Long-chain perfluorinated chemicals in digested sewage sludges in Switzerland

This study focused on the occurrence of long-chain perfluorinated chemicals (PFCs) in anaerobically stabilized sewage sludges from 20 municipal WWTPs using current and historic samples to evaluate the levels of PFCs and to identify the relative importance of commercial and industrial sources. A quantitative analytical method was developed based on solvent extraction of the analytes and a LC-MS/MS system. For total perfluoralkyl carboxylates (PFCAs), the concentrations ranged from 14 to 50 μg/kg dry matter. Concentrations of perfluorooctane sulfonic acid (PFOS) ranged from 15 to 600 μg/kg dry matter. In three WWTPs, the PFOS levels were six to nine times higher than the average values measured in the other plants. These elevated PFOS concentrations did not correlate with higher levels of PFCAs, indicating specific additional local sources for PFOS at these WWTPs. Average concentrations in selected samples from the years 1993, 2002, and 2008 did not change significantly.     

Characterization of non-extractable ¹⁴C- and ¹³C-sulfadiazine residues in soil including simultaneous amendment of pig manure

Recently, we reported on soil fate of SDZ residues amended with pig manure treated with 1?C-labeled sulfadiazine 1?C-SDZ). The first objective of the present study was to determine whether this strategy can be substituted by application of 1?C-SDZ to soil. The second objective was to characterize non-extractable SDZ residues by fractionation, size exclusion chromatography (SEC) and solid state 13C-NMR. The fate of 1?C-SDZ was examined for 28 d, using two soils with and without amendment of pig manure. Mineralization of 1?C-SDZ was low; extractable residues decreased to 7-30%. Compared to the previous study, results were similar. 1?C-SDZ derived bound radioactivity was found in HCl-washings, fulvic, humic acids and humin. According to SEC, one bound 1?C portion (70%) co-eluted with fulvic acids (above 910 g mol?1); the other consisted of adsorbed/entrapped 1?C-SDZ. The 13C-SDZ study was performed for 30 d; humic acids were examined by 13C-NMR. A signal (100-150 ppm) was referred to 13C-SDZ. SEC and 13C-NMR demonstrated rapid integration of SDZ into humics.     

über die Notwendigkeit der wirkungsorientierten Analytik in einer umfassenden Wasserforschung

Ohne Zusammenfassung Verantwortliche Herausgeber: Jan Schwarzbauer · Peter Heininger · Evelyn Claus

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Pesticide transport pathways from a sloped Litchi orchard to an adjacent tropical stream as identified by hydrograph separation

This study was performed to identify the transport pathways of pesticides from a sloped litchi ( Sonn.) orchard to a nearby stream based on a three-component hydrograph separation (baseflow, interflow, surface runoff). Dissolved silica and electrical conductivity were chosen as representative tracers. During the study period (30 d), 0.4 and 0.01% of the applied mass of atrazine and chlorpyrifos, respectively, were detected in the stream after 151 mm of rainfall. Baseflow (80-96%) was the dominant hydrological flow component, followed by interflow (3-18%) and surface runoff (1-7%). Despite its small contribution to total discharge, surface runoff was the dominant atrazine transport pathway during the first days after application because pesticide concentrations in the surface runoff flow component declined quickly within several days. Preferential transport with interflow became the dominant pathway of atrazine. Because chlorpyrifos was detected in the stream water only twice, it was not included in the hydrograph separation. A feature of the surface runoff pathway was the coincidence of pesticide and discharge peaks. In contrast, peak concentrations of pesticides transported by interflow occurred during the hydrograph recession phases. Stormflow generation and pesticide transport depended on antecedent rainfall. The combination of high-resolution pesticide concentration measurements with a three-component hydrograph separation has been shown to be a suitable method to identify pesticide transport pathways under tropical conditions.     

Climate Change Adaptation Among Tibetan Pastoralists: Challenges in Enhancing Local Adaptation Through Policy Support

While researchers are aware that a mix of Local Ecological Knowledge (LEK), community-based resource management institutions, and higher-level institutions and policies can facilitate pastoralists' adaptation to climate change, policy makers have been slow to understand these linkages. Two critical issues are to what extent these factors play a role, and how to enhance local adaptation through government support. We investigated these issues through a case study of two pastoral communities on the Tibetan Plateau in China employing an analytical framework to understand local climate adaptation processes. We concluded that LEK and community-based institutions improve adaptation outcomes for Tibetan pastoralists through shaping and mobilizing resource availability to reduce risks. Higher-level institutions and policies contribute by providing resources from outside communities. There are dynamic interrelationships among these factors that can lead to support, conflict, and fragmentation. Government policy could enhance local adaptation through improvement of supportive relationships among these factors. While central government policies allow only limited room for overt integration of local knowledge/institutions, local governments often have some flexibility to buffer conflicts. In addition, government policies to support market-based economic development have greatly benefited adaptation outcomes for pastoralists. Overall, in China, there are still questions over how to create innovative institutions that blend LEK and community-based institutions with government policy making.     

Water mass interaction in the confluence zone of the Daning River and the Yangtze River—a driving force for algal growth in the Three Gorges Reservoir

Increasing eutrophication and algal bloom events in the Yangtze River Three Gorges Reservoir, China, are widely discussed with regard to changed hydrodynamics and nutrient transport and distribution processes. Insights into water exchange and interaction processes between water masses related to large-scale water level fluctuations in the reservoir are crucial to understand water quality and eutrophication dynamics. Therefore, confluence zones of tributaries with the Yangtze River main stream are dedicated key interfaces. In this study, water quality data were recorded in situ and on-line in varying depths with the MINIBAT towed underwater multi-sensor system in the confluence zone of the Daning River and the Yangtze River close to Wushan City during 1 week in August 2011. Geostatistical evaluation of the water quality data was performed, and results were compared to phosphorus contents of selective water samples. The strongly rising water level throughout the measurement period caused Yangtze River water masses to flow upstream into the tributary and supply their higher nutrient and particulate loads into the tributary water body. Rapid algal growth and sedimentation occurred immediately when hydrodynamic conditions in the confluence zone became more serene again. Consequently, water from the Yangtze River main stream can play a key role in providing nutrients to the algal bloom stricken water bodies of its tributaries.     

Assessment of the natural attenuation of chlorinated ethenes in an anaerobic contaminated aquifer in the Bitterfeld/Wolfen area using stable isotope techniques, microcosm studies and molecular biomarkers

The in situ degradation of chlorinated ethenes was assessed in an anaerobic aquifer using stable isotope fractionation approaches, microcosm studies and taxon specific detection of specific dehalogenating groups of bacteria. The aquifer in the Bitterfeld/Wolfen region in Germany contained all chlorinated ethenes, benzene and toluene as contaminants. The concentrations and isotope composition of the chlorinated ethenes indicated biodegradation of the contaminants. Microcosm studies confirmed the presence of in situ microbial communities capable of the complete dechlorination of tetrachloroethene. Taxon specific investigation of the microbial communities indicated the presence of various potential dechlorinating organisms including Dehalococcoides, Desulfuromonas, Desulfitobacterium and Dehalobacter. The integrated approach, using metabolite spectra, molecular marker analysis and isotope studies, provided several lines of evidence for natural attenuation of the chlorinated ethenes.     

Applicability of the bioluminescence inhibition test in the 96-well microplate format for PAH-solutions and elutriates of PAH-contaminated soils

The use of conventional plastic microplates for a miniaturised luminescent bacteria test may result in an underestimation of the toxicity for poorly water soluble highly adsorbing toxicants such as PAHs. In this study, the suitability of microplates for testing elutriates of PAH-contaminated soils was investigated. The LUMIStox test was performed as the standard test in the miniaturised format using contaminated soil elutriates and aqueous solutions of four selected PAHs (viz. naphthalene (NAP), acenaphthene (ACE), fluorene (FLU), and phenanthrene (PHE)). For the aqueous PAH-solutions, we observed reduced light inhibition values for the miniaturised bioassay when using black microplates made of polypropylene (PP) and polystyrene (PS) compared to the standard LUMIStox test. This phenomenon was most likely due to adsorption of toxicants to the microplate surfaces with PAHs of lower water solubility being significantly more affected; however, after minimizing the exposure of samples to plastic surfaces, polystyrene microplates revealed equivalent performance (>80% 'relative' light inhibition) to the standard glass cuvette test system. For soil elutriates, black microplates again exhibited slightly lower light inhibition values while white plates made of PS and Barex resulted in a pronounced overestimation of toxicity for a coloured soil elutriate. In general, microplates were applicable for testing elutriates of PAH-contaminated soils. In cases where samples are coloured or turbid, the application of black microplates is recommended.     

Solid-state conformations and absolute configurations of (+) and (-) alpha-, beta-, and gamma-hexabromocyclododecanes (HBCDs)

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.     

In situ transformations of fine lead oxide particles in different soils

We present a field application of a new in situ technique to analyze phase transformations of fine lead oxide particles (50-100mum) in different soils directly in the field over 18 months. After the first month of exposure to a calcareous sand we found newly precipitated secondary mineral phases on the lead oxide. The samples exposed to two loamy soils (Dystric Cambisol and Luvisol) showed only very few traces of new phases. We identified the new phases as mainly lead-hydroxy carbonates (hydrocerussite). Whereas the results confirm the transformation of lead phases to lead carbonates in calcareous soil, they also show that an easily soluble phase such as PbO may persist in soils virtually unweathered for more than one year. The formation of a weathering crust is therefore not necessarily needed for preservation of easily soluble phases. The use of experimental in situ methods is thus giving new information on contaminant mineral behavior under field conditions.