Influence of vegetation and substrate type on removal of emerging organic contaminants and microbial dynamics in horizontal subsurface constructed wetlands.

Constructed wetlands (CWs) offer an efficient alternative technology for removing emerging organic contaminants (EOCs) from wastewater. Optimizing CW performance requires understanding the impact of CW configuration on EOC removal and microbial community dynamics. This study investigated EOC removal and microbial communities in horizontal subsurface flow (HSSF) CWs over a 26-month operational period. Comparison between tuff-filled and gravel-filled CWs highlighted the superior EOC removal in tuff-filled CWs during extended operation, likely caused by the larger surface area of the tuff substrate fostering microbial growth, sorption, and biodegradation. Removal of partially positively charged EOCs, like atenolol (29-98 %) and fexofenadine (21-87 %), remained constant in the different CWs, and was mainly attributed to sorption. In contrast, removal rates for polar non-sorbing compounds, including diclofenac (3-64 %), acyclovir (9-85 %), and artificial sweeteners acesulfame (5-60 %) and saccharin (1-48 %), seemed to increase over time due to enhanced biodegradation. The presence of vegetation and different planting methods (single vs. mixed plantation) had a limited impact, underscoring the dominance of substrate type in the CW performance. Microbial community analysis identified two stages: a startup phase (1-7 months) and a maturation phase (19-26 months). During this transition, highly diverse communities dominated by specific species in the early stages gave way to more evenly distributed and relatively stable communities. Proteobacteria and Bacteroidetes remained dominant throughout. Alphaproteobacteria, Acidobacteria, Planctomycetes, Salinimicrobium, and Sphingomonas were enriched during the maturation phase, potentially serving as bioindicators for EOC removal. In conclusion, this study emphasizes the pivotal role of substrate type and maturation in the removal of EOCs in HSSF CW, considering the complex interplay with EOC physicochemical properties. Insights into microbial community dynamics underscore the importance of taxonomic and functional diversity in assessing CW effectiveness. This knowledge aids in optimizing HSSF CWs for sustainable wastewater treatment, EOC removal, and ecological risk assessment, ultimately contributing to environmental protection.

Occurrence and distribution of emerging micropollutants in the central part of the German Bight.

Micropollutants (MPs) are transported via rivers from industrial and urban areas to the German Bight (G.B.). In contrast to the mounting rivers less information is available on the occurrence of MPs and their transformation products (TPs) in the marine environment of the G.B. In this study 83 compounds, including 26 metabolites of pharmaceuticals and environmental TPs were measured in water at 46 sampling sites in estuaries of Ems, Weser, Elbe, and the G.B. 36 MPs were even detected in the open sea areas (salinity > 34 psu) at 0.07-5.1 ng/L and to the best of our knowledge 10 MPs were detected in the marine environment for the first time. Concentrations of 8 MPs exceeded PNEC values suggesting a potential risk for sea life. Spatial distribution and relation of MPs with salinity allowed identifying emission paths for certain compounds and revealed the emissions from the River Elbe and Rhine.

Pesticide dynamics in three small agricultural creeks in Hesse, Germany.

Background: Due to their high biodiversity, small water bodies play an important role for freshwater ecosystems. Nonetheless, systematic pesticide monitoring in small creeks with a catchment <30 km2 is rarely conducted. Methods: In this study, event-driven water samples were taken from May until November 2017 and March until July 2018 after 20 rain events at three sampling sites with catchment areas of <27 km2 in the Wetterau, a region with intensive agriculture in Southern Hesse, Germany. Additionally, enriched extracts of the native water samples from the campaign in 2018 were used for the Microtox assay to determine baseline toxicity to invertebrates over time and sum of toxic units (STU) were calculated to compare the potential toxicity of the samples. Results: Overall, 37 pesticides and 17 transformation products were found, whereby the herbicide metamitron (79 µg/L) showed the highest concentration. Regularly, pesticide concentrations peaked at the time of the highest water level within each sampling event. Within each sampling event maximum pesticide concentration was mostly reached in water samples taken during the first two hours. The sum of the time-weighted mean concentration values of all pesticides was between 2.0 µg/L and 7.2 µg/L, whereby the measured concentrations exceeded their regulatory acceptable concentration (RAC) at 55% of all sampling events for at least one pesticide. The mean EC50 values varied between 28.6 ± 13.1 to 41.3 ± 12.1 REF (relative enrichment factor). The results indicated that several samples caused baseline toxicity, whereby the highest activity was measured at the time of highest water levels and pesticides concentrations, and then steadily decreased in parallel with the water level. Median STUs of invertebrates ranged from -2.10 to -3.91, of algae/aquatic plants from -0.79 to -1.84 and of fish from -2.47 to -4.24. For one of the three sampling sites, a significant linear correlation between baseline toxicity and STUinvertebratewas found (r2 = 0.48). Conclusion: The results of the present study suggest that (1) current pesticide monitoring programs underestimate risks posed by the exposure to pesticides for aquatic organisms and (2) pre-authorization regulatory risk assessment schemes are insufficient to protect aquatic environments.

Infection with acanthocephalans increases tolerance of Gammarus roeselii (Crustacea: Amphipoda) to pyrethroid insecticide deltamethrin.

Crustacean amphipods serve as intermediate hosts for parasites and are at the same time sensitive indicators of environmental pollution in aquatic ecosystems. The extent to which interaction with the parasite influences their persistence in polluted ecosystems is poorly understood. Here, we compared infections of Gammarus roeselii with two species of Acanthocephala, Pomphorhynchus laevis, and Polymorphus minutus, along a pollution gradient in the Rhine-Main metropolitan region of Frankfurt am Main, Germany. Prevalence of P. laevis was very low at the unpolluted upstream reaches (P ≤ 3%), while higher prevalence (P ≤ 73%) and intensities of up to 9 individuals were found further downstream-close to an effluent of a large wastewater treatment plant (WWTP). Co-infections of P. minutus and P. laevis occurred in 11 individuals. Highest prevalence of P. minutus was P ≤ 9% and one parasite per amphipod host was the maximum intensity recorded. In order to assess whether the infection affects survival in the polluted habitats, we tested the sensitivity of infected and uninfected amphipods towards the pyrethroide insecticide deltamethrin. We found an infection-dependent difference in sensitivity within the first 72 h, with an effect concentration (24 h EC50) of 49.8 ng/l and 26.6 ng/l for infected and uninfected G. roeselii, respectively. Whereas final host abundance might partially explain the high prevalence of P. laevis in G. roeselii, the results of the acute toxicity test suggest a beneficial effect of acanthocephalan infection for G. roeselii at polluted sites. A strong accumulation of pollutants in the parasite could serve as a sink for pesticide exposure of the host. Due to the lack of a co-evolutionary history between parasite and host and a lack of behavioral manipulation (unlike in co-evolved gammarids), the predation risk by fish remains the same, explaining high local prevalence. Thus, our study exemplifies how organismic interaction can favor the persistence of a species under chemical pollution.

Quantification of Poly(vinyl chloride) Microplastics via Pressurized Liquid Extraction and Combustion Ion Chromatography.

A reliable analytical method has been developed to quantify poly(vinyl chloride) (PVC) in environmental samples. Quantification was conducted via combustion ion chromatography (C-IC). Hydrogen chloride (HCl) was quantitatively released from PVC during thermal decomposition and trapped in an absorption solution. Selectivity of the marker HCl in complex environmental samples was ensured using cleanup via pressurized liquid extraction (PLE) with methanol at 100 °C (discarded) and tetrahydrofuran at 185 °C (collected). Using this method, recoveries of 85.5 ± 11.5% and a limit of quantification down to 8.3 µg/g were achieved. A variety of hard and soft PVC products could be successfully analyzed via C-IC with recoveries exceeding >95%. Furthermore, no measurable overdetermination was found for various organic and inorganic matrix ingredients, such as sodium chloride, sucralose, hydroxychloroquine, diclofenac, chloramphenicol, triclosan, or polychlorinated biphenyls. In addition, sediments and suspended particular matter showed PVC concentrations ranging up to 16.0 and 220 µg/g, respectively. However, the gap between determined polymer mass and particle masses could be significant since soft PVC products contain plasticizers up to 50 wt %. Hence, the results of the described method represent a sum of all chlorine-containing polymers, which are extractable under the chosen conditions.

Protein fractionation and shotgun proteomics analysis of enriched bacterial cultures shed new light on the enzymatically catalyzed degradation of acesulfame.

The removal of organic micropollutants in municipal wastewater treatment is an extensively studied field of research, but the underlying enzymatic processes have only been elucidated to a small extent so far. In order to shed more light on the enzymatic degradation of the artificial sweetener acesulfame (ACE) in this context, we enriched two bacterial taxa which were not yet described to be involved in the degradation of ACE, an unknown Chelatococcus species and Ensifer adhaerens, by incubating activated sludge in chemically defined media containing ACE as sole carbon source. Cell-free lysates were extracted, spiked with ACE and analyzed via target LC-MS/MS, demonstrating for the first time enzymatically catalyzed ACE degradation outside of living cells. Fractionation of the lysate via two-dimensional fast protein liquid chromatography (FPLC) succeeded in a partial separation of the enzymes catalyzing the initial transformation reaction of ACE from those catalyzing the further transformation pathway. Thereby, an accumulation of the intermediate transformation product acetoacetamide-n-sulfonic acid (ANSA) in the ACE-degrading fractions was achieved, providing first quantitative evidence that the cleavage of the sulfuric ester moiety of ACE is the initial transformation step. The metaproteome of the enrichments was analyzed in the FPLC fractions and in the unfractionated lysate, using shotgun proteomics via UHPLC-HRMS/MS and label-free quantification. The comparison of protein abundances in the FPLC fractions to the corresponding ACE degradation rates revealed a metallo-ß-lactamase fold metallo-hydrolase as most probable candidate for the enzyme catalyzing the initial transformation from ACE to ANSA. This enzyme was by far the most abundant of all detected proteins and amounted to a relative protein abundance of 91% in the most active fraction after the second fractionation step. Moreover, the analysis of the unfractionated lysate resulted in a list of further proteins possibly involved in the transformation of ACE, most striking a highly abundant amidase likely catalyzing the further transformation of ANSA, and an ABC transporter substrate-binding protein that may be involved in the uptake of ACE into the cell.

Identification and trend analysis of organic cationic contaminants via non-target screening in suspended particulate matter of the German rivers Rhine and Saar.

Non-target screening of suspended particulate matter (SPM), collected from the German rivers Rhine and Saar, was conducted with the goal of identifying organic, permanent cationic contaminants and of estimating their temporal trends over an extended period. Therefore, annual composite samples of SPM, provided by the German Environmental Specimen Bank, were extracted and analyzed with high resolution LC-QToF-MS/MS. To facilitate the identification of substances belonging to the class "permanent cations", prioritization methods were applied utilizing the physicochemical properties of these compounds. These methods include both interactions of the analyte molecules with cation exchange resins and analyzing mass deviations when changing from non-deuterated to deuterated mobile phase solvents during LC-MS analysis. By applying both methods in a combined approach, 123 of the initially detected 2695 features were prioritized, corresponding to a 95% data reduction. This led to the identification of 22 permanent cationic species. The organic dyes Basic Yellow 28 and Fluorescent Brightener 363 as well as two quaternary ammonium compounds (QACs) were detected in environmental samples for the first time to best of or knowledge. The other compounds include additional QACs, as well as quaternary tri-phenylphosphonium compounds (QPC/TPP). In addition to identification, we determined temporal trends of all compounds over a period of 13 years and assessed their ecotoxicological relevance based on estimated concentrations. The two QACs oleyltrimethylammonium and eicosyltrimethylammonium show significant increasing trends in the Rhine SPM and maximum concentrations in the Saar SPM of about 900 and 1400 µg/kg, respectively. In the case of the dyes, constant trends have been observed at the end of the studied period, but also maximum concentrations of 400 µg/kg for Basic Yellow 28 in 2006 and 1000 µg/kg for Fluorescent Brightener 363 in 2015, potentially indicating a strong ecotoxicological risk.

Making waves: Time for chemical surface water quality monitoring to catch up with its technical potential.

A comprehensive real-time evaluation of the chemical status of surface water bodies is still utopian, but in our opinion, it is time to use the momentum delivered by recent advanced technical, infrastructural, and societal developments to get significantly closer. Procedures like inline and online analysis (in situ or in a bypass) with close to real-time analysis and data provision are already available in several industrial sectors. In contrast, atline and offline analysis involving manual sampling and time-decoupled analysis in the laboratory is still common practice in aqueous environmental monitoring. Automated tools for data analysis, verification, and evaluation are changing significantly, becoming more powerful with increasing degrees of automation and the introduction of self-learning systems. In addition, the amount of available data will most likely in near future be increased by societal awareness for water quality and by citizen science. In this analysis, we highlight the significant potential of surface water monitoring techniques, showcase "lighthouse" projects from different sectors, and pin-point gaps we must overcome to strike a path to the future of chemical monitoring of inland surface waters.

Open-source feature detection for non-target LC-MS analytics.

RATIONALE: Non-target screening techniques using high-resolution mass spectrometers become more and more important for environmental sciences. Highly reliable and sophisticated software solutions are required to deal with the large amount of data obtained from such analyses. METHODS: Processing of high-resolution LC-HRMS data was performed upon conversion into an open, XML-based data format followed by an automated assignment of chromatographic peaks using the open-source programming language R. Raw data from three different LC-HRMS systems were processed as a proof of principle. RESULTS: We present a simple and straightforward algorithm to extract chromatographic peaks from previously m/z-centroided data based on the open-source programming language R and C++. The working principle and processing parameters are explained in detail. A ready-to-use script is provided in the supporting information. CONCLUSIONS: The developed algorithm enables a comprehensible automated peak picking of non-target LC-MS data. Application to three completely different HRMS raw data files showed reasonable False Positives and False Negatives detection and moderate calculation times.

Biotransformation of pregabalin in surface water matrices and the occurrence of transformation products in the aquatic environment - comparison to the structurally related gabapentin.

The biodegradability of the anticonvulsant pregabalin (PGB) was studied in laboratory incubation experiments in contact with water/sediment systems under different redox conditions. PGB was degraded by biological processes under aerobic conditions reaching half-lives of 8 to 10 d, while inactivated and anaerobic control experiments revealed no significant decrease of PGB concentrations. Within experiments spiked with elevated PGB concentrations, 12 TPs were formed and tentative chemical structures could be proposed by accurate masses and fragmentation pathways detected via measurements with high resolution mass spectrometry (LC-QToF-MS). Four of the proposed TPs were finally confirmed either by authentic reference standards (PGB-Lactam, ISA, TP 157-A (II)) or a self-synthesized standard (NA-PGB). PGB-Lactam was identified as the quantitatively most relevant TP formed via intramolecular cyclization under aerobic conditions, reaching up to 33% of the initial PGB concentration. Incubation experiments spiked with PGB-Lactam revealed three times higher half-lives compared to the parent compound, indicating that PGB-Lactam is more stable than PGB. A comparison with results gained from water/sediment incubation experiments with the structurally related compound gabapentin (GBP) revealed, that the transformation behaviour can be mainly extrapolated to PGB. Most of the observed transformation reactions found for PGB were comparable to the ones found for GBP. The TPs PGB-Lactam and NA-PGB as well as three GBP TPs (GBP-Lactam, NA-GBP and CCHA) have been detected in German wastewater treatment plants (WWTPs) effluents and the river Rhine including some of its tributaries such as Main, Neckar, Moselle and Aare. Moreover, GBP and PGB as well as some of their TPs were detected in German bank filtrates and finished drinking waters up to 260 ng L-1. For that reason these compounds should be monitored in drinking water in the future.

Micropollutant transformation and taxonomic composition in hybrid MBBR - A comparison of carrier-attached biofilm and suspended sludge.

The suspended sludge and carrier-attached biofilms of three different hybrid moving bed biofilm reactor (MBBR) systems were investigated with respect to their transformation potential for a broad range of micropollutants (MPs) as well as their microbial community composition. For this purpose, laboratory-scale batch experiments were conducted with the separated suspended sludge and the carrier-attached biofilm of every system in triplicate. For all batches the removal of 31 MPs as well as the composition of the microbial community were analyzed. The carrier-attached biofilms from two hybrid MBBR systems showed a significant higher overall transformation potential in comparison to the respective suspended sludge. Especially for the MPs trimethoprim, diclofenac, mecoprop, climbazole and the human metabolite 10,11-dihydro-10-hydroxycarbamazepine consistently higher pseudo-first-order transformation rates could be observed in all three systems. The analysis of the taxonomic composition revealed taxa showing higher relative abundances in the carrier-attached biofilms (e. g. Nitrospirae and Chloroflexi) and in the suspended biomasses (e. g. Bacteroidetes and Betaproteobacteria). Correlations of the biodiversity indices and the MP biotransformation rates resulted in significant positive associations for 11 compounds in suspended sludge, but mostly negative associations for the carrier-attached biofilms. The distinct differences in MP removal between suspended sludge and carrier-attached biofilm of the three different MBBR systems were also reflected by a statistically significant link between the occurrence of specific bacterial taxa (Acidibacter, Nitrospira and Rhizomicrobium) and MP transformation rates of certain MPs. Even though the identified correlations might not necessarily be of causal nature, some of the identified taxa might serve as suitable indicators for the transformation potential of suspended sludge or carrier-attached biofilms.

Fate and behavior of progestogens in activated sludge treatment: Kinetics and transformation products.

Previous studies have shown the high ecotoxicological potential of progestogens (PGs) on the reproductive system of aquatic organisms. Yet the ubiquitous presence of several PGs in wastewater treatment plant (WWTP) effluents indicates an incomplete removal during treatment. To investigate the fate and behavior of PGs during biological wastewater treatment, nine commonly used PGs were incubated in aerobic lab-scale degradation experiments with activated sludge taken from a municipal WWTP. The degradation kinetics revealed a fast removal after 48 h for most of the compounds. Cyproterone acetate and dienogest were the most recalcitrant of the analyzed steroids with half-lives of 8.65 h and 4.55 h, respectively. Thus, only moderate removals of these PGs can be predicted in full-scale WWTPs. Moreover, numerous transformation products (TPs) were detected via high-resolution mass spectrometry. Hydrogenation or dehydrogenation of ring A and non-selective hydroxylations of 17α-hydroxyprogesterone derivatives (medroxyprogesterone acetate, chlormadinone acetate, cyproterone acetate) as well as for 19-nortestosterone derivatives (dienogest, norethisterone acetate, etonogestrel) were observed as major transformation reactions. Seven of the identified TPs were confirmed by reference standards. The biodegradation of cyproterone acetate revealed an almost quantitative transformation to 3α­hydroxy cyproterone acetate which is reported to be genotoxic. In a comparative evaluation of the TPs formed and the steroid structure, it was observed that molecular structure played a role in the inhibition of several transformation reactions, explaining the increased recalcitrance of these compounds. In addition, aromatization of the steroid ring A was identified for the 19-nortestosterone derivatives leading to the formation of estrogen-like TPs. For instance, the degradation of norethisterone acetate led to the formation of 17α-ethinylestradiol, a well-known and very potent synthetic estrogen. The evidence of the conversion of progestogenic to estrogenic compounds and the formation of potentially hazardous TPs indicates the need of a more comprehensive environmental risk assessment for synthetic steroids. Two of the newly identified TPs (3α-hydroxy cyproterone acetate and ∆9,11-dehydro-17α-cyanomethyl estradiol) were detected in WWTP effluents for the first time.

Fate and removal of bacteria and antibiotic resistance genes in horizontal subsurface constructed wetlands: Effect of mixed vegetation and substrate type.

This study aimed to investigate the influence of cropping method and substrate type on the fate and the removal of bacterial and antibiotic resistance genes (ARGs) indicators from primary wastewater by constructed wetlands (CWs) during startup and maturation stages. Four small-scale CWs differing in their plantation pattern (monoculture vs. polyculture) and substrate type were constructed and operated under field conditions. While for bacteria, the greatest impact of the cropping method and substrate type on removal was during the startup stage rather than the maturation stage, for ARGs, such impact was significant at both stages. During startup, the removal efficiencies of heterotrophic bacteria, fecal coliforms, E. coli, 16S rRNA genes and lacZ increased with the operation time. At maturation, the removal efficiencies were constant and were within the range of 89.2-99.4%, 93.7-98.9%, 89-98.8%, 94.1-99.6% and 92.9-98.7%, respectively. The removal efficiencies of intl1, tetM, intl1, sul1, ermB and total ARGs were also increased with the operation time. However, they were ARG type and configuration-dependent; at maturation they ranged between 50.7%-89.4%, 85.9%-97%, 49.6%-92.9%, 58.2%-96.7% and 79.9-94.3%, respectively. The tuff-filled serially planted CW was also the only one capable of removing these genes at similar high efficiency. Metagenomic analysis showed that none of the ARGs was among the most common ARGs in water and biofilm samples; rather most ARGs belonged to bacterial efflux transporter superfamilies. Although ARGs were removed, they were still detected in substrate biofilm and their relative concentrations were increased in the effluents. While the removal of both bacteria and ARGs was higher during summer compared to winter, the season had no effect on the removal pattern of ARGs. Hence, combination of the serial plantation with substrate having high surface area is a potential strategy that can be used to improve the performance of CWs.

Development of an analytical method to quantify pharmaceuticals in fish tissues by liquid chromatography-tandem mass spectrometry detection and application to environmental samples.

A sensitive multiresidue method was developed to quantify 35 pharmaceuticals and 28 metabolites/transformation products (TPs) in fish liver, fish fillet and fish plasma via LC-MS/MS. The method was designed to cover a broad range of substance polarities. This objective was realized by using non-discriminating sample clean-ups including separation technique based on size exclusion, namely restricted access media (RAM) chromatography. This universal clean-up allows for an easy integration of further organic micropollutants into the analytical method. Limits of quantification (LOQ) ranged from 0.05 to 5.5 ng/mL in fish plasma, from 0.1 to 19 ng/g d.w. (dry weight) in fish fillet and from 0.46 to 48 ng/g d.w. in fish liver. The method was applied for the analysis of fillets and livers of breams from the rivers Rhine and Saar, the Teltow Canal as well as carps kept in fish monitoring ponds fed by effluent from municipal wastewater treatment plants. This allowed for the first detection of 17 analytes including 10 metabolites/TPs such as gabapentin lactam and norlidocaine in fish tissues. These results highlight the importance of including metabolites and transformation products of pharmaceuticals in fish monitoring campaigns and further investigating their potential effects.

Ozonation of Sitagliptin: Removal Kinetics and Elucidation of Oxidative Transformation Products.

Due to the increasing use and high excretion rates, high quantities of the antidiabetic drug sitagliptin (STG) enter wastewater treatment plants (WWTPs). In conventional biological treatment, only a moderate removal was achieved, and thus, STG can be detected in WWTP effluents with concentrations in the higher ng/L range. Ozonation is a widely discussed technique for advanced wastewater treatment. In lab-scale experiments, STG showed pH-dependent removal kinetics with a maximum apparent rate constant of k ∼1 × 104 M-1 s-1 at pH ≥ 9. With an apparent rate constant of kO3 = (1.8 ± 0.7) × 103 M-1 s-1 at pH 8, STG can be considered to be readily degraded by ozonation of WWTP effluents. Ozone attacks the primary amine moiety of STG, leading to nitro-STG (TP 437) (the primary amine moiety is transformed into a nitro group). Furthermore, a diketone (TP 406) was formed, which can be further degraded by ozone. Lab-scale and pilot-scale experiments on ozonation of WWTP effluents confirmed that the ozone attack of STG was incomplete even at high ozone doses of 1.7 and 0.9 mg O3/mg DOC, respectively. These experiments confirmed that nitro-STG was formed as the main TP in the wastewater matrix. Two other TPs, TP 421c and TP 206b, were also detected, albeit with low intensities.

Application of a non-target workflow for the identification of specific contaminants using the example of the Nidda river basin.

Non-target screening of water samples from the Nidda river basin in central Germany was conducted with the goal to identify previously unknown chemical contaminants and their emission sources. The focus was on organic, water-borne contaminants which were not typical to municipal wastewater. Grab samples of river water from 13 locations on the Nidda and 15 of its tributaries, in sum 112 samples, were analysed with high resolution LC-QToF-MS/MS. To facilitate the identification of substances, features originating from the same compound such as adducts and isotopologues as well as in-source fragments and species with multiple charge states were registered and grouped by a componentization step utilizing both retention times and peak shapes of the features to combine them in a single component. This led to a reduction of the number of features by an average of 1235 per sample (46%). These grouped features were prioritized if these were detected only in specific tributaries or specific river sections, reducing the number of components by an average of 913 per sample (78%). In addition, grouped features were labelled as typically found in municipal wastewater by combining data from 16 wastewater treatment plants located across Germany and Switzerland and comparing this to components detected in the Nidda basin. These were removed, leading to a further reduction of components by an average of 72 per sample (30%) for an average total reduction of 2536 per sample (93%). Finally, nine compounds, with emission sources in three specific tributaries, were identified, including the textile additive Nylostab S-EED®, which was previously not known to be an environmental contaminant, as well as naturally occurring compounds such as highly toxic microcystins.

Under the radar - Exceptionally high environmental concentrations of the high production volume chemical sulfamic acid in the urban water cycle.

Elevated concentrations of sulfamate, the anion of sulfamic acid, were found in surface waters and finished drinking water in Germany with concentrations up to 580 µg/L and 140 µg/L, respectively. Wastewater treatment plant (WWTP) effluent was identified as the dominant source of sulfamate in the urban water cycle, as sulfamate concentrations correlated positively (0.77 > r < 0.99) with concentrations of the wastewater tracer carbamazepine in samples from different waterbodies. Ozonation and activated sludge experiments proved that sulfamate can be formed from chemical and biological degradation of various precursors. Molar sulfamate yields were highly compound-specific and ranged from 2% to 56%. However, the transformation of precursors to sulfamate in WWTPs and wastewater-impacted waterbodies was found to be quantitatively irrelevant, since concentrations of sulfamate in these compartments are already high, presumably due to its primary use as an acidic cleaning agent. Sulfamate concentrations in the influent and effluent of studied WWTPs ranged from 520 µg/L to 1900 µg/L and from 490 µg/L to 1600 µg/L, respectively. Laboratory batch experiments were performed to assess the recalcitrance of sulfamate for chemical oxidation. In combination with the results from sampling conducted at full-scale waterworks, it was shown that common drinking water treatment techniques, including ozonation and filtration with activated carbon, are not capable to remove sulfamate. The results of biodegradation tests and from the analysis of samples taken at four bank filtration sites indicate that sulfamate is attenuated in the sediment/water interface of aquatic systems and during aquifer passage under aerobic and anaerobic conditions. Sulfamate concentrations decreased by between 62% and 99% during aquifer passage at the bank filtration sites. Considering the few data on short term ecotoxicity, about 30% of the presented sulfamate levels in ground and surface water samples did exceed the predicted no-effect concentration (PNEC) of sulfamate, and thus effects of sulfamate on the aquatic ecosystem of wastewater-impacted waterbodies in Germany cannot be excluded so far. Toxicological estimations suggest that no risk to human health is expected by concentrations of sulfamate typically encountered in tap water.

Analysis of the aerobic biodegradation of glucocorticoids: Elucidation of the kinetics and transformation reactions.

Glucocorticoids (GCs) are one of the most prescribed pharmaceutical classes worldwide. They have reached the focus as environmental pollutants in the current scientific research, due to their potential risks to aquatic organisms even in the lower ng L-1 range. The objective of this study was to determine the kinetic behavior of selected GCs and to identify their main transformation products (TPs) in lab scaled biodegradation experiments. Therefore, we analyzed the removal of 13 GCs in aerated incubation experiments with activated sludge taken from a German municipal wastewater treatment plant (WWTP) as inoculum. For all steroids, an exponential decrease of the concentrations was observed, which was modelled by pseudo-first order kinetics. Overall, the rate constants kbiol. ranged from 0.07 L gss-1 d-1 (triamcinolone acetonide) to 250 L gss-1 d-1 (prednisolone). These results emphasize the broad variation in the biodegradability and recalcitrance of certain GCs. The selection of the studied GCs enabled a deduction of microbiological stability related to functional groups. Based on the identified TPs, a variety of enzymatically mediated reactions were postulated. Moreover, the identified TPs are characterized by an intact steroid core structure. Thus residual endocrine activity cannot be ruled out. The main observed reactions were regioselective hydrogenation of carbon double-bonds, degradation of the steroid C17 side-chain, ester hydrolysis and oxidative hydroxylation. In total, 41 TPs were tentatively identified and 22 of them were unambiguously confirmed via reference standards. Additionally, 12 TPs were detected in the effluents of municipal WWTPs and, to the best of our knowledge, the occurrence of eight of these TPs has been shown for the first time. These TPs might significantly contribute to the detected residual endocrine activities in the aquatic environments. Therefore, there is a strong need for efficient removal strategies, in particular for persistent steroid hormones with elevated potencies.

Comparing mass, retention time and tandem mass spectra as criteria for the automated screening of small molecules in aqueous environmental samples analyzed by liquid chromatography/quadrupole time-of-flight tandem mass spectrometry.

RATIONALE: The adoption of database screening using high-resolution liquid chromatography/mass spectrometry data is promising as a river water monitoring and surveillance tool but depends on the ability to perform reliable data processing on a large number of samples in a unified workflow. Strategies to minimize errors have been proposed but automated procedures are rare. METHODS: High-resolution LC/ESI-QTOFMS/MS in data-dependent MS2 acquisition mode was performed for the analysis of surface water samples by direct injection. Data processing was achieved with software tools written in R. A database containing MS2 spectra of 693 compounds formed the basis of the workflow. Standard mixes and a time series of 361 samples of river water were analyzed and processed with the optimized workflow. RESULTS: Using the database and a mix of 70 standards for testing, it was found that an identification strategy including (i) mass, (ii) retention time, and (iii) MS2 spectral matching achieved a two- to three-fold improvement in the fraction of false positives compared with using only two criteria, while the number of false negatives remained low. The optimized workflow was applied to the sample series of river water. In total, 135 compounds were identified by a library match. CONCLUSIONS: The developed automated database screening approach minimizes the proportion of false positives, while still allowing for the screening of hundreds of water samples for hundreds of compounds in a single run.

Spatial distribution and temporal trends of pharmaceuticals sorbed to suspended particulate matter of German rivers.

Although several studies confirmed a wide distribution of pharmaceuticals in rivers and streams, a limited knowledge is available about the partitioning of pharmaceuticals between the water phase and suspended particulate matter (SPM). To close this gap of knowledge, we developed and validated a sensitive and high throughput analytical method for the analysis of 57 pharmaceuticals, 42 metabolites and transformation products (TP) as well as the artificial sweetener acesulfame sorbed to SPM. The method was based on pressurized liquid extraction (PLE) followed by a clean-up via solvent exchange and detection via direct injection-reversed phase LC-MS/MS and freeze-drying-HILIC-MS/MS. Freundlich isotherms were determined for 90 analytes. All showed a linear sorption behavior. Distribution coefficients (Kd) ranged from 0.64 L/kg to 9300 L/kg. For 18 pharmaceuticals, Kd values were found to be above 100 L/kg. SPM of annual composite samples were analyzed to determine the pharmaceutical concentrations between 2005 and 2015 at four sites of the river Rhine: Weil, Iffezheim, Koblenz and Bimmen as well as between 2006 and 2015 at one site of the river Saar, at Rehlingen. In these SPM samples, up to 61 of the 100 analytes were detected with concentrations up to 190 ng/g d.w. (dry weight) for guanylurea, a transformation product of the antidiabetic metformin. For most analytes, increasing concentrations were found along the length of the Rhine and higher concentrations were measured in Rehlingen/Saar. Normalization of the data with the antiepileptic drug carbamazepine as an intrinsic tracer for municipal wastewater indicated possible industrial discharges for four analytes. For most pharmaceuticals, the annual concentrations exhibited a good correlation with the consumption volumes in Germany.