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Persistent and mobile organic substances (PM substances) are a threat to the quality of our water resources. While screening studies revealed widespread occurrence of many PM substances, rapid trace analytical methods for their quantification in large sample sets are missing. We developed a quick and generic analytical method for highly mobile analytes in surface water, groundwater, and drinking water samples based on enrichment through azeotrope evaporation (4 mL water and 21 mL acetonitrile), supercritical fluid chromatography (SFC) coupled to high-resolution mass spectrometry (HRMS), and quantification using a compound-specific correction factor for apparent recovery. The method was validated using 17 PM substances. Sample preparation recoveries were between 60 and 110% for the vast majority of PM substances. Strong matrix effects (most commonly suppressive) were observed, necessitating a correction for apparent recoveries in quantification. Apparent recoveries were neither concentration dependent nor dependent on the water matrix (surface or drinking water). Method detection and quantification limits were in the single- to double-digit ng L−1 ranges, precision expressed as relative standard deviation of quadruplicate quantifications was on average < 10%, and trueness experiments showed quantitative results within ± 30% of the theoretical value in 77% of quantifications. Application of the method to surface water, groundwater, raw water, and finished drinking water revealed the presence of acesulfame and trifluoromethanesulfonic acid up to 70 and 19 μg L−1, respectively. Melamine, diphenylguanidine, p-dimethylbenzenesulfonic acid, and 4-hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine were found in high ng L−1 concentrations.

Ethane is the second most abundant component of natural gas in addition to methane, and—similar to methane—is chemically unreactive. The biological consumption of ethane under anoxic conditions was suggested by geochemical profiles at marine hydrocarbon seeps 1 – 3 , and through ethane-dependent sulfate reduction in slurries 4 – 7 . Nevertheless, the microorganisms and reactions that catalyse this process have to date remained unknown 8 . Here we describe ethane-oxidizing archaea that were obtained by specific enrichment over ten years, and analyse these archaea using phylogeny-based fluorescence analyses, proteogenomics and metabolite studies. The co-culture, which oxidized ethane completely while reducing sulfate to sulfide, was dominated by an archaeon that we name ‘ Candidatus Argoarchaeum ethanivorans’; other members were sulfate-reducing Deltaproteobacteria. The genome of Ca . Argoarchaeum contains all of the genes that are necessary for a functional methyl-coenzyme M reductase, and all subunits were detected in protein extracts. Accordingly, ethyl-coenzyme M (ethyl-CoM) was identified as an intermediate by liquid chromatography–tandem mass spectrometry. This indicated that Ca . Argoarchaeum initiates ethane oxidation by ethyl-CoM formation, analogous to the recently described butane activation by ‘ Candidatus Syntrophoarchaeum’ 9 . Proteogenomics further suggests that oxidation of intermediary acetyl-CoA to CO 2 occurs through the oxidative Wood–Ljungdahl pathway. The identification of an archaeon that uses ethane (C 2 H 6 ) fills a gap in our knowledge of microorganisms that specifically oxidize members of the homologous alkane series (C n H 2 n +2 ) without oxygen. Detection of phylogenetic and functional gene markers related to those of Ca . Argoarchaeum at deep-sea gas seeps 10 – 12 suggests that archaea that are able to oxidize ethane through ethyl-CoM are widespread members of the local communities fostered by venting gaseous alkanes around these seeps. An archaeon, ‘ Candidatus Argoarchaeum ethanivorans’, which is involved in the oxidation of ethane observed in anoxic marine habitats, is identified and metabolically characterized.

Fish embryos are widely used as an alternative model to study toxicity in vertebrates. Due to their complexity, embryos are believed to more resemble an adult organism than in vitro cellular models. However, concerns have been raised with respect to the embryo's metabolic capacity. We recently identified allyl alcohol, an industrial chemical, to be several orders of magnitude less toxic to zebrafish embryo than to adult zebrafish (embryo LC50 = 478 mg/L vs. fish LC50 = 0.28 mg/L). Reports on mammals have indicated that allyl alcohol requires activation by alcohol dehydrogenases (Adh) to form the highly reactive and toxic metabolite acrolein, which shows similar toxicity in zebrafish embryos and adults. To identify if a limited metabolic capacity of embryos indeed can explain the low allyl alcohol sensitivity of zebrafish embryos, we compared the mRNA expression levels of Adh isoenzymes (adh5, adh8a, adh8b and adhfe1) during embryo development to that in adult fish. The greatest difference between embryo and adult fish was found for adh8a and adh8b expression. Therefore, we hypothesized that these genes might be required for allyl alcohol activation. Microinjection of adh8a, but not adh8b mRNA led to a significant increase of allyl alcohol toxicity in embryos similar to levels reported for adults (LC50 = 0.42 mg/L in adh8a mRNA-injected embryos). Furthermore, GC/MS analysis of adh8a-injected embryos indicated a significant decline of internal allyl alcohol concentrations from 0.23-58 ng/embryo to levels below the limit of detection (< 4.6 µg/L). Injection of neither adh8b nor gfp mRNA had an impact on internal allyl alcohol levels supporting that the increased allyl alcohol toxicity was mediated by an increase in its metabolization. These results underline the necessity to critically consider metabolic activation in the zebrafish embryo. As demonstrated here, mRNA injection is one useful approach to study the role of candidate enzymes involved in metabolization.

A rarely used hydroponic plant root mat filter (PRMF, of 6 m²) and a horizontal subsurface flow constructed wetland (HSSF CW, of 6 m²), operating in continuous flow and discontinuous outflow flushing modes, were investigated for treating sulfate-rich and organic carbon-lean groundwater contaminated with monochlorobenzene (MCB); 1,2-dichlorobenzene (1,2-DCB); 1,4-dichlorobenzene (1,4-DCB); and 2-chlorotoluene. Whereas the mean inflow loads ranged from 1 to 247 mg m⁻²days⁻¹, the range of mean inflow concentrations of the chlorobenzenes recorded over a period of 7 months was within 0.04 and 8 mg L⁻¹. A hydraulic surface loading rate of 30 L m⁻²days⁻¹was obtained in both systems. The mean load removal efficiencies were found to vary between 87 and 93 % in the PRMF after a flow path of 4 m, while the removal efficiencies were found to range between 46 and 70 % and 71 to 73 % in the HSSF CW operating in a continuous flow mode and a discontinuous outflow flushing mode, respectively. Seasonal variations in the removal efficiencies were observed for all low-chlorinated hydrocarbons both in the PRMF and the HSSF CW, whereby the highest removal efficiencies were reached during the summer months. Sulfide formation occurred in the organic carbon-lean groundwater particularly in summer, which is probably due to the plant-derived organic carbon that fostered the microbial dissimilatory sulfate reduction. Higher redox potential in water was observed in the PRMF. In conclusion, the PRMF could be an option for the treatment of water contaminated with compounds which in particular need oxic conditions for their microbial degradation, such as in the case of low-chlorinated benzenes.

The variability of hydrogeochemical conditions can affect groundwater microbial communities and the natural attenuation of organic chemicals in contaminated aquifers. It is suspected that in situ biodegradation in anoxic plumes of chloroethenes depends on the spatial location of the contaminants and the electron donors and acceptors, as well as the patchiness of bacterial populations capable of reductive dechlorination. However, knowledge about the spatial variability of bacterial communities and in situ biodegradation of chloroethenes in aquifers is limited. Here, we show that changes of the bacterial communities, the distribution of putative dechlorinating bacteria and in situ biodegradation at the border of a chloroethenes plume (Bitterfeld, Germany) are related to local hydrogeochemical conditions. Biotic reductive dechlorination occurred along a 50 m vertical gradient, although significant changes of the hydrogeochemistry and contaminant concentrations, bacterial communities and distribution of putative dechlorinating bacteria ( Dehalobacter spp., Desulfitobacterium spp., Dehalococcoides spp., and Geobacter spp.) were observed. The occurrence and variability of in situ biodegradation of chloroethenes were revealed by shifts in the isotope compositions of the chloroethenes along the vertical gradient (δ 13 C ranging from −14.4‰ to −4.4‰). Our results indicate that habitat characteristics were compartmentalized along the vertical gradient and in situ biodegradation occurred with specific reaction conditions at discrete depth. The polyphasic approach that combined geochemical and biomolecular methods with compound-specific analysis enabled to characterize the spatial variability of hydrochemistry, bacterial communities and in situ biodegradation of chloroethenes in a heterogeneous aquifer.

A new approach for headspace sorptive extraction is presented and demonstrated for the determination of 12 chlorobenzenes in water samples. It consists of a silicone tube (15-mm length) arranged around a stainless steel rod. This device is fixed on a septum cap and exposed to the headspace of 50 mL of a salt-saturated water sample. After extraction (60-min optimized extraction time), thermodesorption is carried out by direct insertion of the silicone tube into the thermodesorption-gas chromatography-mass spectrometry system. Desorption of the analytes is performed at 250 °C for 5 min with a gas flow of 50 mL/min. Repeatability (relative standard deviation 5-10%), extraction yields (9-46%), enrichment factors (129-657), and detection limits (0.002-0.012 μg/L) were determined and four real water samples were analyzed with the headspace tube extraction. The results were verified by standard addition. A comparison of headspace tube extraction with other headspace enrichment techniques underlined the high extraction capacity of the proposed method. A big advantage of tube extraction is the low cost of the silicone material. The tubes can be discarded after single use, avoiding carryover problems and cross-contamination. [graphic removed]

Fish embryos are widely used as an alternative model to study toxicity in vertebrates. Due to their complexity, embryos are believed to more resemble an adult organism than in vitro cellular models. However, concerns have been raised with respect to the embryo's metabolic capacity. We recently identified allyl alcohol, an industrial chemical, to be several orders of magnitude less toxic to zebrafish embryo than to adult zebrafish (embryo LC50 = 478 mg/L vs. fish LC50 = 0.28 mg/L). Reports on mammals have indicated that allyl alcohol requires activation by alcohol dehydrogenases (Adh) to form the highly reactive and toxic metabolite acrolein, which shows similar toxicity in zebrafish embryos and adults. To identify if a limited metabolic capacity of embryos indeed can explain the low allyl alcohol sensitivity of zebrafish embryos, we compared the mRNA expression levels of Adh isoenzymes (adh5, adh8a, adh8b and adhfe1) during embryo development to that in adult fish. The greatest difference between embryo and adult fish was found for adh8a and adh8b expression. Therefore, we hypothesized that these genes might be required for allyl alcohol activation. Microinjection of adh8a, but not adh8b mRNA led to a significant increase of allyl alcohol toxicity in embryos similar to levels reported for adults (LC50 = 0.42 mg/L in adh8a mRNA-injected embryos). Furthermore, GC/MS analysis of adh8a-injected embryos indicated a significant decline of internal allyl alcohol concentrations from 0.23-58 ng/embryo to levels below the limit of detection (< 4.6 mu g/L). Injection of neither adh8b nor gfp mRNA had an impact on internal allyl alcohol levels supporting that the increased allyl alcohol toxicity was mediated by an increase in its metabolization. These results underline the necessity to critically consider metabolic activation in the zebrafish embryo. As demonstrated here, mRNA injection is one useful approach to study the role of candidate enzymes involved in metabolization.