrations of 0, 10, 30, 300 microg/L (n = 3), and 600, 1000, and 3000 microg/L (n = 1) were evaluated as part of separate ANOVA and regression analyses over an exposure period of 35 days. Fate of tylosin was monitored over time in the highest three treatments, where dissipation followed pseudo-first order kinetics with associated half-lives ranging from 9 to 10 days. For both M. spicatum and L. gibba, tylosin was found to cause no biologically significant changes to any endpoint assessed compared to controls at a Type I error rate of 0.1. However, subsequent power analyses revealed that there was generally insufficient power to declare that there were no significant differences at a Type II error rate of 0.2. Conclusions concerning biologically significant impacts were therefore further assessed based on other statistical criteria including comparisons of percent differences between replicated treatments and controls, minimum significant and minimum detectable differences, and coefficients of variation. Based on these criteria, at an ecological effect size of >20% change, tylosin was concluded to elicit no biologically or ecologically significant toxicity to M. spicatum or L. gibba. A hazard quotient assessment indicated that tylosin poses little risk to either species of macrophyte, with an HQ value calculated to be nearly three orders of magnitude below 1 (0.002).     

An assessment of the sensitivity and reliability of the relative reduction factor approach in the development of 8-hr ozone attainment plans

The updated regulatory framework for demonstrating that future 8-hr ozone (O3) design values will be at or below the National Ambient Air Quality Standards (NAAQS) provides guidelines for the development of a State Implementation Plan (SIP) that includes methods based on photochemical modeling and analytical techniques. One of the suggested approaches is the relative reduction factor (RRF) for estimating the efficacy of emission reductions. In this study, the sensitivity of model-predicted responses towards emission reductions to the choice of meteorology and chemical mechanisms was examined. While the different modeling simulations generally were found to be in agreement on whether predicted future-year design values would be above or below the NAAQS for 8-hr O3 at a majority of the monitoring locations in the eastern United States, differences existed for a small percentage of monitors (approximately 6.4%). Another issue investigated was the ability of the attainment demonstration procedure to predict changes in monitored O3 design values. A retrospective analysis was performed by comparing predicted O3 design values from model simulations using emission estimates for 1996 and 2001 with monitored O3 design values for 2001. Results indicated that an average gross error of approximately 5 ppb was present between modeled and observed design values and that, at approximately 27% of all sites, model-predicted and observed design values disagreed as to whether the design value was above or below the NAAQS. Retrospective analyses such as the one presented in this study can provide valuable insights into the strengths and limitations of modeling and analysis techniques used to predict future design values over time periods of a decade or more for the purpose of developing SIPs. Furthermore, such analyses could provide avenues for improvement and added confidence in the use of the RRF approach for addressing attainment of the NAAQS.     

Partielle Ordnung

Zusammenfassung  Sollen Chemikalien oder Umweltbelastungen ?kotoxikologisch beurteilt werden, so erfordert die Komplexit?t ?kosystemarer Zusammenh?nge, da? Bewertungsverfahren Informationen m?glichst nicht aggregieren soilten. Es gibt keine ?kologisch begründete, allgemein verwendbare Zielfunktion. Die Technik, dennoch beispielsweise Chemikalien miteinander vergleichen zu k?nnen, beruht auf der Verallgemeinerung des Ordnungsbegriffs und der Visualisierungsmethode durch Hasse-Diagramme. Am Beispiel von sechs Chemikalien wird das Verfahren erl?utert und gezeigt, da? ungünstige Einstufungen von Chemikalien verschiedene Ursachen haben k?nnen, die dann auch unterschiedliche ?kotoxikologische Konsequenzen bewirken.      

Nonylphenolic compounds in drinking and surface waters downstream of treated textile and pulp and paper effluents: a survey and preliminary assessment of their potential effects on public health and aquatic life

Eleven drinking water treatment plants, located downstream of textile plants or pulp and paper mills, have been sampled monthly during a year for the analysis of 17 nonylphenol ethoxylates (NP1-17EO) and two nonylphenoxycarboxylic acids (NP1-2EC). At all but one plant, results in the drinking water, for the sum of these 19 substances, range between below detection levels and 6.7 microg/l. Annual means are between 0.02 and 2.8 microg/l. At the other plant, the yearly average concentration is 10.4 microg/l and the monthly maximum is 43.3 microg/l. In the surface (pre-treatment) water, the annual mean concentrations of the 11 plants range between 0.14 and 17.8 microg/l and the recorded instantaneous maximum is 55.3 microg/l. According to Canadian health authorities, drinking water is a negligible route of human exposure to nonylphenolic compounds, even at the highest concentrations found in this study. After transformation of the data into nonylphenol equivalents, about 20% of the surface water samples exceed the Canadian 1 microg/l nonylphenol water quality guideline for the protection of aquatic life. Some results also exceed Québec's 6 microg/l nonylphenol guideline. The efficiency of the plants in removing nonylphenolic compounds from drinking water is highly variable, ranging from 11% to 99%.     

Fate of herbicides and nonylphenol in soil–plant–water systems amended with contaminated sewage sludge

We studied the fate of sludge spiked with ¹⁴C-labelled diuron, glyphosate and nonylphenol applied to the soil by the way of contaminated sewage sludge in the soil-plant-water system. Here we show that the mineralization of the chemicals in mixture is reduced by 40–80% by comparison with a direct soil contamination. The persistence of the chemicals in soils is increased in the presence of sludge. We showed also that the chemicals present in the sludge are mobile and partly transferred to soil leachates and plant seedlings. These results allow postulating that these compounds may induce an ecotoxicological impact on the soil ecosystem.     

Fate of the veterinary medicine ivermectin in soil

We investigated the fate of the drug ivermectin in the soil. We found that ivermectin was transformed solely by photos, leading to the formation of two ivermectin isomers. We indeed failed to detect any biotransformation reaction of the chemical either in the soil or in fungal liquid cultures. According to its limited water solubility, the bioavailability of ivermectin was very low in the soil solution. Here, we show that ivermectin, transferred to the soil from faeces of drug-treated cattle, could be stored for long periods in the soil.     

Age-related foetal sex ratio bias in Iberian red deer (<Emphasis Type="Italic">Cervus elaphus hispanicus</Emphasis>): are male calves too expensive for growing mothers?

Several theories predict offspring biases towards males or females with increasing reproductive resources of the mother to maximize reproductive returns by offspring, or as a result of prohibitive cost of the most expensive sex for young mothers or those in poor condition. This study examines foetus sex of 221 harvested hinds in a food-supplemented game estate for 10 years, according to hind age class (yearlings, subadults or adults), precise age, body mass and condition, and jaw length. A logistic model showed that hinds had a greater probability of bearing a male foetus with increasing age class, but not with any other variable. The greatest bias was found in yearling hinds. After controlling for age class and mass, jaw length was smaller in pregnant compared to non-pregnant yearlings and subadults, which suggests a trade-off between reproduction and growth. The bias towards females in yearlings increased as gestation proceeded, which suggests that the bias might be a result of selective abortion of male foetuses. Although results do not exclude an investment in males to increase number of grand-offspring, they suggest that young hinds may produce daughters as a trade-off between low energetic-cost offspring and their need to grow.Communicated by S. Krackow