Abteilung Umweltchemie

To optimize removal of organic micropollutants from the water cycle, understanding the processes during activated sludge treatment is essential. In this study, we hypothesize that aliphatic amines, which are highly abundant among organic micropollutants, are partly removed from the water phase in activated sludge through ion trapping in protozoa. In ion trapping, which has been extensively investigated in medical research, the neutral species of amine-containing compounds diffuse through the cell membrane and further into acidic vesicles present in eukaryotic cells such as protozoa. There they become trapped because diffusion of the positively charged species formed in the acidic vesicles is strongly hindered. We tested our hypothesis with two experiments. First, we studied the distribution of the fluorescent amine acridine orange in activated sludge by confocal fluorescence imaging. We observed intense fluorescence in distinct compartments of the protozoa, but not in the bacterial biomass. Second, we investigated the distribution of 12 amine-containing and eight control micropollutants in both regular activated sludge and sludge where the protozoa had been inactivated. In contrast to most control compounds, the amine-containing micropollutants displayed a distinctly different behavior in the noninhibited sludge compared to the inhibited one: (i) more removal from the liquid phase; (ii) deviation from first-order kinetics for the removal from the liquid phase; and (iii) higher amounts in the solid phase. These results provide strong evidence that ion trapping in protozoa occurs and that it is an important removal mechanism for amine-containing micropollutants in batch experiments with activated sludge that has so far gone unnoticed. We expect that our findings will trigger further investigations on the importance of this process in full-scale wastewater treatment systems, including its relevance for accumulation of ammonium.

One open question in environmental sciences is whether effective management of natural resources depends on the fit between the bio-physical and the governance system. To address this question, we investigate water quality in transboundary rivers and ask to what extent a fit between the area covered by the physical extent of pollution and the area in which this pollution is addressed through management and policy regulation can be observed. We adopt a spatial approach and argue that the visualization of social-ecological overlap and misfit supports science and practice when taking decisions about how best to explain or address ineffectiveness and cause-effect mismatches in transboundary river management.
We focus on drinking water supply in the international river basin of the Rhine focusing on micropollutants. These persistent trace compounds have potential toxic effects on humans and ecosystems, which makes them a relevant type of pollution that needs to be taken into consideration. Based on a combination of mass flow and social network analysis, we can conclude that the Rhine River is characterized by large social-ecological overlap, but that some parts of the catchment area still lack integration.

A large amount of residues from active pharmaceutical ingredients (API) that are currently in use are known to reach aquatic ecosystems and have potentially adverse effects on living organisms. Prioritization methods are useful tools for both regulation and surveillance purposes in the environmental policy of APIs. Their use has largely increased over the last decade, and the different existing methodologies can lead to large discrepancies between the highlighted substances. This chapter aims at discussing studies conducted in the context of hospitals. Perhaps more important than the results themselves, the methodologies with the set of selected criteria are discussed, as well as their advantages and associated uncertainties. A case study of API prioritization applied to a Swiss university hospital is presented with two different approaches: a ranking-based OPBT approach (Occurrence, Persistence, Bioaccumulation, and Toxicity) and an environmental risk assessment (ERA), with the calculation of risk quotient (RQ). The ERA results combined with those of other studies dealing with ERA-based API prioritization in hospitals highlighted several compounds presenting high risks for the aquatic ecosystems (RQ > 1): antibiotics (ciprofloxacin, amoxicillin, piperacillin, azithromycin), anti-inflammatory drugs (diclofenac, mesalazine), as well as the hormone estradiol and the antidiabetic metformin. Nevertheless, only the antibiotic ciprofloxacin was commonly determined as problematic. Finally, the most critical issues for API prioritization in hospitals were identified from the literature overview and the results of the presented case study: handling of the consumption data, involvement of expert judgment, uncertainties linked with the predicted environmental concentration (PEC) calculation, and quality of the hazard evaluation. Although prioritization procedures applied to hospitals can be burdensome to apply in practice and many associated uncertainties remain, they represent essential tools to establish lists of priority molecules to follow via monitoring programs and allow their theoretical risk assessment.

In nontarget screening, structure elucidation of small molecules from high resolution mass spectrometry (HRMS) data is challenging, particularly the selection of the most likely candidate structure among the many retrieved from compound databases. Several fragmentation and retention prediction methods have been developed to improve this candidate selection. In order to evaluate their performance, we compared two in silico fragmenters (MetFrag and CFM-ID) and two retention time prediction models (based on the chromatographic hydrophobicity index (CHI) and on log D). A set of 78 known organic micropollutants was analyzed by liquid chromatography coupled to a LTQ Orbitrap HRMS with electrospray ionization (ESI) in positive and negative mode using two fragmentation techniques with different collision energies. Both fragmenters (MetFrag and CFM-ID) performed well for most compounds, with average ranking the correct candidate structure within the top 25% and 22 to 37% for ESI+ and ESI− mode, respectively. The rank of the correct candidate structure slightly improved when MetFrag and CFM-ID were combined. For unknown compounds detected in both ESI+ and ESI−, generally positive mode mass spectra were better for further structure elucidation. Both retention prediction models performed reasonably well for more hydrophobic compounds but not for early eluting hydrophilic substances. The log D prediction showed a better accuracy than the CHI model. Although the two fragmentation prediction methods are more diagnostic and sensitive for candidate selection, the inclusion of retention prediction by calculating a consensus score with optimized weighting can improve the ranking of correct candidates as compared to the individual methods.

Urban regions of the world are expanding rapidly, placing additional stress on water resources. Urban water bodies serve many purposes from washing and sources of drinking water to transport and conduits for storm drainage and effluent discharge. These water bodies receive chemical emissions arising from either single or multiple point sources, diffuse sources which can be continuous, intermittent or seasonal. Thus, aquatic organisms in these water bodies are exposed to temporally and compositionally variable mixtures. We have delineated source-specific signatures of these mixtures for diffuse urban runoff and urban point source exposure scenarios to support risk assessment and management of these mixtures. The first step in a tiered approach to assessing chemical exposure has been developed based on the Event Mean Concentration concept with chemical concentrations in runoff defined by volumes of water leaving each surface and the chemical exposure mixture profiles for different urban scenarios. Although generalizations can be made about the chemical composition of urban sources and event mean exposure predictions for initial prioritization, such modelling needs to be complemented with biological monitoring data. It is highly unlikely that the current paradigm of routine regulatory chemical monitoring alone will provide a realistic appraisal of urban aquatic chemical mixture exposures. Future consideration is also needed on the role of non-chemical stressors in such highly modified urban water bodies.

Drinking water production in the vicinity of rivers not only requires the consideration of different spatiotemporal scales and settings of river-groundwater interaction processes, but also of local and regional scale groundwater regimes.
Selected case studies in combination with field-experiments and the setup of high-resolution groundwater flow models enabled the investigation of the spatiotemporal development of microbial (classical fecal indicator bacteria and total cell counts) and selected organic micropollutants in riverine and regional groundwater for different hydrological settings, including low and high flow conditions. Proxy indicators suitable as surrogates for the diverse contaminations in alluvial aquifers with different settings could be identified.
Based on the study results, the basic elements for both groundwater management and river restoration concepts are derived, which include the: (1) compilation and evaluation of the "current state" concerning hydrogeology, microbiology and contamination by organic micropollutants, (2) definition of field-experiments to qualitatively assess variability related to the "current state", and (3) quantitative assessment of groundwater regimes, including variability of groundwater components and inflow areas, by application of high-resolution groundwater flow models.
The validity and transferability of the concept and inferred controls (specifically drivers and controls of river-groundwater interaction) are tested by evaluations derived from hydraulic relationships to river sections with comparable settings and regional groundwater flow regimes in general.
The results of our investigations illustrate the influence of dynamic hydrologic boundary conditions on river-groundwater interaction and of regional scale groundwater flow regimes on the water composition of riverine groundwater systems. It is demonstrated how to identify river sections and their variations with intensified river-groundwater exchange processes and how to quantify the transient character of the different groundwater components that constitute the raw water quality of drinking water wells near rivers.

Iron (oxyhydr-)oxide reduction has been extensivelystudied because of its importance in pollutant redoxdynamics and biogeochemical processes. Yet, experimentalstudies linking oxide reduction kinetics to thermodynamicsremain scarce. Here, we used mediated electrochemicalreduction (MER) to directly quantify the extents and rates offerrihydrite, goethite, and hematite reduction over a range ofnegative reaction free energies, Δ_rG, that were obtained bysystematically varying pH (5.0 to 8.0), applied reductionpotentials (−0.53 to −0.17 V vs SHE), and Fe²⁺ concentrations(up to 40 μM). Ferrihydrite reduction was complete and fast atall tested Δ_rG values, consistent with its comparatively lowthermodynamic stability. Reduction of the thermodynamicallymore stable goethite and hematite changed from complete and fast to incomplete and slow as Δ_rG values became less negative.Reductions at intermediate Δ_rG values showed negative linear correlations between the natural logarithm of the reduction rateconstants and Δ_rG. These correlations imply that thermodynamics controlled goethite and hematite reduction rates. Beyondallowing to study iron oxide reduction under defined thermodynamic conditions, MER can also be used to capture changes iniron oxide reducibility during phase transformations, as shown for Fe²⁺-facilitated transformation of ferrihydrite to goethite.

Um das Wissen bezüglich der Auswirkung von Flussrevitalisierungen auf die aquatischen und terrestrischen Kompartimente zu verbessern, wurden die beiden interdisziplinären Forschungsprojekte RECORD und RECORD Catchment in den Jahren 2007 bis 2017 durchgeführt. Wesentliche Untersuchungen fanden im Einzugsgebiet der Thur statt. Hinweise lassen darauf schliessen, dass in revitalisierten Abschnitten der mikrobielle Abbau bei der Flusswasserinfiltration höher ist als in kanalisierten.

In 2005, the European Commission funded the NORMAN project to promote a permanent network of reference laboratories and research centers, including academia, industry, standardization bodies, and NGOs. Since then, NORMAN has (i) facilitated a more rapid and wide-scope exchange of data on the occurrence and effects of contaminants of emerging concern (CECs), (ii) improved data quality and comparability via validation and harmonization of common sampling and measurement methods (chemical and biological), (iii) provided more transparent information and monitoring data on CECs, and (iv) established an independent and competent forum for the technical/scientific debate on issues related to emerging substances. NORMAN plays a significant role as an independent organization at the interface between science and policy, with the advantage of speaking to the European Commission and other public institutions with the “bigger voice” of more than 70 members from 20 countries. This article provides a summary of the first 10 years of the NORMAN network. It takes stock of the work done so far and outlines NORMAN’s vision for a Europe-wide collaboration on CECs and sustainable links from research to policy-making. It contains an overview of the state of play in prioritizing and monitoring emerging substances with reference to several innovative technologies and monitoring approaches. It provides the point of view of the NORMAN network on a burning issue - the regulation of CECs - and presents the positions of various stakeholders in the field (DG ENV, EEA, ECHA, and national agencies) who participated in the NORMAN workshop in October 2016. The main messages and conclusions from the round table discussions are briefly presented.

Many Swiss streams exhibit high levels ofplant-protection product (PPP) inputs, witherosion and runoff being important entrypaths. This article furnishes an overview ofmeasures for reducing PPP inputs intobodies of water from arable land due toerosion, runoff and drainage, and providesan expert-based qualitative evaluation ofthese measures in terms of state ofresearch, practical feasibility, acceptance,progress with implementation, and potentialfor reduction. The effectiveness ofmany measures is scientifically proven, andpractical feasibility is also given in manycases. There is significant room forimprovement in terms acceptance of themeasures by farmers, and regardingimplementation in particular. Whereasmany of the measures have great potentialfor reducing PPP inputs in a specific location,only a few show potential for nationwideimplementation. Consequently, thelarge variation in site factors across Switzerlandmeans that reduction measuresmust be taken regionally and be adapted tothe site in question.

Many Swiss streams exhibit high levels ofplant-protection product (PPP) inputs, witherosion and runoff being important entrypaths. This article furnishes an overview ofmeasures for reducing PPP inputs intobodies of water from arable land due toerosion, runoff and drainage, and providesan expert-based qualitative evaluation ofthese measures in terms of state ofresearch, practical feasibility, acceptance,progress with implementation, and potentialfor reduction. The effectiveness ofmany measures is scientifically proven, andpractical feasibility is also given in manycases. There is significant room forimprovement in terms acceptance of themeasures by farmers, and regardingimplementation in particular. Whereasmany of the measures have great potentialfor reducing PPP inputs in a specific location,only a few show potential for nationwideimplementation. Consequently, thelarge variation in site factors across Switzerlandmeans that reduction measuresmust be taken regionally and be adapted tothe site in question.

Little is known about the forces that determine the assembly of diverse bacterial communities inhabiting drinking water treatment filters and how this affects drinking water quality. Two contrasting ecological theories can help to understand how natural microbial communities assemble; niche theory and neutral theory, where environmental deterministic factors or stochastic factors predominate respectively. This study investigates the development of the microbial community on two common contrasting filter materials (quartz sand and granular activated carbon-GAC), to elucidate the main factors governing their assembly, through the evaluation of environmental (i.e. filter medium type) and stochastic forces (random deaths, births and immigration). Laboratory-scale filter columns were used to mimic a rapid gravity filter; the microbiome of the filter materials, and of the filter influent and effluent, was characterised using next generation 16S rRNA gene amplicon sequencing and flow-cytometry. Chemical parameters (i.e. dissolved organic carbon, trihalomethanes formation) were also monitored to assess the final effluent quality. The filter communities seemed to be strongly assembled by selection rather than neutral processes, with only 28% of those OTUs shared with the source water detected on the filter medium following predictions using a neutral community model. GAC hosted a phylogenetically more diverse community than sand. The two filter media communities seeded the effluent water, triggering differences in both water quality and community composition of the effluents. Overall, GAC proved to be better than sand in controlling microbial growth, by promoting higher bacterial decay rates and hosting less bacterial cells, and showed better performance for putative pathogen control by leaking less Legionella cells into the effluent water.

In vitro bioassays are increasingly used for water quality monitoring. Surface water samples often need to be enriched to observe an effect and solid-phase extraction (SPE) is commonly applied for this purpose. The applied methods are typically optimised for the recovery of target chemicals and not for effect recovery for bioassays. A review of the few studies that have evaluated SPE recovery for bioassays showed a lack of experimentally determined recoveries. Therefore, we systematically measured effect recovery of a mixture of 579 organic chemicals covering a wide range of physicochemical properties that were spiked into a pristine water sample and extracted using large volume solid-phase extraction (LVSPE). Assays indicative of activation of xenobiotic metabolism, hormone receptor-mediated effects and adaptive stress responses were applied, with non-specific effects determined through cytotoxicity measurements. Overall, effect recovery was found to be similar to chemical recovery for the majority of bioassays and LVSPE blanks had no effect. Multi-layer SPE exhibited greater recovery of spiked chemicals compared to LVSPE, but the blanks triggered cytotoxicity at high enrichment. Chemical recovery data together with single chemical effect data were used to retrospectively estimate with reverse recovery modelling that there was typically less than 30% effect loss expected due to reduced SPE recovery in published surface water monitoring studies. The combination of targeted experiments and mixture modelling clearly shows the utility of SPE as a sample preparation method for surface water samples, but also emphasizes the need for adequate controls when extraction methods are adapted from chemical analysis workflows.

Im Rahmen des Projekts ReTREAT wurden verschiedene Verfahren auf deren Eignung als biologische Nachbehandlung nach einer Ozonung getestet. Der Fokus lag dabei – neben allgemeinen Reinigungseffekten – insbesondere auf dem Abbau von labilen Reaktionsprodukten sowie deren ökotoxikologischen Wirkungen.

The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L⁻¹. Two pilot-scale ozonation reactors (4–5 m³ h⁻¹), a 4-chamber reactor and a tubular reactor were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O₃/H₂O₂. The effects of selected operational parameters, such as ozone dose (0.5–3 mg L⁻¹) and H₂O₂ dose (O₃:H₂O₂ = 1:3–3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5–8.5) and initial bromide concentration (15–200 μg L⁻¹), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constant k_O3>10⁴ M⁻¹ s⁻¹ for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg/L. Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (·OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H₂O₂ addition accelerated the ozone conversion to radical ·OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr⁻ with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX) respectively, was assessed by chemical analysis and kinetic modelling. Both selected TPs were quickly formed initially to reach a maximum concentration followed by a decrease of their concentrations for longer contact times. For the studied conditions, the TP's concentrations at the outlet of the reactors ranged from 0 to 61% of the initial parent compound concentration, CTZ being a more persistent TP than TRA-NOX. Finally, it was demonstrated in both reactors that the formation of bromate (BrO₃−), a potentially carcinogenic oxidation by-product, could be controlled by H₂O₂ addition with a general improvement on micropollutant abatement. Post-treatment by granular activated carbon (GAC) filtration enabled the reduction of micropollutants and TPs concentrations but no changes in bromate were observed. The combined algae assays showed that water quality was significantly improved after oxidation and GAC post-treatment, driven by the abatement of the spiked pesticides (diuron and atrazine).

Water is a vital resource for natural ecosystems and human life, and assuring a high quality of water and protecting it from chemical contamination is a major societal goal in the European Union. The Water Framework Directive (WFD) and its daughter directives are the major body of legislation for the protection and sustainable use of European freshwater resources. The practical implementation of the WFD with regard to chemical pollution has faced some challenges. In support of the upcoming WFD review in 2019 the research project SOLUTIONS and the European monitoring network NORMAN has analyzed these challenges, evaluated the state-of-the-art of the science and suggested possible solutions. We give 10 recommendations to improve monitoring and to strengthen comprehensive prioritization, to foster consistent assessment and to support solution-oriented management of surface waters. The integration of effect-based tools, the application of passive sampling for bioaccumulative chemicals and an integrated strategy for prioritization of contaminants, accounting for knowledge gaps, are seen as important approaches to advance monitoring. Including all relevant chemical contaminants in more holistic “chemical status” assessment, using effect-based trigger values to address priority mixtures of chemicals, to better consider historical burdens accumulated in sediments and to use models to fill data gaps are recommended for a consistent assessment of contamination. Solution-oriented management should apply a tiered approach in investigative monitoring to identify toxicity drivers, strengthen consistent legislative frameworks and apply solutions-oriented approaches that explore risk reduction scenarios before and along with risk assessment.

N-Nitrosamines are potent mutagens and carcinogens that can be formed during oxidative water treatment. This study describes a novel method for the determination of total N-nitrosamines by UV-photolysis and subsequent chemiluminescence detection of nitric oxide. Denitrosation of N-nitrosamines was accomplished with a microphotochemical reactor consisting of a knitted reaction coil and a low-pressure mercury lamp. The detection limits for differing N-nitrosamines ranged between 0.07 μM (14 pmol injected) and 0.13 μM (26 pmol injected). The nitric oxide formation from selected N-nitrosamines was linear (R² = 0.98–0.99) from 0.1 to 10 μM. The small cross-section and volume of the microphotochemical reactor used in this study was optimal to reach a sensitivity level comparable to chemical denitrosation-based methods. In addition, this method had several advantages over other similar methods: (i) compared to chemical denitrosation with copper monochloride or triiodide, the UV-photolysis does not require chemicals and is not affected by interferences of byproducts (e.g., formation of NOI), (ii) the reproducibility of replicates was enhanced compared to the triiodide-based method, and (iii) a commercially available photoreactor and NO analyzer were used. The application of this method for the determination of the N-nitrosamine formation potential of personal care products demonstrates its utility for assessing whether N-nitrosodimethylamine (NDMA) or other specific nitrosamines of current interest are dominant or minor components, respectively, of the total N-nitrosamine pool in technical aquatic systems or biological samples.

Fenamates are a class of non-steroidal anti-inflammatory drugs (NSAIDs) that are not fully removed during wastewater treatment and can be released to surface waters. Here, near-surface photochemical half-lives were evaluated to range from minutes to hours of four fenamates and the closely related diclofenac. While quantum yields for direct photochemical reactions at the water surface vary widely from 0.071 for diclofenac to <0.001 for mefenamic acid, all fenamates showed significant reactivity towards singlet oxygen and hydroxyl radical with bimolecular reaction rate constants of 1.3-2.8 x 10⁷ M^-1 s^-1 and 1.1-2.7 x 10¹⁰ M^-1 s^-1, respectively. Photodecay rates increased in the presence of dissolved organic matter (DOM) for diclofenac (+19%), tolfenamic acid (+9%), and mefenamic acid (+95%), but decreased for flufenamic acid (-2%) and meclofenamic acid (-14%) after accounting for light screening effects. Fast reaction rate constants of all NSAIDs with model triplet sensitizers were quantified by laser flash photolysis. Here, the direct observation of diphenylamine radical intermediates by transient absorption spectroscopy demonstrates one-electron oxidation of all fenamates. Quenching rate constants of these radical intermediates by ascorbic acid, a model antioxidant, were also quantified. These observations suggest that the balance of oxidation by photoexcited triplet DOM and quenching of the formed radical intermediates by antioxidant moieties determines whether net sensitization or net quenching by DOM occurs in the photochemical degradation of fenamates.

Flussnahe Trinkwasserfassungen sind oft gekennzeichnet durch variierende Anteile an jungem Flusswasserinfiltrat mit kurzen Aufenthaltszeiten und regionalem älterem Grundwasser. Durch die Überlagerung von natürlichen Randbedingungen und dem Pumpbetrieb in einer Trinkwasserfassung entsteht somit eine hohe Variabilität der Rohwasserqualität in den Trinkwasserfassungen.

The design and evaluation of solutions for integrated surface water quality management requires an integrated modelling approach. Integrated models have to be comprehensive enough to cover the aspects relevant for management decisions, allowing for mapping of larger-scale processes such as climate change to the regional and local contexts. Besides this, models have to be sufficiently simple and fast to apply proper methods of uncertainty analysis, covering model structure deficits and error propagation through the chain of sub-models. Here, we present a new integrated catchment model satisfying both conditions. The conceptual "iWaQa" model was developed to support the integrated management of small streams. It can be used to predict traditional water quality parameters, such as nutrients and a wide set of organic micropollutants (plant and material protection products), by considering all major pollutant pathways in urban and agricultural environments. Due to its simplicity, the model allows for a full, propagative analysis of predictive uncertainty, including certain structural and input errors. The usefulness of the model is demonstrated by predicting future surface water quality in a small catchment with mixed land use in the Swiss Plateau. We consider climate change, population growth or decline, socio-economic development, and the implementation of management strategies to tackle urban and agricultural point and non-point sources of pollution. Our results indicate that input and model structure uncertainties are the most influential factors for certain water quality parameters. In these cases model uncertainty is already high for present conditions. Nevertheless, accounting for today's uncertainty makes management fairly robust to the foreseen range of potential changes in the next decades. The assessment of total predictive uncertainty allows for selecting management strategies that show small sensitivity to poorly known boundary conditions. The identification of important sources of uncertainty helps to guide future monitoring efforts and pinpoints key indicators, whose evolution should be closely followed to adapt management. The possible impact of climate change is clearly demonstrated by water quality substantially changing depending on single climate model chains. However, when all climate trajectories are combined, the human land use and management decisions have a larger influence on water quality against a time horizon of 2050 in the study.

In der vorliegenden Studie wurde für fünf kleine Schweizer Fliessgewässer anhand akuter und chronischer Risikoquotienten eine Risikobewertung für chemisch analysierte Pflanzenschutzmittelmischungen durchgeführt. An vier der fünf Standorte wurde ein zeitweise hohes Risiko der Mischung für Pflanzen oder wirbellose Organismen nachgewiesen. Biologische Untersuchungen unterstützen diese Risikoeinschätzung.

The Joux Valley (Swiss Jura Mountains) has a rather unusual history of human occupation, characterized by tardive but extensive settlement since the Late Middle Ages, followed by an intensive period of industrial development. To estimate the links between human activities and environmental consequences, sediment cores were retrieved in Lake Joux and submitted to a multiproxy analysis (high-resolution photographs, magnetic susceptibility, density, x-ray fluorescence, grain size, organic geochemistry, ¹⁴C, ²¹⁰Pb and ¹³⁷Cs dating). The diversity of anthropication phases, defined from historical data, is clearly recognized in the lake archive. The record suggests the region was mainly under climatic influence until the end of the 13th century. The growth of settlements in the valley and the associated massive deforestation is recorded by increasing terrestrial inputs, reflecting large-scale soil destabilization, which subsequently persists despite the transition from farming to industrial activities. Autochthonous contributions then dominate the record, both in response to climatic and anthropogenic influences. Construction works conducted at the outlet of the lake affected water flow, sedimentation and aquatic community (macrophytes, ostracods) dynamics. The substantial increase of anthropogenic heavy metals (Fe, Zn, Pb) recorded during the 20th century could reflect the development of the watch-making industry in the area, as well as the use of leaded gasoline. Historical information facilitated interpretation of the observed paleolimnological evolution in the context of varied coexisting human activities. This study highlights the importance of applying an integrated paleolimnological-historical approach in order to establish clear links between well-defined human activities and their subsequent environmental responses through time.

Ozonation of secondary wastewater effluents can reduce the discharge of micropollutants by transforming their chemical structures. Therefore, a better understanding of the formation of transformation products during ozonation is important. In this study, a computer-based prediction platform for the kinetics and mechanisms of the reactions of ozone with organic compounds was developed to enable in silico predictions of transformation products. With the developed prediction platform, reaction kinetics expressed as second-order rate constants for the reactions of ozone with selected organic compounds (k_O3, M⁻¹ s⁻¹) can be predicted based on an adapted k_O3 prediction model from a previous study (Lee et al., Environ. Sci. Technol., 2015, 49 , 9925–9935) (average model error of about a factor of 6 for 14 compound classes with 284 model compounds). Ozone reaction mechanisms reported in the literature have been reviewed and, using chemoinformatics tools, encoded into about 340 individual reaction rules that can be generally applied to predict the transformation products of micropollutants. Predictions for k_O3 and/or transformation products were overall consistent with the experimental data for three micropollutants used as validation compounds (e.g., carbamazepine, tramadol, and triclosan). However, limitations of the current k_O3 prediction platform were also identified: ambiguous assignment of the n-th highest occupied molecular orbital energy (E_HOMO−n) to the reactive sites, potential errors associated with the use of a gas-phase geometry, and a poor k_O3 prediction for certain compounds (cetirizine). Therefore, the current prediction tool should not be considered as a substitute for experimental studies and experimental data are still required in the future to obtain a more robust prediction model. Nonetheless, the developed prediction platform, made available as a stand-alone graphical user interface (GUI) application, will provide useful information about aqueous ozone chemistry to various groups of end-users such as environmental chemists, engineers, or toxicologists.

Improved micropollutant (MP) biotransformation during biological wastewater treatment has been associated with high ammonia oxidation activities, suggesting co-metabolic biotransformation by ammonia oxidizing bacteria as an underlying mechanism. The goal of this study was to clarify the contribution of ammonia oxidizing bacteria to increased MP degradation in nitrifying activated sludge (NAS) communities using a series of inhibition experiments. To this end, we treated a NAS community with two different ammonia oxidation inhibitors, namely octyne (OCT), a mechanistic inhibitor that covalently binds to ammonia monooxygenases, and allylthiourea (ATU), a copper chelator that depletes copper ions from the active center of ammonia monooxygenases. We investigated the biotransformation of 79 structurally different MPs by the inhibitor-treated and untreated sludge communities. Fifty-five compounds exhibited over 20% removal in the untreated control after a 46 h-incubation. Of these, 31 compounds were significantly inhibited by either ATU and/or OCT. For 17 of the 31 MPs, the inhibition by ATU at 46 h was substantially higher than by OCT despite the full inhibition of ammonia oxidation by both inhibitors. This was particularly the case for almost all thioether and phenylurea compounds tested, suggesting that in nitrifying activated sludge communities, ATU does not exclusively act as an inhibitor of bacterial ammonia oxidation. Rather, ATU also inhibited enzymes contributing to MP biotransformation but not to bulk ammonia oxidation. Thus, inhibition studies with ATU tend to overestimate the contribution of ammonia-oxidizing bacteria to MP biotransformation in nitrifying activated sludge communities. Biolog tests revealed only minor effects of ATU on the heterotrophic respiration of common organic substrates by the sludge community, suggesting that ATU did not affect enzymes that were essential in energy conservation and central metabolism of heterotrophs. By comparing ATU- and OCT-treated samples, as well as before and after ammonia oxidation was recovered in OCT-treated samples, we were able to demonstrate that ammonia-oxidizing bacteria were highly involved in the biotransformation of four compounds: asulam, clomazone, monuron and trimethoprim.

Measuring the exposome remains a challenge due to the range and number of anthropogenic molecules that are encountered in our daily lives, as well as the complex systemic responses to these exposures. One option for improving the coverage, dynamic range and throughput of measurements is to incorporate ion mobility spectrometry (IMS) into current MS-based analytical methods. The implementation of IMS in exposomics studies will lead to more frequent observations of previously undetected chemicals and metabolites. LC-IMS-MS will provide increased overall measurement dynamic range, resulting in detections of lower abundance molecules. Alternatively, the throughput of IMS-MS alone will provide the opportunity to analyze many thousands of longitudinal samples over lifetimes of exposure, capturing evidence of transitory accumulations of chemicals or metabolites. The volume of data corresponding to these new chemical observations will almost certainly outpace the generation of reference data to enable their confident identification. In this perspective, we briefly review the state-of-the-art in measuring the exposome, and discuss the potential use for IMS-MS and the physico-chemical property of collisional cross section in both exposure assessment and molecular identification.

Das Trinkwassergewinnungsgebiet Hardwald ist geologisch und hydrogeologisch komplex, zudem existieren zahlreiche Randeinflüsse sowie diverse historische Belastungen. Um eine gute Trinkwasserqualität zu gewährleisten, ist es deshalb von grosser Bedeutung, mögliche Mischungsprozesse verschiedener Wässer zu identifizieren. Hierfür wurde im Rahmen des Projekts «Regionale Wasserversorgung Basel-Landschaft 21» die zur Verfügung stehende Datenmenge zur Hydrochemie ausgewertet.

Micropollutants enter surface waters through various pathways, of which wastewater treatment plants (WWTPs) are a major source. The large diversity of micropollutants and their many modes of toxic action pose a challenge for assessing environmental risks. In this study, we investigated the potential impact of WWTPs on receiving ecosystems by describing concentration patterns of micropollutants, predicting acute risks for aquatic organisms and validating these results with macroinvertebrate biomonitoring data. Grab samples were taken upstream, downstream and at the effluent of 24 Swiss WWTPs during low flow conditions across independent catchments with different land uses. Using liquid chromatography high resolution tandem mass spectrometry, a comprehensive target screening of almost 400 organic substances, focusing mainly on pesticides and pharmaceuticals, was conducted at two time points, and complemented with the analysis of a priority mixture of 57 substances over eight time points. Acute toxic pressure was predicted using the risk assessment approach of the multi-substance potentially affected fraction, first applying concentration addition for substances with the same toxic mode of action and subsequently response addition for the calculation of the risk of the total mixture. This toxic pressure was compared to macroinvertebrate sensitivity to pesticides (SPEAR index) upstream and downstream of the WWTPs. The concentrations were, as expected, especially for pharmaceuticals and other household chemicals higher downstream than upstream, with the detection frequency of plant protection products upstream correlating with the fraction of arable land in the catchments. While the concentration sums downstream were clearly dominated by pharmaceuticals or other household chemicals, the acute toxic pressure was mainly driven by pesticides, often caused by the episodic occurrence of these compounds even during low flow conditions. In general, five single substances explained much of the total risk, with diclofenac, diazinon and clothianidin as the main drivers. Despite the low predicted acute risk of 0%–2.1% for affected species, a significant positive correlation with macroinvertebrate sensitivity to pesticides was observed. However, more effect data for pharmaceuticals and a better quantification of episodic pesticide pollution events are needed for a more comprehensive risk assessment.

Surface waters can contain a range of micropollutants from point sources, such as wastewater effluent, and diffuse sources, such as agriculture. Characterizing the source of micropollutants is important for reducing their burden and thus mitigating adverse effects on aquatic ecosystems. In this study, chemical analysis and bioanalysis were applied to assess the micropollutant burden during low flow conditions upstream and downstream of three wastewater treatment plants (WWTPs) discharging into small streams in the Swiss Plateau. The upstream sites had no input of wastewater effluent, allowing a direct comparison of the observed effects with and without the contribution of wastewater. Four hundred and five chemicals were analyzed, while the applied bioassays included activation of the aryl hydrocarbon receptor, activation of the androgen receptor, activation of the estrogen receptor, photosystem II inhibition, acetylcholinesterase inhibition and adaptive stress responses for oxidative stress, genotoxicity and inflammation, as well as assays indicative of estrogenic activity and developmental toxicity in zebrafish embryos. Chemical analysis and bioanalysis showed higher chemical concentrations and effects for the effluent samples, with the lowest chemical concentrations and effects in most assays for the upstream sites. Mixture toxicity modeling was applied to assess the contribution of detected chemicals to the observed effect. For most bioassays, very little of the observed effects could be explained by the detected chemicals, with the exception of photosystem II inhibition, where herbicides explained the majority of the effect. This emphasizes the importance of combining bioanalysis with chemical analysis to provide a more complete picture of the micropollutant burden. While the wastewater effluents had a significant contribution to micropollutant burden downstream, both chemical analysis and bioanalysis showed a relevant contribution of diffuse sources from upstream during low flow conditions, suggesting that upgrading WWTPs will not completely reduce the micropollutant burden, but further source control measures will be required.

Bei der ökotoxikologischen Bewertung von Pharmazeutika stehen bisher vor allem die Muttersubstanzen im Fokus. Dies ist vor allem dem Umstand geschuldet, dass für ihre Transformationsprodukte (TP) meist nur wenige, wenn überhaupt, ökotoxikologische Effektwerte vorhanden sind. Am Beispiel von Carbamazepin, Clarithromycin und Metformin und deren fünf Haupt-TP wurden verschiedene Bewertungskonzepte für TP angewendet und verglichen. Basierend auf diesem Vergleich werden Handlungsmöglichkeiten für die Bewertung von TP aufgezeigt und diskutiert.

We quantified the concentrations of two little-studied brominated pollutants, 1,3,5-tribromobenzene (TBB) and 4-bromobiphenyl (4BBP), in the deep water column and sediments of Lake Geneva. We found aqueous concentrations of 625 ± 68 pg L^–1 for TBB and 668 ± 86 pg L^–1 for 4BBP over a depth range of 70–191.5 m (near-bottom depth), based on duplicate measurements taken at five depths during three separate 1 month sampling periods at our sampling site near Vidy Bay. These levels of TBB and 4BBP were 1 or 2 orders of magnitude higher than the quantified aqueous concentrations of the components of the pentabrominated biphenyl ether technical mixture, which is a flame retardant product that had a high production volume in Europe before 2001. We observed statistically significant vertical concentration trends for both TBB and 2,2′,4,4′,6-pentabromobiphenyl ether in the deep water column, which indicates that transport and/or degradation processes affect these compounds. These measurements were enabled by application of a comprehensive two-dimensional gas chromatograph coupled to an electron capture negative chemical ionization time-of-flight mass spectrometer (GC×GC-ENCI-TOFMS) and to a micro-electron capture detector (GC×GC-μECD). GC×GC-ENCI-TOFMS and GC×GC-μECD were found to be >10× more sensitive toward brominated pollutants than conventional GC×GC-EI-TOFMS (with an electron impact (EI) ionization source), the latter of which had insufficient sensitivity to detect these emerging brominated pollutants in the analyzed samples. GC×GC also enabled the estimation of several environmentally relevant partitioning properties of TBB and 4BBP, further confirming previous evidence that these pollutants are bioaccumulative and have long-range transport potential.

The implementation of targeted and nontargeted chemical screening analysis in combination with in vitro and organism-level bioassays is a prerequisite for a more holistic monitoring of water quality in the future. For chemical analysis, little or no sample enrichment is often sufficient, while bioanalysis often requires larger sample volumes at a certain enrichment factor for conducting comprehensive bioassays on different endpoints or further effect-directed analysis (EDA). To avoid logistic and technical issues related to the storage and transport of large volumes of water, sampling would benefit greatly from onsite extraction. This study presents a novel onsite large volume solid phase extraction (LVSPE) device tailored to fulfill the requirements for the successful effect-based and chemical screening of water resources and complies with available international standards for automated sampling devices. Laboratory recovery experiments using 251 organic compounds in the log D range from−3.6 to 9.4 (at pH 7.0) spiked into pristine water resulted in acceptable recoveries and from 60 to 123% for 159 out of 251 substances. Within a European-wide demonstration program, the LVSPE was able to enrich compounds in concentration ranges over three orders of magnitude (1 ng L⁻¹ to 2400 ng L⁻¹). It was possible to discriminate responsive samples from samples with no or only low effects in a set of six different bioassays (i.e. acetylcholinesterase and algal growth inhibition, androgenicity, estrogenicity, fish embryo toxicity, glucocorticoid activity). The LVSPE thus proved applicable for onsite extraction of sufficient amounts of water to investigate water quality thoroughly by means of chemical analysis and effect-based tools without the common limitations due to small sample volumes.

Background: The fourth round of the Critical Assessment of Small Molecule Identification (CASMI) Contest (www.casmi-contest.org) was held in 2016, with two new categories for automated methods. This article covers the 208 challenges in Categories 2 and 3, without and with metadata, from organization, participation, results and post-contest evaluation of CASMI 2016 through to perspectives for future contests and small molecule annotation/identification.
Results: The Input Output Kernel Regression (CSI:IOKR) machine learning approach performed best in “Category 2: Best Automatic Structural Identification—In Silico Fragmentation Only”, won by Team Brouard with 41% challenge wins. The winner of “Category 3: Best Automatic Structural Identification—Full Information” was Team Kind (MS-FINDER), with 76% challenge wins. The best methods were able to achieve over 30% Top 1 ranks in Category 2, with all methods ranking the correct candidate in the Top 10 in around 50% of challenges. This success rate rose to 70% Top 1 ranks in Category 3, with candidates in the Top 10 in over 80% of the challenges. The machine learning and chemistry-based approaches are shown to perform in complementary ways.
Conclusions: The improvement in (semi-)automated fragmentation methods for small molecule identification has been substantial. The achieved high rates of correct candidates in the Top 1 and Top 10, despite large candidate numbers, open up great possibilities for high-throughput annotation of untargeted analysis for “known unknowns”. As more high quality training data becomes available, the improvements in machine learning methods will likely continue, but the alternative approaches still provide valuable complementary information. Improved integration of experimental context will also improve identification success further for “real life” annotations. The true “unknown unknowns” remain to be evaluated in future CASMI contests.

Im Projekt EcoImpact wurden die ökotoxikologischen und ökologischen Effekte von Mikroverunreinigungen aus Kläranlagen auf aquatische Lebensgemeinschaften untersucht. Chemische und biologische Untersuchungen oberhalb und unterhalb von Kläranlagen deuten auf Effekte dieser Stoffe hin, die von physiologischen Antworten der Organismen bis hin zu veränderten Ökosystemfunktionen wie z. B. dem Laubabbau reichen. Gezielte Rinnenexperimente mit kontrollierter Wasserqualität unterstützen diese Befunde.

Phytoplankton constitute an important component of surface water ecosystems; however little is known about their contribution to biotransformation of organic micropollutants. To elucidate biotransformation processes, batch experiments with two cyanobacterial species (Microcystis aeruginosa and Synechococcus sp.) and one green algal species (Chlamydomonas reinhardtii) were conducted. Twenty-four micropollutants were studied, including 15 fungicides and 9 pharmaceuticals. Online solid phase extraction (SPE) coupled with liquid chromatography (LC)-high resolution tandem mass spectrometry (HRMS/MS) was used together with suspect and nontarget screening to identify transformation products (TPs). 14 TPs were identified for 9 micropollutants, formed by cytochrome P450-mediated oxidation, conjugation and methylation reactions. The observed transformation pathways included reactions likely mediated by promiscuous enzymes, such as glutamate conjugation to mefenamic acid and pterin conjugation of sulfamethoxazole. For 15 compounds, including all azole fungicides tested, no TPs were identified. Environmentally relevant concentrations of chemical stressors had no influence on the transformation types and rates.

The overarching aim of this field study was to examine causal links between in-situ exposure to complex mixtures of micropollutants from wastewater treatment plants and effects on freshwater microbial communities in the receiving streams. To reach this goal, we assessed the toxicity of serial dilutions of micropollutant mixtures, extracted from deployed passive samplers at the discharge sites of four Swiss wastewater treatment plants, to in situ periphyton from upstream and downstream of the effluents. On the one hand, comparison of the sensitivities of upstream and downstream periphyton to the micropollutant mixtures indicated that algal and bacterial communities composing the periphyton displayed higher tolerance towards these micropollutants downstream than upstream. On the other hand, molecular analyses of the algal and bacterial structure showed a clear separation between upstream and downstream periphyton across the sites. This finding provides an additional line of evidence that micropollutants from the wastewater discharges were directly responsible for the change in the community structure at the sampling sites by eliminating the micropollutant-sensitive species and favouring the tolerant ones. What is more, the fold increase of algal and bacterial tolerance from upstream to downstream locations was variable among sampling sites and was strongly correlated to the intensity of contamination by micropollutants at the respective sites. Overall, our study highlights the sensitivity of the proposed approach to disentangle effects of micropollutant mixtures from other environmental factors occurring in the field and, thus, establishing a causal link between exposure and the observed ecological effects on freshwater microbial communities.

Im Hardwald bei Muttenz wird zur Trinkwasseraufbereitung Rheinwasser versickert. Während der Bodenpassage wird rund die Hälfte der vorhandenen Spurenstoffe im Rheinwasser entfernt. Ein Grossteil der restlichen Substanzen wird durch die Aktivkohlefiltration des angereicherten Grundwassers entfernt. Wie gut die Spurenstoffe im Aktivkohlefilter zurückgehalten werden und ob eine vor- oder nachgeschaltete Oxidation zu einer besseren Entfernung führen kann, wird in der nachfolgend vorgestellten Studie aufgezeigt. Die Studie wurde im Rahmen des Projekts "Regionale Wasserversorgung Basel-Landschaft 21" realisiert.

Citalopram (CTR) is a worldwide highly consumed antidepressant which has demonstrated incomplete removal by conventional wastewater treatment. Despite its global ubiquitous presence in different environmental compartments, little is known about its behaviour and transformation processes during wastewater treatment. The present study aims to expand the knowledge on fate and transformation of CTR during the biological treatment process. For this purpose, batch reactors were set up to assess biotic, abiotic and sorption losses of this compound. One of the main objectives of the study was the identification of the formed transformation products (TPs) by applying suspect and non-target strategies based on liquid chromatography quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS). The complementary use of reversed phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC) for the identification of polar TPs, and the application of in-house developed quantitative structure-retention relationship (QSRR) prediction models, in addition to the comprehensive evaluation of the obtained MS/MS spectra, provided valuable information to support identification. In total, fourteen TPs were detected and thirteen of them were tentatively identified. Four compounds were confirmed (N-desmethylCTR, CTR amide, CTR carboxylic acid and 3-oxo-CTR) through the purchase of the corresponding reference standard. Probable structures based on diagnostic evidence were proposed for the additional nine TPs. Eleven TPs are reported for the first time. A transformation pathway for the biotransformation of CTR was proposed. The presence of the identified TPs was assessed in real wastewater samples through retrospective analysis, resulting in the detection of five compounds. Finally, the potential ecotoxicological risk posed by CTR and its TPs to different trophic levels of aquatic organisms was evaluated by means of risk quotients.

Human-induced environmental changes are causing major shifts in ecosystems around the globe. To support environmental management, scientific research has to infer both general trends and context dependency in these shifts at global and local scales. Combining replicated real-world experiments, which take advantage of implemented mitigation measures or other forms of human impact, with research-led experimental manipulations can provide powerful scientific tools for inferring causal drivers of ecological change and the generality of their effects. Additionally, combining these two approaches can facilitate communication with stakeholders involved in implementing management strategies. We demonstrate such an integrative approach using the case study EcoImpact, which aims at empirically unravelling the impacts of wastewater-born micropollutants on aquatic ecosystems.

Citalopram (CTR) is a worldwide highly consumed antidepressant which has demonstrated incomplete removal by conventional wastewater treatment. Despite its global ubiquitous presence in different environmental compartments, little is known about its behaviour and transformation processes during wastewater treatment. The present study aims to expand the knowledge on fate and transformation of CTR during the biological treatment process. For this purpose, batch reactors were set up to assess biotic, abiotic and sorption losses of this compound. One of the main objectives of the study was the identification of the formed transformation products (TPs) by applying suspect and non-target strategies based on liquid chromatography quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS). The complementary use of reversed phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC) for the identification of polar TPs, and the application of in-house developed quantitative structure-retention relationship (QSRR) prediction models, in addition to the comprehensive evaluation of the obtained MS/MS spectra, provided valuable information to support identification. In total, fourteen TPs were detected and thirteen of them were tentatively identified. Four compounds were confirmed (N-desmethylCTR, CTR amide, CTR carboxylic acid and 3-oxo-CTR) through the purchase of the corresponding reference standard. Probable structures based on diagnostic evidence were proposed for the additional nine TPs. Eleven TPs are reported for the first time. A transformation pathway for the biotransformation of CTR was proposed. The presence of the identified TPs was assessed in real wastewater samples through retrospective analysis, resulting in the detection of five compounds. Finally, the potential ecotoxicological risk posed by CTR and its TPs to different trophic levels of aquatic organisms was evaluated by means of risk quotients.

The Dagstuhl Seminar 15492 on Computational Metabolomics brought together leading experimental(analytical chemistry and biology) and computational (computer science and bioinformatics)experts with the aim to foster the exchange of expertise needed to advance computationalmetabolomics. The focus was on a dynamic schedule with overview talks followed by breakoutsessions, selected by the participants, covering the whole experimental-computational continuumin mass spectrometry, as well as the use of metabolomics data in applications. A general observationwas that metabolomics is in the state that genomics was 20 years ago and that while theavailability of data is holding back progress, several good initiatives are present. The importanceof small molecules to life should be communicated properly to assist initiating a global metabolomicsinitiative, such as the Human Genome project. Several follow-ups were discussed, includingworkshops, hackathons, joint paper(s) and a new Dagstuhl Seminar in two years to follow up onthis one.

The efficiency of wastewater ozonation for the abatement of three nitrogen-containing pharmaceuticals, two antihistamine drugs, cetirizine (CTR) and fexofenadine (FXF), and the diuretic drug, hydrochlorothiazide (HCTZ), was investigated. Species-specific second-order rate constants for the reactions of the molecular, protonated (CTR, FXF) or deprotonated (HCTZ) forms of these compounds with ozone were determined. All three compounds are very reactive with ozone (apparent second order rate constants at pH 7: k_O3,pH7 = 1.7·10⁵ M⁻¹s⁻¹, 8.5·10⁴ M⁻¹s⁻¹ and 9.0·10³ M⁻¹s⁻¹ for CTR, HCTZ and FXF, respectively). Transformation product (TP) structures were elucidated using liquid chromatography coupled with high-resolution tandem mass spectrometry, including isotope-labeled standards. For cetirizine and hydrochlorothiazide 8 TPs each and for fexofenadine 7 TPs were identified. The main TPs of cetirizine and fexofenadine are their respective N-oxides, whereas chlorothiazide forms to almost 100% from hydrochlorothiazide. In the bacteria bioluminescence assay the toxicity was slightly increased only during the ozonation of cetirizine at very high cetirizine concentrations. The main TPs detected in bench-scale experiments were also detected in full-scale ozonation of a municipal wastewater, for >90% elimination of the parent compounds.

This study aimed at gaining knowledge on the degradation pathway during biological treatment of wastewater of diclofenac and 4′-hydroxydiclofenac, its main human metabolite. For that purpose, an aerobic MBR was acclimatised to diclofenac, and the MBR biomass subsequently incubated with ¹⁴C-diclofenac or ¹⁴C-4′hydroxydiclofenac over 25 days. It was demonstrated that diclofenac degradation was much slower and limited than that of 4′-hydroxydiclofenac. Indeed, after 18 days of batch incubation, diclofenac was removed up to 40%, this rate remained stable till the end of the experiment, while 4′-hydroxydiclofenac was completely degraded within nine days. The analyses of supernatant samples have shown that diclofenac degradation led to four transformation products, more polar than the parent compound, one of them being 4′-hydroxydiclofenac. The degradation of 4′-hydroxydiclofenac led to the formation of the same metabolites than those detected during diclofenac degradation. With these results, the hydroxylation of diclofenac to 4′-hydroxydiclofenac was identified as one major bottleneck in diclofenac degradation during biological treatment of wastewater.

Aquatic environments are often contaminated with complex mixtures of chemicals that may pose a risk to ecosystems and human health. This contamination cannot be addressed with target analysis alone but tools are required to reduce this complexity and identify those chemicals that might cause adverse effects. Effect-directed analysis (EDA) is designed to meet this challenge and faces increasing interest in water and sediment quality monitoring. Thus, the present paper summarizes current experience with the EDA approach and the tools required, and provides practical advice on their application. The paper highlights the need for proper problem formulation and gives general advice for study design. As the EDA approach is directed by toxicity, basic principles for the selection of bioassays are given as well as a comprehensive compilation of appropriate assays, including their strengths and weaknesses. A specific focus is given to strategies for sampling, extraction and bioassay dosing since they strongly impact prioritization of toxicants in EDA. Reduction of sample complexity mainly relies on fractionation procedures, which are discussed in this paper, including quality assurance and quality control. Automated combinations of fractionation, biotesting and chemical analysis using so-called hyphenated tools can enhance the throughput and might reduce the risk of artifacts in laboratory work. The key to determining the chemical structures causing effects is analytical toxicant identification. The latest approaches, tools, software and databases for target-, suspect and non-target screening as well as unknown identification are discussed together with analytical and toxicological confirmation approaches. A better understanding of optimal use and combination of EDA tools will help to design efficient and successful toxicant identification studies in the context of quality monitoring in multiply stressed environments.

Marine environments are frequently exposed to oil spills as a result of transportation, oil drilling or fuel usage. Whereas large oil spills and their effects have been widely documented, more common and recurrent small spills typically escape attention. To fill this important gap in the assessment of oil-spill effects, we performed two independent supervised full sea releases of 5 m³ of crude oil, complemented by on-board mesocosm studies and sampling of accidentally encountered slicks. Using rapid on-board biological assays, we detect high bioavailability and toxicity of dissolved and dispersed oil within 24 h after the spills, occurring fairly deep (8 m) below the slicks. Selective decline of marine plankton is observed, equally relevant for early stages of larger spills. Our results demonstrate that, contrary to common thinking, even small spills have immediate adverse biological effects and their recurrent nature is likely to affect marine ecosystem functioning.

Human land uses and population growth represent major global threats to biodiversity and ecosystem services. Understanding how biological communities respond to multiple drivers of human-induced environmental change is fundamental for conserving ecosystems and remediating degraded habitats. Here, we used a replicated ‘real-world experiment’ to study the responses of invertebrate communities to wastewater perturbations across a land-use intensity gradient in 12 Swiss streams. We used different taxonomy and trait-based community descriptors to establish the most sensitive indicators detecting impacts and to help elucidate potential causal mechanisms of change. First, we predicted that streams in catchments adversely impacted by human land-uses would be less impaired by wastewater inputs because their invertebrate communities should be dominated by pollution-tolerant taxa (‘environmental context’). Second, we predicted that the negative effects of wastewater on stream invertebrate communities should be larger in streams that receive proportionally more wastewater (‘magnitude of disturbance’). In support of the ‘environmental context’ hypothesis, we found that change in the Saprobic Index (a trait-based indicator of tolerance to organic pollution) was associated with upstream community composition; communities in catchments with intensive agricultural land uses (e.g., arable cropping and pasture) were generally more resistant to eutrophication associated with wastewater inputs. We also found support for the ‘magnitude of disturbance’ hypothesis. The SPEAR Index (a trait-based indicator of sensitivity to pesticides) was more sensitive to the relative input of effluent, suggesting that toxic influences of wastewater scale with dilution. Whilst freshwater pollution continues to be a major environmental problem, our findings highlight that the same anthropogenic pressure (i.e., inputs of wastewater) may induce different ecological responses depending on the environmental context and community metrics used. Thus, remediation strategies aiming to improve stream ecological status (e.g., rehabilitating degraded reaches) need to consider upstream anthropogenic influences and the most appropriate indicators of restoration success.

The main removal process for polar organic micropollutants during activated sludge treatment is biotransformation, which often leads to the formation of stable transformation products (TPs). Because the analysis of TPs is challenging, the use of pathway prediction systems can help by generating a list of suspected TPs. To complete and refine pathway prediction, comprehensive biotransformation studies for compounds exhibiting pertinent functional groups under environmentally relevant conditions are needed. Because many polar organic micropollutants present in wastewater contain one or several amine functional groups, we systematically explored amine biotransformation by conducting experiments with 19 compounds that contained 25 structurally diverse primary, secondary, and tertiary amine moieties. The identification of 144 TP candidates and the structure elucidation of 101 of these resulted in a comprehensive view on initial amine biotransformation reactions. The reactions with the highest relevance were N-oxidation, N-dealkylation, N-acetylation, and N-succinylation. Whereas many of the observed reactions were similar to those known for the mammalian metabolism of amine-containing xenobiotics, some N-acylation reactions were not previously described. In general, different reactions at the amine functional group occurred in parallel. Finally, recommendations on how these findings can be implemented to improve microbial pathway prediction of amine-containing micropollutants are given.

Rationale: Oxygen isotope fractionation of molecular O₂ is an important process for the study of aerobic metabolism, photosynthesis, and formation of reactive oxygen species. The latter is of particular interest for investigating the mechanism of enzyme-catalyzed reactions, such as the oxygenation of organic pollutants, which is an important detoxification mechanism.
Methods: We developed a simple method to measure the δ¹⁸O values of dissolved O₂ in small samples using automated split injection for gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). After creating a N₂ headspace, the dissolved O₂ partitions from aqueous solution to the headspace, from which it can be injected into the gas chromatograph.
Results: In aqueous samples of 10 mL and in diluted air samples, we quantified the δ¹⁸O values at O₂ concentrations of 16 μM and 86 μM, respectively. The chromatographic separation of O₂ and N₂ with a molecular sieve column made it possible to use N₂ as the headspace gas for the extraction of dissolved O₂ from water. We were therefore able to apply a rigorous δ¹⁸O blank correction for the quantification of ¹⁸O/¹⁶O ratios in 20 nmol of injected O₂.
Conclusions: The successful quantification of ¹⁸O-kinetic isotope effects associated with enzymatic and chemical reduction of dissolved O₂ illustrates how the proposed method can be applied for studying enzymatic O₂ activation mechanisms in a variety of (bio)chemical processes.

Background: The in silico fragmenter MetFrag, launched in 2010, was one of the first approaches combining compound database searching and fragmentation prediction for small molecule identification from tandem mass spectrometry data. Since then many new approaches have evolved, as has MetFrag itself. This article details the latest developments to MetFrag and its use in small molecule identification since the original publication.
Results: MetFrag has gone through algorithmic and scoring refinements. New features include the retrieval of reference, data source and patent information via ChemSpider and PubChem web services, as well as InChIKey filtering to reduce candidate redundancy due to stereoisomerism. Candidates can be filtered or scored differently based on criteria like occurence of certain elements and/or substructures prior to fragmentation, or presence in so-called "suspect lists". Retention time information can now be calculated either within MetFrag with a sufficient amount of user-provided retention times, or incorporated separately as "user-defined scores" to be included in candidate ranking. The changes to MetFrag were evaluated on the original dataset as well as a dataset of 473 merged high resolution tandem mass spectra (HR-MS/MS) and compared with another open source in silico fragmenter, CFM-ID. Using HR-MS/MS information only, MetFrag2.2 and CFM-ID had 30 and 43 Top 1 ranks, respectively, using PubChem as a database. Including reference and retention information in MetFrag2.2 improved this to 420 and 336 Top 1 ranks with ChemSpider and PubChem (89 and 71 %), respectively, and even up to 343 Top 1 ranks (PubChem) when combining with CFM-ID. The optimal parameters and weights were verified using three additional datasets of 824 merged HR-MS/MS spectra in total. Further examples are given to demonstrate flexibility of the enhanced features.
Conclusions: In many cases additional information is available from the experimental context to add to small molecule identification, which is especially useful where the mass spectrum alone is not sufficient for candidate selection from a large number of candidates. The results achieved with MetFrag2.2 clearly show the benefit of considering this additional information. The new functions greatly enhance the chance of identification success and have been incorporated into a command line interface in a flexible way designed to be integrated into high throughput workflows. Feedback on the command line version of MetFrag2.2 available at c-ruttkies.github.io/MetFrag/ is welcome.

Online solid-phase extraction was combined with nano-liquid chromatography coupled to high-resolution mass spectrometry (HRMS) for the analysis of micropollutants in environmental samples from small volumes. The method was validated in surface water, Microcystis aeruginosa cell lysate, and spent Microcystis growth medium. For 41 analytes, quantification limits of 0.1–28 ng/L (surface water) and 0.1–32 ng/L (growth medium) were obtained from only 88 μL of sample. In cell lysate, quantification limits ranged from 0.1–143 ng/L or 0.33–476 ng/g dry weight from a sample of 88 μL, or 26 μg dry weight, respectively. The method matches the sensitivity of established online and offline solid-phase extraction–liquid chromatography–mass spectrometry methods but requires only a fraction of the sample used by those techniques, and is among the first applications of nano-LC-MS for environmental analysis. The method was applied to the determination of bioconcentration in Microcystis aeruginosa in a laboratory experiment, and the benefit of coupling to HRMS was demonstrated in a transformation product screening.

At present, mass spectrometry (MS)-based metabolomics has been widely used to obtain new insights into human, plant, and microbial biochemistry; drug and biomarker discovery; nutrition research; and food control. Despite the high research interest, identifying and characterizing the structure of metabolites has become a major drawback for converting raw MS data into biological knowledge. Comprehensive and well-annotated MS-based spectral databases play a key role in serving this purpose via the formation of metabolite annotations. The main characteristics of the mass spectral databases currently used in MS-based metabolomics are reviewed in this study, underlining their advantages and limitations. In addition, the overlap of compounds with MSⁿ (n ≥ 2) spectra from authentic chemical standards in most public and commercial databases has been calculated for the first time. Finally, future prospects of mass spectral databases are discussed in terms of the needs posed by novel applications and instrumental advancements.

The University of Minnesota Biocatalysis/Biodegradation Database and Pathway Prediction System (UM-BBD/PPS) has been a unique resource covering microbial biotransformation pathways of primarily xenobiotic chemicals for over 15 years. This paper introduces the successor system, enviPath (The Environmental Contaminant Biotransformation Pathway Resource), which is a complete redesign and reimplementation of UM-BBD/PPS. enviPath uses the database from the UM-BBD/PPS as a basis, extends the use of this database, and allows users to include their own data to support multiple use cases. Relative reasoning is supported for the refinement of predictions and to allow its extensions in terms of previously published, but not implemented machine learning models. User access is simplified by providing a REST API that simplifies the inclusion of enviPath into existing workflows. An RDF database is used to enable simple integration with other databases. enviPath is publicly available at envipath.org with free and open access to its core data.

During rain events, biocides and plant protection products are transported from agricultural fields but also from urban sources to surface waters. Originally designed to be biologically active, these compounds may harm organisms in aquatic ecosystems. Although several models allow either urban or agricultural storm events to be predicted, only few combine these two sources, and none of them include biocide losses from building envelopes. This study therefore aims to develop a model designed to predict water and substance flows from urban and agricultural sources to surface waters. We developed a model based on physical principles for water percolation and substance flow including micro- (also called matrix-) and macropore-flows for the agricultural areas together with a model representing sources, sewer systems and a wastewater treatment plant for urban areas. In a second step, the combined model was applied to a catchment where an extensive field study had been conducted. The modelled and measured discharge and compound results corresponded reasonably well in terms of quantity and dynamics. The total cumulative discharge was only slightly lower than the total measured discharge (factor 0.94). The total modelled losses of the agriculturally used herbicide atrazine were slightly lower (∼25%) than the measured losses when the soil pore water distribution coefficient (describing the partition between soil particles and pore water) (K_d) was kept constant and slightly higher if it was increased with time. The modelled urban losses of diuron from facades were within a factor of three with respect to the measured values. The results highlighted the change in importance of the flow components during a rain event from urban sources during the most intensive rain period towards agricultural ones over a prolonged time period. Applications to two other catchments, one neighbouring and one on another continent showed that the model can be applied using site specific data for land use, pesticide application, weather and literature data for soil related parameters such as saturated water content, hydraulic conductivity or lateral distances of the drainage pipes without any further calibration of parameters. This is a promising basis for using the model in a wide range of catchments.

DNA-encoded chemical libraries (DECLs) are collections of organic compounds that are individually linked to different oligonucleotides, serving as amplifiable identification barcodes. As all compounds in the library can be identified by their DNA tags, they can be mixed and used in affinity-capture experiments on target proteins of interest. In this protocol, we describe the screening process that allows the identification of the few binding molecules within the multiplicity of library members. First, the automated affinity selection process physically isolates binding library members. Second, the DNA codes of the isolated binders are PCR-amplified and subjected to high-throughput DNA sequencing. Third, the obtained sequencing data are evaluated using a C++ program and the results are displayed using MATLAB software. The resulting selection fingerprints facilitate the discrimination of binding from nonbinding library members. The described procedures allow the identification of small organic ligands to biological targets from a DECL within 10 d.

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe²⁺ and Fe³⁺ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe²⁺ associated with iron oxide surfaces (i.e., oxide-associated Fe²⁺) often reduces oxidized contaminants much faster than aqueous Fe²⁺ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe²⁺ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (E_H) values in solutions containing these oxides at different pH values and aqueous Fe²⁺ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (E_H⁰) values of 768 ± 1 mV for the aqueous Fe²⁺–goethite redox couple and 769 ± 2 mV for the aqueous Fe²⁺–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering E_H values of aqueous Fe³⁺/Fe²⁺ redox couples.

With the expansion of offshore petroleum extraction, validated models are needed to simulate the behaviors of petroleum compounds released in deep (>100 m) waters. We present a thermodynamic model of the densities, viscosities, and gas–liquid−water partitioning of petroleum mixtures with varying pressure, temperature, and composition based on the Peng–Robinson equation-of-state and the modified Henry’s law (Krychevsky−Kasarnovsky equation). The model is applied to Macondo reservoir fluid released during the Deepwater Horizon disaster, represented with 279–280 pseudocomponents, including 131–132 individual compounds. We define >n-C₈ pseudocomponents based on comprehensive two-dimensional gas chromatography (GC × GC) measurements, which enable the modeling of aqueous partitioning for n-C₈ to n-C₂₆ fractions not quantified individually. Thermodynamic model predictions are tested against available laboratory data on petroleum liquid densities, gas/liquid volume fractions, and liquid viscosities. We find that the emitted petroleum mixture was ∼29–44% gas and ∼56–71% liquid, after cooling to local conditions near the broken Macondo riser stub (∼153 atm and 4.3 °C). High pressure conditions dramatically favor the aqueous dissolution of C₁−C₄ hydrocarbons and also influence the buoyancies of bubbles and droplets. Additionally, the simulated densities of emitted petroleum fluids affect previous estimates of the volumetric flow rate of dead oil from the emission source.

A model to predict the mass flows and concentrations of pharmaceuticals predominantly used in hospitals across a large number of sewage treatment plant (STP) effluents and river waters was developed at high spatial resolution. It comprised 427 geo-referenced hospitals and 742 STPs serving 98% of the general population in Switzerland. In the modeled base scenario, domestic, pharmaceutical use was geographically distributed according to the population size served by the respective STPs. Distinct hospital scenarios were set up to evaluate how the predicted results were modified when pharmaceutical use in hospitals was allocated differently; for example, in proportion to number of beds or number of treatments in hospitals. The hospital scenarios predicted the mass flows and concentrations up to 3.9 times greater than in the domestic scenario for iodinated X-ray contrast media (ICM) used in computed tomography (CT), and up to 6.7 times greater for gadolinium, a contrast medium used in magnetic resonance imaging (MRI). Field measurements showed that ICM and gadolinium were predicted best by the scenarios using number of beds or treatments in hospitals with the specific facilities (i.e., CT and/or MRI). Pharmaceuticals used both in hospitals and by the general population (e.g., cyclophosphamide, sulfamethoxazole, carbamazepine, diclofenac) were predicted best by the scenario using the number of beds in all hospitals, but the deviation from the domestic scenario values was only small. Our study demonstrated that the bed number-based hospital scenarios were effective in predicting the geographical distribution of a diverse range of pharmaceuticals in STP effluents and rivers, while the domestic scenario was similarly effective on the scale of large river-catchments.

The biotransformation of some micropollutants has previously been observed to be positively associated with ammonia oxidation activities and the transcript abundance of the archaeal ammonia monooxygenase gene (amoA) in nitrifying activated sludge. Given the increasing interest in and potential importance of ammonia-oxidizing archaea (AOA), we investigated the capabilities of an AOA pure culture, Nitrososphaera gargensis, to biotransform ten micropollutants belonging to three structurally similar groups (i.e., phenylureas, tertiary amides, and tertiary amines). N. gargensis was able to biotransform two of the tertiary amines, mianserin (MIA) and ranitidine (RAN), exhibiting similar compound specificity as two ammonia-oxidizing bacteria (AOB) strains that were tested for comparison. The same MIA and RAN biotransformation reactions were carried out by both the AOA and AOB strains. The major transformation product (TP) of MIA, α-oxo MIA was likely formed via a two-step oxidation reaction. The first hydroxylation step is typically catalyzed by monooxygenases. Three RAN TP candidates were identified from nontarget analysis. Their tentative structures and possible biotransformation pathways were proposed. The biotransformation of MIA and RAN only occurred when ammonia oxidation was active, suggesting cometabolic transformations. Consistently, a comparative proteomic analysis revealed no significant differential expression of any protein-encoding gene in N. gargensis grown on ammonium with MIA or RAN compared with standard cultivation on ammonium only. Taken together, this study provides first important insights regarding the roles played by AOA in micropollutant biotransformation.

Compound-specific isotope analysis (CSIA) is a promising approach for tracking biotransformation of organic pollutants, but isotope fractionation associated with aromatic oxygenations is only poorly understood. We investigated the dioxygenation of a series of nitroaromatic compounds to the corresponding catechols by two enzymes, namely, nitrobenzene and 2-nitrotoluene dioxygenase (NBDO and 2NTDO) to elucidate the enzyme- and substrate-specificity of C and H isotope fractionation. While the apparent ¹³C- and ²H-kinetic isotope effects of nitrobenzene, nitrotoluene isomers, 2,6-dinitrotoluene, and naphthalene dioxygenation by NBDO varied considerably, the correlation of C and H isotope fractionation revealed a common mechanism for nitrobenzene and nitrotoluenes. Similar observations were made for the dioxygenation of these substrates by 2NTDO. Evaluation of reaction kinetics, isotope effects, and commitment-to-catalysis based on experiment and theory showed that rates of dioxygenation are determined by the enzymatic O₂ activation and aromatic C oxygenation. The contribution of enzymatic O₂ activation to the reaction rate varies for different nitroaromatic substrates of NBDO and 2NTDO. Because aromatic dioxygenation by nonheme iron dioxygenases is frequently the initial step of biodegradation, O₂ activation kinetics may also have been responsible for the minor isotope fractionation reported for the oxygenation of other aromatic contaminants.

Biotransformation is a key process that can greatly influence the bioaccumulation potential and toxicity of organic compounds. In this study, biotransformation of seven frequently used azole fungicides (triazoles: cyproconazole, epoxiconazole, fluconazole, propiconazole, tebuconazole and imidazoles: ketoconazole, prochloraz) was investigated in the aquatic invertebrate Gammarus pulex in a 24 h exposure experiment. Additionally, temporal trends of the whole body internal concentrations of epoxiconazole, prochloraz, and their respective biotransformation products (BTPs) were studied to gain insight into toxicokinetic processes such as uptake, elimination and biotransformation. By the use of high resolution tandem mass spectrometry in total 37 BTPs were identified. Between one (ketoconazole) and six (epoxiconazole) BTPs were identified per parent compound except for prochloraz, which showed extensive biotransformation reactions with 18 BTPs detected that were mainly formed through ring cleavage or ring loss. In general, most BTPs were formed by oxidation and conjugation reactions. Ring loss or ring cleavage was only observed for the imidazoles as expected from the general mechanism of oxidative ring openings of imidazoles, likely affecting the bioactivity of these BTPs. Overall, internal concentrations of BTPs were up to 3 orders of magnitude lower than that of the corresponding parent compound. Thus, biotransformation did not dominate toxicokinetics and only played a minor role in elimination of the respective parent compound, with the exception of prochloraz.

Studies according to OECD 308 and OECD 309 are performed to simulate the biodegradation of chemicals in water–sediment systems in support of persistence assessment and exposure modeling. However, several shortcomings of OECD 308 have been identified that hamper data evaluation and interpretation, and its relation to OECD 309 is still unclear. The present study systematically compares OECD 308 and OECD 309 and two variants thereof to derive recommendations on how to experimentally address any shortcomings and improve data for persistence and risk assessment. To this end, four ¹⁴C-labeled compounds with different biodegradation and sorption behavior were tested across standard OECD 308 and 309 test systems and two modified versions thereof. The well-degradable compounds showed slow equilibration and the least mineralization in OECD 308, whereas the modified systems provided the highest degree of mineralization. Different lines of evidence suggest that this was due to increased oxygenation of the sediment in the modified systems. Particularly for rapidly degrading compounds, non-extractable residue formation was in line with degradation and did not follow the sediment–water ratio. For the two more slowly degrading compounds, sorption in OECD 309 (standard and modified) increased with time beyond levels proposed by equilibrium partitioning, which could be attributed to the grinding of the sediment through the stirring of the sediment suspension. Overall, the large differences in degradation observed across the four test systems suggest that refined specifications in test guidelines are required to reduce variability in test outcomes. At the same time, the amount of sediment and its degree of oxygenation emerged as drivers across all test systems. This suggests that a unified description of the systems was possible and would pave the way toward a more consistent consideration of degradation in the water–sediment systems across different exposure situations and regulatory frameworks.

To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIE_aq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIE_aq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIE_aq, was found to range from ≈−0.5 to −0.91 eV. The ΔVIE_aq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIE_aq appeared largely controlled by differences in solute–solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV.

Chloramines, bromamines, and bromochloramines are halogen-containing oxidants that arise from the reaction of hypohalous acids with ammonia in water. Although relevant to both water disinfection chemistry and biochemistry, these molecules are difficult to study in the laboratory, and their thermochemical properties remain poorly established. We developed a benchmark level ab initio calculation protocol, termed TA14, adapted from the Weizmann theory and Feller–Peterson–Dixon approaches to determine the molecular structures and thermochemical properties of these compounds. We find that the halamine molecules are bound largely, and in some cases entirely, by electron correlation forces. This presumably explains their high reactivity as electrophilic oxidants. We provide computed heats of formation at 0 K (Δ_fH⁰_{0 K}) and at 298 K (Δ_fH⁰_{298 K}) and Gibbs free energies of formation at 298 K (Δ_fG⁰_{298 K}) for the 9 inorganic chloramines, bromamines, bromochloramines in gas phase. Based on comparisons to previous theoretical and experimental data for a set of 11 small molecules containing N, O, H, Cl, and Br, we propose uncertainties ranging from 1 to 3 kJ mol⁻¹ for computed thermodynamic properties of the halamines. Reported thermochemical data enable the determination of equilibrium constants for reactions involving halamines, opening possibilities for more quantitative studies of the chemistry of these poorly understood compounds.

In recent years, a large number of urine-diverting dehydration toilets (UDDTs) have been installed in eThekwini to ensure access to adequate sanitation. The initial purpose of these toilets was to facilitate faeces drying, while the urine was diverted into a soak pit. This practice can lead to environmental pollution, since urine contains high amounts of nutrients. Instead of polluting the environment, these nutrients should be recovered and used as fertiliser. In 2010 the international and transdisciplinary research project VUNA was initiated in order to explore technologies and management methods for better urine management in eThekwini. Three treatment technologies have been chosen for the VUNA project. The first is struvite precipitation, a technology which has already been tested in multiple projects on urine treatment. Struvite precipitation is a simple and fast process for phosphorus recovery. Other nutrients, such as nitrogen and potassium, remain in the effluent and pathogens are not completely inactivated. Therefore, struvite precipitation has to be combined with other treatment processes to prevent environmental pollution and hygiene risks. The second process is a combination of nitrification and distillation. This process combination is more complex than struvite precipitation, but it recovers all nutrients in one concentrated solution, ensures safe sanitisation and produces only distilled water and a small amount of sludge as by-products. The third process is electrolysis. This process could be used for very small on-site reactors, because conversion rates are high and the operation is simple, as long as appropriate electrodes and voltages are used. However, nitrogen is removed and not recovered and chlorinated by-products are formed, which can be hazardous for human health. While urine electrolysis requires further research in the laboratory, struvite precipitation and nitrification/distillation have already been operated at pilot scale.

Ozone transforms various organic compounds that absorb light within the UV and visible spectra. UV absorbance can therefore be used to detect the transformation of chemicals during ozonation. In wastewater, decolourisation can be observed after ozonation. This study investigates the correlation of the UV absorbance difference between the ozonation inlet and outlet and the removal efficiency of micropollutants in wastewater. The absorbance at 254 and 366 nm was measured at the ozonation inlet and outlet, as was the concentration of 24 representative micropollutants and the dissolved organic carbon (DOC). The results clearly showed that the relative decrease of absorbance (ΔAbs) is positively correlated with the relative removal efficiency of micropollutants. We therefore suggest that UV absorbance can be used as a feedback control parameter to achieve optimal ozone dosage in wastewater treatment plants and to gain a fast insight into the process efficiency and stability of the ozonation.

The occurrence and levels of perfluoroalkyl acids (PFAAs) emitted from specific pollution sources into the aquatic environment in Switzerland were studied using digested sewage sludges from 45 wastewater treatment plants in catchments containing a wide range of potential industrial emitters. Concentrations of individual PFAAs show a high spatial and temporal variability, which infers different contributions from industrial technologies and activities. Perfluorooctane sulfonic acid (PFOS) was generally the predominant PFAA with concentrations varying between 4 and 2440 μg kg⁻¹ (median 75 μg kg⁻¹). Elevated emissions were especially observed in catchments capturing discharges from metal plating industries (median 82 μg kg⁻¹), aqueous firefighting foams (median 215 μg kg⁻¹) and landfill leachates (median 107 μg kg⁻¹). Some elevated perfluoroalkyl carboxylic acids (PFCAs) levels could be attributed to emissions from textile finishing industries with concentrations up to 233 μg kg⁻¹ in sewage sludge. Assuming sorption to sludge for PFOS and PFCAs of 15% and 2%, respectively, concentrations in wastewater effluents up to the low μg L⁻¹ level were estimated. Even if wastewater may be expected to be diluted between 10 and 100 times by the receiving waters, elevated concentrations may be reached at specific locations. Although sewage sludge is a minor compartment for PFAAs in WWTPs, these investigations are helpful for the identification of hot-spots from industrial emitters as well as to estimate monthly average concentrations in wastewater.

Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.

Der Reinigungseffekt weitergehender Abwasserbehandlungsverfahren wie Ozonung oder Pulveraktivkohle-Adsorption soll anhand einzelner Spurenstoffe überprüft werden. Dazu werden zwölf Mikroverunreinigungen vorgeschlagen, die schweizweit verbreitet vorkommen, mit gängigen analytischen Methoden messbar sind, in der biologischen Reinigungsstufe ungenügend abgebaut werden und repräsentativ für die Gesamtfracht an organischen Spurenstoffen aus kommunalem Abwasser sind.

In a large field study, the in-situ calibration of the Chemcatcher^® passive sampler – styrenedivinylbenzene (SDB) covered by a polyether sulfone (PES) membrane – was evaluated for 322 polar organic micropollutants. Five rivers with different agricultural and urban influences were monitored from March to July 2012 with two methods i) two-week time-proportional composite water samples and ii) two-week passive sampler deployment. All substances – from different substance classes with logK_ow −3 to 5, and neutral, anionic, cationic, and zwitterionic species – were analyzed by liquid-chromatography high-resolution tandem mass spectrometry. This study showed that SDB passive samplers are well-suited for the qualitative screening of polar micropollutants because the number of detected substances was similar (204 for SDB samples vs. 207 for composite water samples), limits of quantification were comparable (median: 1.3 ng/L vs. 1.6 ng/L), and the handling in the field and laboratory is fast and easy. The determination of in-situ calibrated sampling rates (field R_s) was possible for 88 compounds where the R² from the regression (water concentration vs. sampled mass on SDB disk) was >0.75. Substances with moderately fluctuating river concentrations such as pharmaceuticals showed much better correlations than substances with highly fluctuating concentrations such as pesticides (R² > 0.75 for 93% and 60% of the investigated substances, respectively). Flow velocity (0.05–0.8 m/s) and temperature (5–20 °C) did not have an evident effect on the field R_s. It was observed that ionic species had significantly lower field R_s than neutral species. Due to the complexity of the different transport processes, a correlation between determined field R_s and logD_ow could only predict R_s with large uncertainties. We conclude that only substances with relatively constant river concentrations can be quantified accurately in the field by passive sampling if substance-specific R_s are determined. For that purpose, the proposed in-situ calibration is a very robust method and the substance specific R_s can be used in future monitoring studies in rivers with similar environmental conditions (i.e., flow velocity, temperature, pH).

Bisher haben Insektizide und Fungizide im Fliessgewässermonitoring eine untergeordnete Rolle gespielt. Dieser Artikel beschreibt, wie und wo diese Substanzen angewendet werden, wie sie ins Gewässer gelangen, welche Exposition in einer schweizweiten Feldstudie bestimmt wurde und welche Auswirkungen auf Gewässerorganismen dadurch erwartet werden. Die Ergebnisse zeigen deutlich, dass mehr Insektizide und Fungizide mit tiefen analytischen Nachweisgrenzen in Routine- Monitoringprogramme aufgenommen werden müssen, um die Wasserqualität umfassender zu beurteilen.

Despite the relevance of resting eggs for ecology and evolution of many aquatic organisms and their exposure to contaminants accumulating in sediments, ecotoxicological studies using resting eggs are vastly underrepresented. The authors established a method to perform exposure assays with resting eggs produced by the Daphnia longispina species complex, key species in large lake ecosystems. A mixture of organic contaminants previously detected in sediments of Lake Greifensee was selected to test the potential effect of organic contaminants present in sediments on the hatching process. Resting eggs were exposed to a mix of 10 chemicals, which included corrosion inhibitors, biocides, pesticides, and personal care products, for a period of 15 d. Using an automated counting software, the authors found a significant increase in hatching success in the exposed resting eggs compared with controls. Such an effect has not yet been reported from ecotoxicological assays with resting eggs. Possible mechanistic explanations as well as the potential implications on the ecology and evolution of aquatic species that rely on a resting egg banks are discussed. Observed increased mortality and developmental abnormalities for hatchlings in the exposure treatments can be explained by toxic contaminant concentrations. The results of the present study highlight the need for additional studies assessing the effects of organic contaminants on resting egg banks and aquatic ecosystems.

Compound-specific isotope analysis is a useful approach to track transformations of many organic soil and water pollutants. Applications of CSIA to characterize photochemical processes, however, have hardly been explored. In this work, we systematically studied C and N isotope fractionation associated with the direct photolysis of 4-Cl-aniline used as a model compound for organic micropollutants that are known to degrade via photochemical processes. Laboratory experiments were carried out at an irradiation wavelength of 254 nm over the pH range 2.0 to 9.0 as well as in the presence of Cs⁺ as a quencher of excited singlet 4-Cl-aniline at pH 7.0 and 9.0. We observed considerable variation of C and N isotope enrichment factors, ϵ_C and ϵ_N, between −1.2 ± 0.2‰ to −2.7 ± 0.2‰ for C and −0.6 ± 0.2‰ to −9.1 ± 1.6‰ for N, respectively, which could not be explained by the speciation of 4-Cl-aniline alone. In the presence of 1 M Cs⁺, we found a marked increase of apparent ¹³C-kinetic isotope effects (¹³C-AKIE) and decrease of 4-Cl-aniline fluorescence lifetimes. Our data suggest that variations of C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and singlet states of 4-Cl-aniline. Linear correlations of ¹³C-AKIE vs ¹⁵N-AKIE were distinctly different for these two reaction pathways and may be explored further for the identification of photolytic aromatic dechlorination reactions.

Comprehensive two-dimensional gas chromatography (GC × GC) is used widely to separate and measure organic chemicals in complex mixtures. However, approaches to quantify analytes in real, complex samples have not been critically assessed. We quantified 7 PAHs in a certified diesel fuel using GC × GC coupled to flame ionization detector (FID), and we quantified 11 target chlorinated hydrocarbons in a lake water extract using GC × GC with electron capture detector (μECD), further confirmed qualitatively by GC × GC with electron capture negative chemical ionization time-of-flight mass spectrometer (ENCI-TOFMS). Target analyte peak volumes were determined using several existing baseline correction algorithms and peak delineation algorithms. Analyte quantifications were conducted using external standards and also using standard additions, enabling us to diagnose matrix effects. We then applied several chemometric tests to these data. We find that the choice of baseline correction algorithm and peak delineation algorithm strongly influence the reproducibility of analyte signal, error of the calibration offset, proportionality of integrated signal response, and accuracy of quantifications. Additionally, the choice of baseline correction and the peak delineation algorithm are essential for correctly discriminating analyte signal from unresolved complex mixture signal, and this is the chief consideration for controlling matrix effects during quantification. The diagnostic approaches presented here provide guidance for analyte quantification using GC × GC.

The rates at which wastewater treatment plant (WWTP) microbial communities biotransform specific substrates can differ by orders of magnitude among WWTP communities. Differences in taxonomic compositions among WWTP communities may predict differences in the rates of some types of biotransformations. In this work, we present a novel framework for establishing predictive relationships between specific bacterial 16S rRNA sequence abundances and biotransformation rates. We selected ten WWTPs with substantial variation in their environmental and operational metrics and measured the in situ ammonia biotransformation rate constants in nine of them. We isolated total RNA from samples from each WWTP and analyzed 16S rRNA sequence reads. We then developed multivariate models between the measured abundances of specific bacterial 16S rRNA sequence reads and the ammonia biotransformation rate constants. We constructed model scenarios that systematically explored the effects of model regularization, model linearity and non-linearity, and aggregation of 16S rRNA sequences into operational taxonomic units (OTUs) as a function of sequence dissimilarity threshold (SDT). A large percentage (greater than 80%) of model scenarios resulted in well-performing and significant models at intermediate SDTs of 0.13–0.14 and 0.26. The 16S rRNA sequences consistently selected into the well-performing and significant models at those SDTs were classified as Nitrosomonas and Nitrospira groups. We then extend the framework by applying it to the biotransformation rate constants of ten micropollutants measured in batch reactors seeded with the ten WWTP communities. We identified phylogenetic groups that were robustly selected into all well-performing and significant models constructed with biotransformation rates of isoproturon, propachlor, ranitidine, and venlafaxine. These phylogenetic groups can be used as predictive biomarkers of WWTP microbial community activity towards these specific micropollutants. This work is an important step towards developing tools to predict biotransformation rates in WWTPs based on taxonomic composition.

Identification of transformation products (TPs) of emerging pollutants is challenging, due to the vast number of compounds, mostly unknown, the complexity of the matrices and their often low concentrations, requiring highly selective, highly sensitive techniques. We compile background information on biotic and abiotic formation of TPs and analytical developments over the past five years. We present a database of biotic or abiotic TPs compiled from those identified in recent years. We discuss mass spectrometric (MS) techniques and workflows for target, suspect and non-target screening of TPs with emphasis on liquid chromatography coupled to MS (LC-MS). Both low- and high-resolution (HR) mass analyzers have been applied, but HR-MS is the technique of choice, due to its high confirmatory capabilities, derived from the high resolving power and the mass accuracy in MS and MS/MS modes, and the sophisticated software developed.

The identification of unknown compounds remains one of the most challenging tasks to link observed toxic effects in complex environmental mixtures to responsible toxicants in effect-directed analysis (EDA). Here, a workflow is presented based on nontarget liquid chromatography-high resolution mass spectrometry (LC-HRMS) starting with molecular formulas determined in a previous study. A compound database search (ChemSpider) was performed to retrieve candidates for each formula. Subsequently, the number of candidates was reduced by applying MS-, physical-chemical, and chromatography-based selection criteria including HRMS/MS fragmentation and plausibility, ionization efficiency with different ion sources and detection modes, acid/base behavior, octanol/water partitioning, retention time prediction and finally toxic effects (mutagenicity caused by aromatic amines). The workflow strongly decreased the number of possible candidates and resulted in the tentative identification of possible mutagens and the positive identification of the nonmutagen benzyl(diphenyl) phosphine oxide in a mutagenic fraction. The positive identification of mutagens was hampered by a lack of commercially available standards. The workflow is an innovative and promising approach and forms an excellent basis for possible further advancements.

The OECD guideline 308 describes a laboratory test method to assess aerobic and anaerobic transformation of organic chemicals in aquatic sediment systems and is an integral part of tiered testing strategies in different legislative frameworks for the environmental risk assessment of chemicals. The results from experiments carried out according to OECD 308 are generally used to derive persistence indicators for hazard assessment or half-lives for exposure assessment. We used Bayesian parameter estimation and system representations of various complexities to systematically assess opportunities and limitations for estimating these indicators from existing data generated according to OECD 308 for 23 pesticides and pharmaceuticals. We found that there is a disparity between the uncertainty and the conceptual robustness of persistence indicators. Disappearance half-lives are directly extractable with limited uncertainty, but they lump degradation and phase transfer information and are not robust against changes in system geometry. Transformation half-lives are less system-specific but require inverse modeling to extract, resulting in considerable uncertainty. Available data were thus insufficient to derive indicators that had both acceptable robustness and uncertainty, which further supports previously voiced concerns about the usability and efficiency of these costly experiments. Despite the limitations of existing data, we suggest the time until 50% of the parent compound has been transformed in the entire system (DegT_50,system) could still be a useful indicator of persistence in the upper, partially aerobic sediment layer in the context of PBT assessment. This should, however, be accompanied by a mandatory reporting or full standardization of the geometry of the experimental system. We recommend transformation half-lives determined by inverse modeling to be used as input parameters into fate models for exposure assessment, if due consideration is given to their uncertainty.

Biodiversities can differ substantially among different wastewater treatment plant (WWTP) communities. Whether differences in biodiversity translate into differences in the provision of particular ecosystem services, however, is under active debate. Theoretical considerations predict that WWTP communities with more biodiversity are more likely to contain strains that have positive effects on the rates of particular ecosystem functions, thus resulting in positive associations between those two variables. However, if WWTP communities were sufficiently biodiverse to nearly saturate the set of possible positive effects, then positive associations would not occur between biodiversity and the rates of particular ecosystem functions. To test these expectations, we measured the taxonomic biodiversity, functional biodiversity, and rates of 10 different micropollutant biotransformations for 10 full-scale WWTP communities. We have demonstrated that biodiversity is positively associated with the rates of specific, but not all, micropollutant biotransformations. Thus, one cannot assume whether or how biodiversity will associate with the rate of any particular micropollutant biotransformation. We have further demonstrated that the strongest positive association is between biodiversity and the collective rate of multiple micropollutant biotransformations. Thus, more biodiversity is likely required to maximize the collective rates of multiple micropollutant biotransformations than is required to maximize the rate of any individual micropollutant biotransformation. We finally provide evidence that the positive associations are stronger for rare micropollutant biotransformations than for common micropollutant biotransformations. Together, our results are consistent with the hypothesis that differences in biodiversity can indeed translate into differences in the provision of particular ecosystem services by full-scale WWTP communities.

There is increasing interest in using meta-omics association studies to investigate contaminant biotransformations. The general strategy is to characterize the complete set of genes, transcripts, or enzymes from in situ environmental communities and use the abundances of particular genes, transcripts, or enzymes to establish associations with the communities' potential to biotransform one or more contaminants. The associations can then be used to generate hypotheses about the underlying biological causes of particular biotransformations. While meta-omics association studies are undoubtedly powerful, they have a tendency to generate large numbers of non-causal associations, making it potentially difficult to identify the genes, transcripts, or enzymes that cause or promote a particular biotransformation. In this perspective, we describe general scenarios that could lead to pervasive non-causal associations or conceal causal associations. We next explore our own published data for evidence of pervasive non-causal associations. Finally, we evaluate whether causal associations could be identified despite the discussed limitations. Analysis of our own published data suggests that, despite their limitations, meta-omics association studies might still be useful for improving our understanding and predicting the contaminant biotransformation capacities of microbial communities.

Dehalococcoides mccartyi are functionally important bacteria that catalyze the reductive dechlorination of chlorinated ethenes. However, these anaerobic bacteria are fastidious to isolate, making downstream genomic characterization challenging. In order to facilitate genomic analysis, a fluorescence-activated cell sorting (FACS) method was developed in this study to separate D. mccartyi cells from a microbial community, and the DNA of the isolated cells was processed by whole genome amplification (WGA) and hybridized onto a D. mccartyi microarray for comparative genomics against four sequenced strains. First, FACS was successfully applied to a D. mccartyi isolate as positive control, and then microarray results verified that WGA from 10⁶ cells or ∼1 ng of genomic DNA yielded high-quality coverage detecting nearly all genes across the genome. As expected, some inter- and intrasample variability in WGA was observed, but these biases were minimized by performing multiple parallel amplifications. Subsequent application of the FACS and WGA protocols to two enrichment cultures containing ∼10% and ∼1% D. mccartyi cells successfully enabled genomic analysis. As proof of concept, this study demonstrates that coupling FACS with WGA and microarrays is a promising tool to expedite genomic characterization of target strains in environmental communities where the relative concentrations are low.

In this study, the contamination by polar organic pollutants was investigated along the Rhine River, an important source of drinking water for 22 million people in central Europe. Following the flow of the river, a traveling water mass was sampled using weekly flow-proportional composite samples at ten different downstream sites, including main tributaries. Using a broad analytical method based on solid phase extraction and high-resolution mass spectrometry, the water was analyzed for more than 300 target substances. While the water in Lake Constance contained only 83 substances in often low concentrations, the number of detects found in the water phase increased to 143 substances and a weekly load of more than 7 tons at the last sampling site, the Dutch-German border. Mostly present were chemicals originating from wastewater treatment plants, especially the artificial sweetener Acesulfam and two pharmaceuticals, Metformin and Gabapentin, which dominate the weekly load up to 58%. Although the sample campaign was performed in a dry period in early spring, a large variety of pesticides and biocides were detected. Several industrial point sources were identified along the waterway's 900 km journey, resulting in high concentrations in the tributaries and loads of up to 160 kg. Additionally, an unbiased non-target analysis was performed following two different strategies for the prioritization of hundreds of potentially relevant unknown masses. While for the first prioritization strategy, only chlorinated compounds were extracted from the mass spectrometer datasets, the second prioritization strategy was performed using a systematic reduction approach between the different sampling sites. Among others, two substances that never had been detected before in this river, namely, the muscle relaxant Tizanidine and the solvent 1,3-Dimethyl-2-imidazolidinone (DMI), were identified and confirmed, and their loads were roughly estimated along the river.

In eThekwini, South Africa, the production of agricultural fertilizers from human urine collected from urine-diverting dry toilets is being evaluated at a municipality scale as a way to help finance a decentralized, dry sanitation system. The present study aimed to assess a range of human and environmental health hazards in source-separated urine, which was presumed to be contaminated with feces, by evaluating the presence of human pathogens, pharmaceuticals, and an antibiotic resistance gene. Composite urine samples from households enrolled in a urine collection trial were obtained from urine storage tanks installed in three regions of eThekwini. Polymerase chain reaction (PCR) assays targeted 9 viral and 10 bacterial human pathogens transmitted by the fecal–oral route. The most frequently detected viral pathogens were JC polyomavirus, rotavirus, and human adenovirus in 100%, 34% and 31% of samples, respectively. Aeromonas spp. and Shigella spp. were frequently detected gram negative bacteria, in 94% and 61% of samples, respectively. The gram positive bacterium, Clostridium perfringens, which is known to survive for extended times in urine, was found in 72% of samples. A screening of 41 trace organic compounds in the urine facilitated selection of 12 priority pharmaceuticals for further evaluation. The antibiotics sulfamethoxazole and trimethoprim, which are frequently prescribed as prophylaxis for HIV-positive patients, were detected in 95% and 85% of samples, reaching maximum concentrations of 6800 μg/L and 1280 μg/L, respectively. The antiretroviral drug emtricitabine was also detected in 40% of urine samples. A sulfonamide antibiotic resistance gene (sul1) was detected in 100% of urine samples. By coupling analysis of pathogens and pharmaceuticals in geographically dispersed samples in eThekwini, this study reveals a range of human and environmental health hazards in urine intended for fertilizer production. Collection of urine offers the benefit of sequestering contaminants from environmental release and allows for targeted treatment of potential health hazards prior to agricultural application. The efficacy of pathogen and pharmaceutical inactivation, transformation or removal during urine nutrient recovery processes is thus briefly reviewed.

Isotope fractionation associated with the photochemical transformation of organic contaminants is not well understood and can arise not only from bond cleavage reactions but also from photophysical processes. In this work, we investigated the photolytic dechlorination of 2-Cl- and 3-Cl-aniline to aminophenols to obtain insights into the impact of the substituent position on the apparent ¹³C and ¹⁵N kinetic isotope effects (AKIEs). Laboratory experiments were performed in aerated aqueous solutions at an irradiation wavelength of 254 nm over the pH range 2.0 to 7.0 in the absence and presence of Cs⁺ used as an excited singlet state quencher. Photolysis of 2-Cl-anilinium cations exhibits normal C and inverse N isotope fractionation, while neutral 2-Cl-aniline species shows inverse C and normal N isotope fractionation. In contrast, the photolysis of 3-Cl-aniline was almost insensitive to C isotope composition and the moderate N isotope fractionation points to rate-limiting photophysical processes. ¹³C- and ¹⁵N-AKIE-values of 2-Cl-aniline decreased in the presence of Cs⁺, whereas those for 3-Cl-aniline were not systematically affected by Cs⁺. Our current and previous work illustrates that photolytic dechlorinations of 2-Cl-, 3-Cl-, and 4-Cl-aniline isomers are each accompanied by distinctly different and highly variable C and N isotope fractionation due to spin selective isotope effects.

Identification of small molecules by liquid chromatography–mass spectrometry (LC–MS) can be greatly improved if the chromatographic retention information is used along with mass spectral information to narrow down the lists of candidates. Linear retention indexing remains the standard for sharing retention data across labs, but it is unreliable because it cannot properly account for differences in the experimental conditions used by various labs, even when the differences are relatively small and unintentional. On the other hand, an approach called “retention projection” properly accounts for many intentional differences in experimental conditions, and when combined with a “back-calculation” methodology described recently, it also accounts for unintentional differences. In this study, the accuracy of this methodology is compared with linear retention indexing across eight different labs. When each lab ran a test mixture under a range of multi-segment gradients and flow rates they selected independently, retention projections averaged 22-fold more accurate for uncharged compounds because they properly accounted for these intentional differences, which were more pronounced in steep gradients. When each lab ran the test mixture under nominally the same conditions, which is the ideal situation to reproduce linear retention indices, retention projections still averaged 2-fold more accurate because they properly accounted for many unintentional differences between the LC systems. To the best of our knowledge, this is the most successful study to date aiming to calculate (or even just to reproduce) LC gradient retention across labs, and it is the only study in which retention was reliably calculated under various multi-segment gradients and flow rates chosen independently by labs.

Redox-active minerals are ubiquitous in the environment and are involved in numerous electron transfer reactions that significantly affect biogeochemical processes and cycles as well as pollutant dynamics. As a consequence, research in different scientific disciplines is devoted to elucidating the redox properties and reactivities of minerals. This review focuses on the characterization of mineral redox properties using electrochemical approaches from an applied (bio)geochemical and environmental analytical chemistry perspective. Establishing redox equilibria between the minerals and working electrodes is a major challenge in electrochemical measurements, which we discuss in an overview of traditional electrochemical techniques. These issues can be overcome with mediated electrochemical analyses in which dissolved redox mediators are used to increase the rate of electron transfer and to facilitate redox equilibration between working electrodes and minerals in both amperometric and potentiometric measurements. Using experimental data on an iron-bearing clay mineral, we illustrate how mediated electrochemical analyses can be employed to derive important thermodynamic and kinetic data on electron transfer to and from structural iron. We summarize anticipated methodological advancements that will further contribute to advance an improved understanding of electron transfer to and from minerals in environmentally relevant redox processes.

Using macroinvertebrates as ecological indicators for different stressors has a long tradition. However, when applied to field data, one often observes correlations between different macroinvertebrate indices that can be attributed to both correlations of stressors and inherent correlations due to the sensitivity of taxa to different stressors. Ignoring the source of any given correlation leads to ambiguous conclusions about the impact of different stressors.
Here, we demonstrate how to distinguish the causes of correlation by means of Monte Carlo simulations. We assessed to which degree trait-based indices are stressor-specific and whether this depends on the pool of taxa and its taxonomic resolution. Therefore, we (1) analysed the frequencies of "sensitive" and "insensitive" taxa for pairwise combinations of different indices, (2) analysed the inherent correlation of indices with random samples from different taxon pools derived from field samples and from a complete species list of a whole ecoregion, and (3) compared this inherent correlation with the actual correlation of the field samples. We exemplified this approach by analysing two existing indices (SPEAR_pesticides, Saprobic Index) and new indices for temperature, flow and pH stress. We used these new indices to illustrate our approach while in-depth testing of their applicability was not the focus of our study. <BR/>We found strong correlations between several indices in our study area at the Swiss Plateau. The probability that this correlation is only due to inherent correlation in the taxa sensitivities was low (maximum of 0.34). The problem of inherent correlation between indices is more severe for the smaller taxon pool with lower taxonomic resolution.
Correlation in the sensitivity of different taxa to different stressors leads to an inherent correlation in trait-based indices, which weakens their explanatory power. Our results highlight the importance of correlation analyses when using trait-based indices to guide ecosystem-management, especially in regions with reduced biodiversity.

In this article, a dataset from a collaborative non-target screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detection. This article focuses mainly on the use of high resolution screening techniques with target, suspect, and non-target workflows to identify substances in environmental samples. Specific examples are given to emphasise major challenges including isobaric and co-eluting substances, dependence on target and suspect lists, formula assignment, the use of retention information, and the confidence of identification. Approaches and methods applicable to unit resolution data are also discussed. Although most substances were identified using high resolution data with target and suspect-screening approaches, some participants proposed tentative non-target identifications. This comprehensive dataset revealed that non-target analytical techniques are already substantially harmonised between the participants, but the data processing remains time-consuming. Although the objective of a "fully-automated identification workflow" remains elusive in the short term, important steps in this direction have been taken, exemplified by the growing popularity of suspect screening approaches. Major recommendations to improve non-target screening include better integration and connection of desired features into software packages, the exchange of target and suspect lists, and the contribution of more spectra from standard substances into (openly accessible) databases.

The series of papers in this issue of AMBIO represent technical presentations made at the 7th International Phosphorus Workshop (IPW7), held in September, 2013 in Uppsala, Sweden. At that meeting, the 150 delegates were involved in round table discussions on major, predetermined themes facing the management of agricultural phosphorus (P) for optimum production goals with minimal water quality impairment. The six themes were (1) P management in a changing world; (2) transport pathways of P from soil to water; (3) monitoring, modeling, and communication; (4) importance of manure and agricultural production systems for P management; (5) identification of appropriate mitigation measures for reduction of P loss; and (6) implementation of mitigation strategies to reduce P loss. This paper details the major challenges and research needs that were identified for each theme and identifies a future roadmap for catchment management that cost-effectively minimizes P loss from agricultural activities.

Incomplete micropollutant elimination in wastewater treatment plants (WWTPs) results in transformation products (TPs) that are released into the environment. Improvements in analytical technologies have allowed researchers to identify several TPs from specific micropollutants but an overall picture of nontarget TPs is missing. In this study, we addressed this challenge by applying multivariate statistics to data collected with liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) and subsequent tandem HRMS (MS/MS) in order to characterize peaks detected in the influent and effluent of a WWTP. Known biotransformation reactions were used to link potential parent compounds and TPs, while the structural similarity of these pairs hypothesized by MS/MS similarity was used for further prioritization. The methodology was validated with a set of spiked compounds, which included 25 parent/TP pairs for which analytical standards were available. This procedure was then applied to nontarget data, and 20 potential parent and TP pairs were selected for identification. In summary, primarily a surfactant homologue series, with associated TPs, was detected. Some obstacles still remain, including spectral interferences from coeluting compounds and identification of TPs, whose structures are less likely to be present in compound databases. The workflow was developed using openly accessible tools and, after parameter adjustment, could be applied to any data set with before and after information about various biological or chemical processes.

The assessment of oxidative pollutant biotransformation by compound specific isotope analysis (CSIA) is often complicated by the variability of kinetic isotope effects associated with carbon oxygenation in enzymatic reactions. Here, we illustrate how information about the kinetics of oxidative biocatalysis by flavin-dependent monooxygenases (FMOs) enables one to assess if CSIA could be applied for tracking contaminant biodegradation. In "cautious" FMOs, which form reactive flavin (hydro)peroxide species after substrate binding, the monooxygenation of organic compounds is not rate-determining and consequently does not lead to substrate isotope fractionation. Conversely, "bold" FMOs generate hydroperoxides regardless of substrate availability, and substrate disappearance is thus subject to isotope fractionation trends, which are typical for hydroxylation reactions. Because monooxygenations of aromatic moieties are often initial steps of organic pollutant transformation, knowledge of the kinetics of FMOs and other oxidative enzymes can support decisions regarding the use of CSIA.

Organic micropollutants containing aniline substructures are susceptible to different light-induced transformation processes in aquatic environments and water treatment operations. Here, we investigated the magnitude and variability of C and N isotope fractionation during the indirect phototransformation of four para-substituted anilines in aerated aqueous solutions. The model photosensitizers, namely 9,10-anthraquinone-1,5-disulfonate and methylene blue, were used as surrogates for dissolved organic matter chromophores generating excited triplet states in sunlit surface waters. The transformation of aniline, 4-CH₃-, 4-OCH₃-, and 4-Cl-aniline by excited triplet states of the photosensitizers was associated with inverse and normal N isotope fractionation, whereas C isotope fractionation was negligible. The apparent ¹⁵N kinetic isotope effects (AKIE) were almost identical for both photosensitizers, increased from 0.9958 ± 0.0013 for 4-OCH₃-aniline to 1.0035 ± 0.0006 for 4-Cl-aniline, and correlated well with the electron donating properties of the substituent. N isotope fractionation is pH-dependent in that H⁺ exchange reactions dominate below and N atom oxidation processes above the pK_a value of the substituted aniline’s conjugate acid. Correlations of C and N isotope fractionation for indirect phototransformation were different from those determined previously for the direct photolysis of chloroanilines and offer new opportunities to distinguish between abiotic degradation pathways.

An integrated workflow based on liquid chromatography coupled to a quadrupole-time-of-flight mass spectrometer (LC-QTOF-MS) was developed and applied to detect and identify suspect and unknown contaminants in Greek wastewater. Tentative identifications were initially based on mass accuracy, isotopic pattern, plausibility of the chromatographic retention time and MS/MS spectral interpretation (comparison with spectral libraries, in silico fragmentation). Moreover, new specific strategies for the identification of metabolites were applied to obtain extra confidence including the comparison of diurnal and/or weekly concentration trends of the metabolite and parent compounds and the complementary use of HILIC. Thirteen of 284 predicted and literature metabolites of selected pharmaceuticals and nicotine were tentatively identified in influent samples from Athens and seven were finally confirmed with reference standards. Thirty four nontarget compounds were tentatively identified, four were also confirmed. The sulfonated surfactant diglycol ether sulfate was identified along with others in the homologous series (SO₄C₂H₄(OC₂H₄)_xOH), which have not been previously reported in wastewater. As many surfactants were originally found as nontargets, these compounds were studied in detail through retrospective analysis.

Lysimeter experiments were carried out to evaluate the applicability of compound-specific isotope analysis (CSIA) for assessing transport and fate of selected herbicides in two agricultural soils cropped with corn. Monitoring of target pesticides, metabolites and tracers in drainage water made apparent the significant role of preferential flow in the mobility of the studied compounds through the soil and the vadose zone during the first days after herbicides application. The detection of metabolites in drainage water confirmed herbicides degradation once higher residence times in the soil zone where achieved. An efficient preconcentration procedure was developed for 10-L drainage water samples to achieve enough analyte enrichment for C, N and Cl isotope ratios measurements. Methods for isotope analyses are currently being developed and the applicability of CSIA for assessing the in situ biodegradation of the target pesticides during transport in soil and vadose zone will be evaluated.

Second-order rate constants (k_O3) for the reaction of ozone with micropollutants are essential parameters for the assessment of micropollutant elimination efficiency during ozonation in water and wastewater treatment. Prediction models for k_O3 were developed for aromatic compounds, olefins, and amines by quantum chemical molecular orbital calculations employing ab initio Hartree–Fock (HF) and density functional theory (B3LYP) methods. The k_O3 values for aromatic compounds correlated well with the energy of a delocalized molecular orbital first appearing on an aromatic ring (i.e., the highest occupied molecular orbital (HOMO) or HOMO–n (n ≥ 0) when the HOMO is not located on the aromatic ring); the number of compounds tested (N) was 112, and the correlation coefficient (R²) values were 0.82–1.00. The k_O3 values for olefins and amines correlated well with the energy of a localized molecular orbital (i.e., the natural bond orbital (NBO)) energy of the carbon–carbon π bond of olefins (N = 45, R² values of 0.82–0.85) and the NBO energy of the nitrogen lone-pair electrons of amines (N = 59, R² values of 0.81–0.83), respectively. Considering the performance of the k_O3 prediction model and the computational costs, the HF/6-31G method is recommended for all aromatic groups and olefins investigated herein, whereas the HF/MIDI!, HF/6-31G*, or HF/6-311++G** methods are recommended for amines. Based on their mean absolute errors, the above models could predict k_O3 within a factor of 4, on average, relative to the experimentally determined values. Overall, good correlations were also observed (R² values of 0.77–0.96) between k_O3 predictions by quantum molecular orbital descriptors in this study and by the Hammett (σ) and Taft (σ*) constants from previously developed quantitative structure–activity relationship (QSAR) models. Hence, the quantum molecular orbital descriptors are an alternative to σ and σ*-values in QSAR applications and can also be utilized to estimate unknown σ or σ*-values.

We report the development and validation of a method to detect and quantify diverse nonpolar halogenated micropollutants in wastewater treatment plant (WWTP) influent, effluent, primary sludge, and secondary sludge matrices (including both the liquid and particle phases) by comprehensive two-dimensional gas chromatography (GC×GC) coupled to micro- electron capture detector (μECD). The 59 target analytes included toxaphenes, polychlorinated naphthalenes, organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, and emerging persistent and bioaccumulative chemicals. The method is robust for a wide range of nonpolar halogenated micropollutants in all matrices. For most analytes, recoveries fell between 70% and 130% in all matrix types. GC×GC-μECD detections of several target analytes were confirmed qualitatively by further analysis with GC×GC coupled to electron capture negative chemical ionization–time-of-flight mass spectrometry (ENCI-TOFMS). We then quantified the concentrations and apparent organic solid–water partition coefficients (K_p) of target micropollutants in samples from a municipal WWTP in Switzerland. Several analyzed pollutants exhibited a high frequency of occurrence in WWTP stream samples, including octachloronaphthalene, PCB-44, PCB-52, PCB-153, PCB-180, several organochlorine pesticides, PBDE-10, PBDE-28, PBDE-116, musk tibetene, and pentachloronitrobenzene. Our results suggest that sorption to dissolved organic carbon (DOC) can contribute substantially to the apparent solids-liquid distribution of hydrophobic micropollutants in WWTP streams.

Quantitative structure - reactivity relationships (QSRRs) were investigated for the estimation of the Mayr nucleophilicity parameter N using data sets with 218 nucleophiles (solvent: CH₂Cl₂) and 88 compounds (solvent: MeCN) extracted from the Mayr's Database of Reactivity Parameters. The best predictions were observed for consensus models of random forests and associative neural networks, trained with empirical 2D and 3D CDK molecular descriptors, which yielded RMSE of 1.54 and 1.97 for independent test sets of the two solvent data sets, respectively. Compounds with silicon atoms were more difficult to predict, as well as classes of compounds with a reduced number of examples in the training set. The models' predictions were consistently more accurate than estimations simply based on the average of the N parameter within the class of the query compound. The possibility of calculating rate constants using the obtained models was also explored.

Diffuse entry of pesticide residues from agriculture into rivers is spatially unevenly distributed. Therefore, the identification of critical source areas (CSAs) may support water quality management in agricultural catchments. In contrast to former studies, we followed the hypothesis that not only hydrological and topographical characteristics but also physico-chemical properties of pesticide residues have a major influence on their loss to rivers and on corresponding formation of CSAs. We designed a virtual experiment, i.e. a numerical experiment as close as possible to environmental conditions, in a headwater catchment where pronounced spatial differences in hydrological transport processes were identified in the past. 144 scenarios with different combinations of adsorption coefficients (K_OC = 10–1000 ml/g) and transformation half-lives (DT50 = 3–60 days) for pesticide parent compounds (PCs) and their transformation products (TPs) were simulated using the catchment-scale spatially distributed reactive transport model ZIN-AgriTra.
Export fractions of substances in the virtual experiment ranged from 0.001–15% for pesticides and 0.001–1.8% for TPs. The results of the scenario investigations suggest that more of the calculated export mass variability could be attributed to K_OC than to DT50 for both PCs and TPs. CSAs for TPs were spatially more equally distributed in the catchment than for PC export which was likely an effect of changing physico-chemical properties during transformation. The ranking of highest export fields was different between PCs and TPs for most of the investigated scenarios but six fields appeared among the top ten export fields in 95% of the scenarios, which shows the influence of site characteristics such as tile drains or soil properties in the catchment. Thus, the highest export fields were determined by a combination of site characteristics and substance characteristics. Therefore, despite the challenge of widely differing physico-chemical characteristics of pesticides on the market, these characteristics are an important consideration when delineating pesticide residue CSAs.

A fast and memory-efficient calculation of theoretical isotope patterns is crucial for the routine interpretation of mass spectrometric data. For high-resolution experiments, calculations must procure the exact masses and probabilities of relevant isotopologues over a wide range of polyisotopic compounds, while pruning low-probable ones. Here, a novel albeit simple treelike structure is introduced to swiftly derive sets of relevant subisotopologues for each element in a molecule, which are then combined to the isotopologues of the full molecule. In contrast to existing approaches, transitions via single replacements of the most abundant isotope per element are used in separable tree branches to derive subisotopologues from each other. Moreover, the underlying transition trees prevent redundant replacements and permit the detection of the most probable isotopologue in a first phase. A relative threshold can then be exploited in a second parallelized phase for a precise prepruning of large fractions of the remaining subisotopologues. The gain in performance from such early pruning and the lower variation in the distortion of simulated data with use of relative rather than absolute thresholds were validated in a large-scale benchmark simulation, unprecedentedly comprising several thousand molecular formulas. Both the algorithm and a wealth of related features are freely available as R-package enviPat and as a user-friendly Web interface.

First principles simulations were used to predict aqueous one-electron oxidation potentials (E_ox) and associated half-cell reorganization energies (λ_aq) for aniline, phenol, methoxybenzene, imidazole, and dimethylsulfide. We employed quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations of the oxidized and reduced species in an explicit aqueous solvent, followed by EOM-IP-CCSD computations with effective fragment potentials for diabatic energy gaps of solvated clusters, and finally thermodynamic integration of the non-linear solvent response contribution using classical MD. A priori predicted E_ox and λ_aq values exhibit mean absolute errors of 0.17 V and 0.06 eV, respectively, compared to experiment. We also disaggregate E_ox into several well-defined free energy properties, including the gas phase adiabatic free energy of ionization (7.73 to 8.82 eV), the solvent-induced shift in the free energy of ionization due to linear solvent response (−2.01 to −2.73 eV), and the contribution from non-linear solvent response (−0.07 to −0.14 eV). The linear solvent response component is further apportioned into contributions from the solvent-induced shift in vertical ionization energy of the reduced species (ΔVIE_aq) and the solvent-induced shift in negative vertical electron affinity of the ionized species (ΔNVEA_aq). The simulated ΔVIE_aq and ΔNVEA_aq are found to contribute the principal sources of uncertainty in computational estimates of E_ox and λ_aq. Trends in the magnitudes of disaggregated solvation properties are found to correlate with trends in structural and electronic features of the solute. Finally, conflicting approaches for evaluating the aqueous reorganization energy are contrasted and discussed, and concluding recommendations are given.

Mitigation of N-nitrosodimethylamine (NDMA) and other hazardous water disinfection byproducts (DBP) is currently hampered by a limited understanding of DBP formation mechanisms. Because variations of the stable isotope composition of NDMA can potentially reveal reaction pathways and precursor compounds, we developed a method for the compound-specific isotope analysis (CSIA) of ¹³C/¹²C, ¹⁵N/¹⁴N, and ²H/¹H ratios of NDMA by gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). Method quantification limits for the accurate isotope analysis of NDMA, N-nitrosodiethyl-, -dipropyl-, and -dibutylamine as well as N-nitrosopyrrolidine were between 0.18 to 0.60 nmol C, 0.40 to 0.80 nmol N, and 2.2 to 5.8 nmol H injected on column. Coupling solid phase extraction (SPE) to GC/IRMS enabled the precise quantification of C, N, and H isotope ratios of NDMA in aqueous samples at concentrations of 0.6 μM (45 μg L^–1). We validated the proposed method with a laboratory experiment, in which NDMA was formed with stoichiometric yield (97 ± 4%) through chloramination of the pharmaceutical ranitidine (3 μM). δ¹³C and δ²H values of NDMA remained constant during NDMA formation while its δ¹⁵N increased due to a reaction at a N atom in the rate-limiting step of NDMA formation. The δ²H value of NDMA determined by SPE-GC/IRMS also corresponded well to the δ²H value of the N(CH₃)₂-group of ranitidine measured by quantitative deuterium nuclear magnetic resonance spectroscopy. This observation implies that the N(CH₃)₂-moiety of ranitidine is transferred to NDMA without being chemically altered and illustrates the accuracy of the proposed method.

Calculations of alternative oxidation pathways of toluene and its ortho-substituted nitro derivatives by permanganate anion have been performed. The competition between methyl group and ring oxidation has been addressed. Acceptable results have been obtained using IEFPCM/B3LYP/6-31+G(d,p) calculations with zero-point (ZPC) and thermal corrections, as validated by comparison with the experimental data. It has been shown that ring oxidation reactions proceed via relatively early transition states that become quite unsymmetrical for reactions involving ortho-nitrosubstituted derivatives. Transition states for the hydrogen atom abstraction reactions, on the other hand, are late. All favored reactions are characterized by the Gibbs free energy of activation, ΔG^≠, of about 25 kcal mol⁻¹. Methyl group oxidations are exothermic by about 20 kcal mol⁻¹ while ring oxidations are around thermoneutrality.

Sediment cores provide a valuable record of historical contamination, but so far, new analytical techniques such as high-resolution mass spectrometry (HRMS) have not yet been applied to extend target screening to the detection of unknown contaminants for this complex matrix. Here, a combination of target, suspect, and nontarget screening using liquid chromatography (LC)-HRMS/MS was performed on extracts from sediment cores obtained from Lake Greifensee and Lake Lugano located in the north and south of Switzerland, respectively. A suspect list was compiled from consumption data and refined using the expected method coverage and a combination of automated and manual filters on the resulting measured data. Nontarget identification efforts were focused on masses with Cl and Br isotope information available that exhibited mass defects outside the sample matrix, to reduce the effect of analytical interferences. In silico methods combining the software MOLGEN-MS/MS and MetFrag were used for direct elucidation, with additional consideration of retention time/partitioning information and the number of references for a given substance. The combination of all available information resulted in the successful identification of three suspect (chlorophene, flufenamic acid, lufenuron) and two nontarget compounds (hexachlorophene, flucofuron), confirmed with reference standards, as well as the tentative identification of two chlorophene congeners (dichlorophene, bromochlorophene) that exhibited similar time trends through the sediment cores. This study demonstrates that complementary application of target, suspect, and nontarget screening can deliver valuable information despite the matrix complexity and provide records of historical contamination in two Swiss lakes with previously unreported compounds.

Cobamides are a family of enzyme cofactors that include vitamin B₁₂ (cobalamin) and are produced solely by prokaryotes. Structural variability in the lower axial ligand has been observed in cobamides produced by diverse organisms. Of the three classes of lower ligands, the benzimidazoles are uniquely found in cobamides, whereas the purine and phenolic bases have additional biological functions. Many organisms acquire cobamides by salvaging and remodeling cobamides or their precursors from the environment. These processes require free benzimidazoles for incorporation as lower ligands, though the presence of benzimidazoles in the environment has not been previously investigated. Here, we report a new purification method and bioassay to measure the total free benzimidazole content of samples from microbial communities and laboratory media components. The bioassay relies on the "calcofluor-bright" phenotype of a bluB mutant of the model cobalamin-producing bacterium Sinorhizobium meliloti. The concentrations of individual benzimidazoles in these samples were measured by liquid chromatography-tandem mass spectrometry. Several benzimidazoles were detected in subpicomolar to subnanomolar concentrations in host-associated and environmental samples. In addition, benzimidazoles were found to be common contaminants of laboratory media components. These results suggest that benzimidazoles present in the environment and in laboratory media have the potential to influence microbial metabolic activities.

We use a Gaussian stochastic process emulator to interpolate the posterior probability density of a computationally demanding application of the biogeochemical-ecological lake model BELAMO to accelerate statistical inference of deterministic model and error model parameters. The deterministic model consists of a mechanistic description of key processes influencing the mass balance of nutrients, dissolved oxygen, organic particles, and phytoplankton and zooplankton in the lake. This model is complemented by a Gaussian stochastic process to describe the remaining model bias and by Normal, independent observation errors. A small subsample of the Markov chain representing the posterior of the model parameters is propagated through the full model to get model predictions and uncertainty estimates. We expect this approximation to be more accurate at only slightly higher computational costs compared to using a Normal approximation to the posterior probability density and linear error propagation to the results as we did in an earlier paper. The performance of the two techniques is compared for a didactical example as well as for the lake model. As expected, for the didactical example, the use of the emulator led to posterior marginals of the model parameters that are closer to those calculated by Markov chain simulation using the full model than those based on the Normal approximation. For the lake model, the new technique proved applicable without an excessive increase in computational requirements, but we faced challenges in the choice of the design data set for emulator calibration. As the posterior is a scalar function of the parameters, the suggested technique is an alternative to the emulation of a potentially more complex, structured output of the simulation model that allows for the use of a less case-specific emulator. This is at the cost that still the full model has to be used for prediction (which can be done with a smaller, approximately independent subsample of the Markov chain).

Spatially distributed models are popular tools in hydrology claimed to be useful to support management decisions. Despite the high spatial resolution of the computed variables, calibration and validation is often carried out only on discharge time series at specific locations due to the lack of spatially distributed reference data. Because of this restriction, the predictive power of these models, with regard to predicted spatial patterns, can usually not be judged.
An example of spatial predictions in hydrology is the prediction of saturated areas in agricultural catchments. These areas can be important source areas for inputs of agrochemicals to the stream. We set up a spatially distributed model to predict saturated areas in a 1.2 km² catchment in Switzerland with moderate topography and artificial drainage. We translated soil morphological data available from soil maps into an estimate of the duration of soil saturation in the soil horizons. This resulted in a data set with high spatial coverage on which the model predictions were validated. In general, these saturation estimates corresponded well to the measured groundwater levels.
We worked with a model that would be applicable for management decisions because of its fast calculation speed and rather low data requirements. We simultaneously calibrated the model to observed groundwater levels and discharge. The model was able to reproduce the general hydrological behavior of the catchment in terms of discharge and absolute groundwater levels. However, the the groundwater level predictions were not accurate enough to be used for the prediction of saturated areas. Groundwater level dynamics were not adequately reproduced and the predicted spatial saturation patterns did not correspond to those estimated from the soil map. Our results indicate that an accurate prediction of the groundwater level dynamics of the shallow groundwater in our catchment that is subject to artificial drainage would require a model that better represents processes at the boundary between the unsaturated and the saturated zone. However, data needed for such a more detailed model are not generally available. This severely hampers the practical use of such models despite their usefulness for scientific purposes.

During rain events, herbicides can be transported from their point of application to surface waters, where they may harm aquatic organisms. Since the spatial variability of herbicide losses to streams can be large, the identification of critical source areas could help to target mitigation measures efficiently to those locations where they reduce herbicide pollution the most. We performed a controlled herbicide application on wheat (isoproturon) and corn fields (atrazine, S-metolachlor and sulcotrione) in an agricultural head-water catchment (about 1 km²) in the Swiss Plateau to investigate the spatial variability of herbicide losses. We performed spatially distributed discharge measurements and high-resolution water sampling during rain events after herbicide application to determine herbicide loads and loss rates for individual fields. The dry weather conditions after the wheat herbicide application resulted in a very low isoproturon loss rate (0.005% of the applied amount). In contrast, the corn herbicide application was followed by several rain events with varying intensities and magnitudes causing loss rates of 0.26, 0.16 and 0.26% for atrazine, S-metolachlor and sulcotrione, respectively. The spatial differences in loss rates between fields were about a factor of three in most events. However, the spatial loss pattern varied between events implying that being a critical source area is not a temporally stable field property. No correlations were observed with several field characteristics (connectivity of the fields to the stream, the tendency for topsoil saturation, field-specific herbicide dissipation rates and sorption affinities). However, the data suggest that critical source areas may depend on the type of rain event because infiltration and saturation-excess runoff affects different parts of the catchment.

Micropollutants (MPs) as individual compounds or in complex mixtures are relevant for water quality and may trigger unwanted ecological effects. MPs originate from different point and diffuse sources and enter water bodies via different flow paths. Effluents from conventional wastewater treatment plants (WWTPs), in which various MPs are not or not completely removed, is one major source. To improve the water quality and avoid potential negative ecological effects by micropollutants, various measures to reduce the discharge should be taken. In this feature we discuss one of these measures; the benefits of upgrading WWTPs toward reduced MP loads and toxicities from wastewater effluents, using the recently decided Swiss strategy as an example. Based on (i) full-scale case studies using ozonation or powder activated carbon treatment, showing substantial reduction of MP discharges and concomitant reduced toxicities, (ii) social and political acceptance, (iii) technical feasibility and sufficient cost-effectiveness, the Swiss authorities recently decided to implement additional wastewater treatment steps as mitigation strategy to improve water quality. Since MPs are of growing global concern, the concepts and considerations behind the Swiss strategy are explained in this feature, which could be of use for other countries as well. It should be realized that upgrading WWTPs is not the only solution to reduce the discharge of MPs entering the environment, but is part of a broader, multipronged mitigation strategy.

Die unterschiedlichen Ziele aus den Bereichen Landwirtschaft, Gewässerschutz und Lebensmittelsicherheit machen Pflanzenschutzmittel (PSM) in Oberflächengewässern zu einem kontroversen Thema. Hinzu kommen regulatorische Widersprüche sowie Unklarheiten im Zusammenhang mit Zulassungs- (RAC) und Überwachungswerten (EQS). Zwei Faktenblätter der Eawag sollen mit klaren und objektiven Darlegungen die gesellschaftliche und politische Diskussion rund ums Thema PSM unterstützen.

Due to steady increase in use and mass production carbon nanotubes (CNTs) will inevitably end up in the environment. Because of their chemical nature CNTs are expected to be recalcitrant and biotransform only at very slow rates. Degradation of CNTs within days has recently been reported, but excluding one study, conclusions relied solely on qualitative results. We incubated 13 different types of CNTs and subjected them to enzymatic oxidation with horseradish peroxidase and concluded that the analytical methods commonly employed for studying degradation of CNTs did not have the sensitivity to unequivocally demonstrate degradation of these materials. To obtain unambiguous results with regard to the biotransformability of CNTs in the horseradish peroxidase system we incubated: (a) ¹⁴C-labeled multiwalled CNTs, homologous to Baytubes CNTs; and (b) ¹³C-depleted single-walled CNTs, used in previous studies. Our results show that ¹⁴C–CO₂ evolved linearly at a rate of about 0.02‰ per day, and at the end of the 30-day incubations the CO₂ evolved amounted to about 0.5‰ of both initial substrates, the ¹⁴C-labeled multiwalled and ¹³C-depleted single-walled CNTs. These results clearly show that CNT material is oxidized in the horseradish peroxidase system but with half-lives of about 80 years and not a few days as has been reported before. Adequately addressing biotransformation rates of CNTs is key toward a better understanding of the fate of these materials in the environment.

The root zone moisture storage capacity (S_R) of terrestrial ecosystems is a buffer providing vegetation continuous access to water and a critical factor controlling land-atmospheric moisture exchange, hydrological response, and biogeochemical processes. However, it is impossible to observe directly at catchment scale. Here, using data from 300 diverse catchments, it was tested that, treating the root zone as a reservoir, the mass curve technique (MCT), an engineering method for reservoir design, can be used to estimate catchment-scale S_R from effective rainfall and plant transpiration. Supporting the initial hypothesis, it was found that MCT-derived S_R coincided with model-derived estimates. These estimates of parameter S_R can be used to constrain hydrological, climate, and land surface models. Further, the study provides evidence that ecosystems dynamically design their root systems to bridge droughts with return periods of 10–40 years, controlled by climate and linked to aridity index, inter-storm duration, seasonality, and runoff ratio.

During the first hours after release of petroleum at sea, crude oil hydrocarbons partition rapidly into air and water. However, limited information is available about very early evaporation and dissolution processes. We report on the composition of the oil slick during the first day after a permitted, unrestrained 4.3 m³ oil release conducted on the North Sea. Rapid mass transfers of volatile and soluble hydrocarbons were observed, with >50% of ≤C₁₇ hydrocarbons disappearing within 25 h from this oil slick of <10 km² area and <10 μm thickness. For oil sheen, >50% losses of ≤C₁₆ hydrocarbons were observed after 1 h. We developed a mass transfer model to describe the evolution of oil slick chemical composition and water column hydrocarbon concentrations. The model was parametrized based on environmental conditions and hydrocarbon partitioning properties estimated from comprehensive two-dimensional gas chromatography (GC×GC) retention data. The model correctly predicted the observed fractionation of petroleum hydrocarbons in the oil slick resulting from evaporation and dissolution. This is the first report on the broad-spectrum compositional changes in oil during the first day of a spill at the sea surface. Expected outcomes under other environmental conditions are discussed, as well as comparisons to other models.

Biodegradation plays a major role in the natural attenuation of oil spills. However, limited information is available about biodegradation of different saturated hydrocarbon classes in surface environments, despite that oils are composed mostly of saturates, due to the limited ability of conventional gas chromatography (GC) to resolve this compound group. We studied eight weathered oil samples collected from four Gulf of Mexico beaches 12–19 months after the Deepwater Horizon disaster. Using comprehensive two-dimensional gas chromatography (GC×GC), we successfully separated, identified, and quantified several distinct saturates classes in these samples. We find that saturated hydrocarbons eluting after n-C22 dominate the GC-amenable fraction of these weathered samples. This compound group represented 8–10%, or 38–68 thousand metric tons, of the oil originally released from Macondo well. Saturates in the n-C₂₂ to n-C₂₉ elution range were found to be partly biodegraded, but to different relative extents, with ease of biodegradation decreasing in the following order: n-alkanes > methylalkanes and alkylcyclopentanes+alkylcyclohexanes > cyclic and acyclic isoprenoids. We developed a new quantitative index designed to characterize biodegradation of >n-C₂₂ saturates. These results shed new light onto the environmental fate of these persistent, hydrophobic, and mostly overlooked compounds in the unresolved complex mixtures (UCM) of weathered oils.

This paper describes the degradation of the X-ray contrast agent iopromide (IOP) and the antibiotic ofloxacin (OFLOX) by the white-rot-fungus Trametes versicolor. Batch studies in synthetic medium revealed that between 60 and 80% of IOP and OFLOX were removed when spiked at approximately 12 mg L⁻¹ and 10 mg L⁻¹, respectively. A significant number of transformation products (TPs) were identified for both pharmaceuticals, confirming their degradation. IOP TPs were attributed to two principal reactions: (i) sequential deiodination of the aromatic ring and (ii) N-dealkylation of the amide at the hydroxylated side chain of the molecule. On the other hand, OFLOX transformation products were attributed mainly to the oxidation, hydroxylation and cleavage of the piperazine ring.
Experiments in 10 L-bioreactor with fungal biomass fluidized by air pulses operated in batch achieved high percentage of degradation of IOP and OFLOX when load with sterile (87% IOP, 98.5% OFLOX) and unsterile (65.4% IOP, 99% OFLOX) hospital wastewater (HWW) at their real concentration (μg L⁻¹ level). Some of the most relevant IOP and OFLOX TPs identified in synthetic medium were also detected in bioreactor samples. Acute toxicity tests indicated a reduction of the toxicity in the final culture broth from both experiments in synthetic medium and in batch bioreactor.

Removal of micropollutants (MPs) during activated sludge treatment can mainly be attributed to biotransformation and sorption to sludge flocs, whereby the latter process is known to be of minor importance for polar organic micropollutants. In this work, we investigated the influence of pH on the biotransformation of MPs with cationic-neutral speciation in an activated sludge microbial community. We performed batch biotransformation, sorption control, and abiotic control experiments for 15 MPs with cationic-neutral speciation, one control MP with neutral-anionic speciation, and two neutral MPs at pHs 6, 7, and 8. Biotransformation rate constants corrected for sorption and abiotic processes were estimated from measured concentration time series with Bayesian inference. We found that biotransformation is pH-dependent and correlates qualitatively with the neutral fraction of the ionizable MPs. However, a simple speciation model based on the assumption that only the neutral species is efficiently taken up and biotransformed by the cells tends to overpredict the effect of speciation. Therefore, additional mechanisms such as uptake of the ionic species and other more complex attenutation mechanisms are discussed. Finally, we observed that the sorption coefficients derived from our control experiments were small and showed no notable pH-dependence. From this we conclude that pH-dependent removal of polar, ionizable organic MPs in activated sludge systems is less likely an effect of pH-dependent sorption but rather of pH-dependent biotransformation. The latter has the potential to cause marked differences in the removal of polar, ionizable MPs at different operational pHs during activated sludge treatment.

Soil incubation experiments using ¹⁴C-labelled sulfamethazine were carried out to assess the factors governing its nonextractable residue (NER) formation via nucleophilic addition reactions. Circumstantial evidence on possible mechanisms of NER formation was derived from a selective manipulation of soil samples. The amount of quinones in soil available for nucleophilic addition was a limiting factor as indicated by (i) an (initial) increase of NER formation by adding quinone precursors or enhancing their formation by manganese oxide addition and (ii) a decrease of NER formation by limiting the formation of quinones under anaerobic conditions. A slow NER formation with time under aerobic conditions is likely caused by covalent bonding as well, because no slow NER formation phase was observed under anaerobic conditions.

Diffuse phosphorus (P) losses are the main cause for eutrophication of surface waters in many regions. Implementing mitigation measures on critical source areas (CSAs) is seen to be the most effective way to reduce P losses. Thus, tools are needed that delineate CSAs on the basis of available data. We compared three models based on different approaches and sets of input data: the rainfall-runoff-phosphorus (RRP) model, the dominant runoff processes (DoRP) model, and the Sensitive Catchment Integrated Modeling Analysis Platform (SCIMAP). The RRP model is a parsimonious dynamic model using the topographic index and a binary soil classification to simulate discharge and P losses. The DoRP model distinguishes eight soil classes based on soil and geological maps. It does not account for topography when calculating runoff. SCIMAP assesses runoff risks solely on the basis of topography using the network index. Compared to surface runoff and soil moisture data available from a catchment in Switzerland, the RRP model and SCIMAP made better predictions than the DoRP model, suggesting that in our study area topography was more important for CSA delineation than soil data. Based on the results, we suggest improvements of SCIMAP to enable average risk predictions and the comparison of risk predictions between catchments.

In this study, the spatial extent of a wastewater-influenced water mass (plume) originating from a wastewater treatment plant outlet in Vidy Bay (Lake Geneva) was monitored by two manned submersibles from June to August 2011. The main goal was to assess whether micropollutants in the wastewater mass cause an ecotoxicological risk to the aquatic environment, and to determine how far the zone of risk extends beyond the wastewater outlet. Real-time measurements of elevated electrical conductivity were used as a proxy to indicate the presence of wastewater-influenced water. Conductivity was highest in immediate proximity to the wastewater outlet, though if all measurements obtained over the duration of the sampling campaign were integrated, elevated conductivity extended over an area of at least 1 km² surrounding the outlet. Additionally, water samples were collected within and outside Vidy Bay, and were analyzed for 39 micropollutants (pharmaceuticals, pesticides, and corrosion inhibitors). Micropollutant concentrations were generally in the low ng/L range, though for some substances >100 ng/L was measured. The concentrations of most pharmaceuticals, which are primarily wastewater-derived, decreased with decreasing conductivity and with increasing distance from the wastewater outlet. Pesticide concentrations, in contrast, were homogeneous throughout Vidy Bay and the lake. An ecotoxicological risk assessment based on the cumulative risk exerted by all measured substances indicated that the wastewater caused a zone of potential ecotoxicological risk that extended well into the deep lake and in the direction of a downstream drinking water intake.

Assessing the pathways and rates of organic pollutant transformation in the environment is a major challenge due to co-occurring transport and degradation processes. Measuring changes of stable isotope ratios (e.g. ¹³C/¹²C, ²H/¹H, ¹⁵N/¹⁴N) in individual organic compounds by compound-specific isotope analysis (CSIA) makes it possible to identify degradation pathways without the explicit need to quantify pollutant concentration dynamics. The so-called isotope fractionation observed in an organic pollutant is related to isotope effects of (bio)chemical reactions and enables one to characterize pollutant degradation even if multiple processes take place simultaneously. Here, we illustrate some principles of CSIA using benzotriazole, a frequently observed aquatic micropollutant, as example. We show subsequently how the combined C and N isotope fractionation analysis of nitroaromatic compounds reveals kinetics and mechanisms of reductive and oxidative reactions as well as their (bio)degradation pathways in the environment.

To characterize a broad range of organic contaminants and their transformation products (TPs) as well as their loads, input pathways and fate in the water cycle, the Department of Environmental Chemistry (Uchem) at Eawag applies and develops high-performance liquid chromatography (LC) methods combined with high-resolution tandem mass spectrometry (HRMS/MS). In this article, the background and state-of-the-art of LC-HRMS/MS for detection of i) known targets, ii) suspected compounds like TPs, and iii) unknown emerging compounds are introduced briefly. Examples for each approach are taken from recent research projects conducted within the department. These include the detection of trace organic contaminants and their TPs in wastewater, pesticides and their TPs in surface water, identification of new TPs in laboratory degradation studies and ozonation experiments and finally the screening for unknown compounds in the catchment of the river Rhine.

A wide variety of micropollutants from Swiss rivers can be found in bank filtrate. While many micropollutants are degraded or retarded as they pass through the subsurface, certain persistent substances end up in drinking water. Even though they do not occur in concentrations hazardous to human health, inputs of these substances to surface waters should be minimized.

De nombreux micropolluants s’infiltrent dans les alluvions avec l’eau des rivières suisses. Beaucoup d’entre eux sont retenus ou dégradés lors de leur passage dans le sol mais certains, particulièrement persistants, parviennent dans l’eau captée pour la production d’eau potable. Même si les concentrations sont alors jugées peu nocives pour la santé, il importe de réduire les émissions dans les rivières.

Eine Reihe von Mikroverunreinigungen gelangt aus Schweizer Flüssen in die Uferfiltrationszone. Viele dieser Substanzen werden während der Passage durch das Ufer und den Grundwasserleiter abgebaut oder zurückgehalten. Gewisse langlebige Stoffe landen trotzdem im Trinkwasser. Auch wenn sie nicht in gesundheitsgefährdenden Konzentrationen vorliegen, gilt es, ihren Eintrag in die Gewässer zu minimieren.

Climate change impact assessments have become more and more popular in hydrology since the middle 1980s with a recent boost after the publication of the IPCC AR4 report. From hundreds of impact studies a quasi-standard methodology has emerged, to a large extent shaped by the growing public demand for predicting how water resources management or flood protection should change in the coming decades. The "standard" workflow relies on a model cascade from global circulation model (GCM) predictions for selected IPCC scenarios to future catchment hydrology. Uncertainty is present at each level and propagates through the model cascade. There is an emerging consensus between many studies on the relative importance of the different uncertainty sources. The prevailing perception is that GCM uncertainty dominates hydrological impact studies. Our hypothesis was that the relative importance of climatic and hydrologic uncertainty is (among other factors) heavily influenced by the uncertainty assessment method. To test this we carried out a climate change impact assessment and estimated the relative importance of the uncertainty sources. The study was performed on two small catchments in the Swiss Plateau with a lumped conceptual rainfall runoff model. In the climatic part we applied the standard ensemble approach to quantify uncertainty but in hydrology we used formal Bayesian uncertainty assessment with two different likelihood functions. One was a time series error model that was able to deal with the complicated statistical properties of hydrological model residuals. The second was an approximate likelihood function for the flow quantiles. The results showed that the expected climatic impact on flow quantiles was small compared to prediction uncertainty. The choice of uncertainty assessment method actually determined what sources of uncertainty could be identified at all. This demonstrated that one could arrive at rather different conclusions about the causes behind predictive uncertainty for the same hydrological model and calibration data when considering different objective functions for calibration.

Benzotriazoles are widely used domestic and industrial corrosion inhibitors and have become omnipresent organic micropollutants in the aquatic environment. Here, the range of aerobic biological degradation mechanisms of benzotriazoles in activated sludge was investigated. Degradation pathways were elucidated by identifying transient and persistent transformation products in batch experiments using liquid chromatography-high-resolution tandem mass spectrometry (LC-HR-MS/MS). In addition, initial reactions were studied using compound-specific isotope analysis (CSIA). Biodegradation half-lives of 1.0 days for 1H-benzotriazole, 8.5 days for 4-methyl-1H-benzotriazole, and 0.9 days for 5-methyl-1H-benzotriazole with activated sludge confirmed their known partial persistence in conventional wastewater treatment. Major transformation products were identified as 4- and 5-hydroxy-1H-benzotriazole for the degradation of 1H-benzotriazole, and 1H-benzotriazole-5-carboxylic acid for the degradation of 5-methyl-1H-benzotriazole. These transformation products were found in wastewater effluents, showing their environmental relevance. Many other candidate transformation products, tentatively identified by interpretation of HR-MS/MS spectra, showed the broad range of possible reaction pathways including oxidation, alkylation, hydroxylation and indicate the significance of cometabolic processes for micropollutant degradation in biological wastewater treatment in general. The combination of evidence from product analysis with the significant carbon and nitrogen isotope fractionation suggests that aromatic monohydroxylation is the predominant step during the biotransformation of 1H-benzotriazole.

New behavioral indexes including combined index (CI), distribution index (DI), toxic index (TI), and altitude index (AI) for a biological early warning system (BEWS) were developed and evaluated using Daphnia magna in this study. The sensitivity and stability of each index were compared to evaluate the performance of the indexes through a real-time exposure test with a synthetic copper solution. The applicability of the CI to the field sample was evaluated through an effluent exposure test. The proportional relationship between toxicity level and magnitude of response was much lower in the effluent due to the complexity of water than in the copper solution. The results showed that the CI was most sensitive among the three indexes, while the DI was confirmed as the most useful index among the individual indexes. The combined index (CI) shows not only sensitivity but also stability in normal conditions below the statistically significant threshold (p < 0.01), whereas the individual indexes displayed unstable index values in normal conditions (p > 0.01). The CI improved performance of the BEWS in terms of sensitivity and stability, and it was confirmed as the higher correlation coefficient between the magnitude of the index and the toxicity level of the water sample.

The number of functional traits of a wastewater treatment plant (WWTP) microbial community (i.e. functional richness) is thought to be an important determinant of its overall functional performance, but the ecological factors that determine functional richness remain unclear. The number of taxa within a community (i.e. taxonomic richness) is one ecological factor that might be important. Communities that contain more taxa are more likely to have more functional traits, and a positive association is therefore expected between functional and taxonomic richness. Empirical tests for this positive association among WWTP communities, however, are lacking. We address this knowledge gap by measuring the functional and taxonomic richness of 10 independent WWTP communities. We demonstrate that functional and taxonomic richness are positively associated with each other. We further demonstrate that functional and taxonomic richness are negatively associated with the effluent NH₄-N and BOD₅ concentrations. This led us to hypothesize that correlated variation in functional and taxonomic richness is likely related to variation in ambient nitrogen and carbon availability. We finally demonstrate that this hypothesis is consistent with the functional and taxonomic attributes of the WWTP communities. Together, our results improve our basic understanding of the ecology and functioning of WWTP communities.

In this study, the kinetics of Fe(II) oxidation in the presence of the iron oxyhydroxides ferrihydrite, Si-ferrihydrite, schwertmannite, lepidocrocite and goethite are investigated over the pH range 4–5.5. Despite limited sorption of Fe(II), the rate of Fe(II) oxidation is up to 70-fold faster than in the absence of any Fe oxyhydroxide phase over pH 4.5–5.5. Enhanced Fe(II) oxidation was minor or negligible at pH 4 with undetectable amounts of Fe(II) adsorbed to the iron oxyhydroxides at this pH. Heterogeneous rate constants derived from kinetic modeling were normalized to the concentration of adsorbed Fe(II) and deviated by no more than 13.8% at pH 4.5, 5 and 5.5, indicating that oxidation is proportional to the concentration of adsorbed Fe(II). Average rate constants were found to be: 2.12 ± 0.20, 1.30 ± 0.09, 1.69 ± 0.22, 1.20 ± 0.08 and 0.68 ± 0.09 M⁻¹ s⁻¹ for ferrihydrite, goethite, lepidocrocite, schwertmannite and Si-ferrihydrite, respectively. The role of reactive oxygen species, such as hydrogen peroxide, the hydroxyl radical and superoxide, towards the overall oxidation of Fe(II) was examined but found to have only a minor impact on Fe(II) oxidation when compared to the effect of heterogeneous oxidation.

This work provides an introduction to mathematical modeling of molecules and the resulting applications (structure generation, structure elucidation, QSAR/QSPR etc.). Most chemists have experimented with some software that represents molecules in an electronic form, and such models and applications are of increasing interest in diverse and growing fields such as drug discovery, environmental science and metabolomics. Furthermore, structure generation remains the only way to systematically create molecules that are not (yet) present in a database. This book starts with the mathematical theory behind representing molecules, explaining chemical concepts in mathematical terms and providing exercises that can be completed online. The later chapters cover applications of the theory, with detailed explanations on QSPR and QSAR investigations and finally structure elucidation combining mass spectrometry and structure generation. This book is aimed in particular at the users of structure generation methods and corresponding techniques, but also for those interested in teaching and learning mathematical chemistry, and for software designers in chemoinformatics.

The potential bioaccumulation and distribution of antibiotics in non-target organisms have been inadequately studied in spite of their widespread occurrence in aquatic systems. We investigated the ability of tetracycline to bioaccumulate through aqueous and dietary routes in an aquatic organism, the freshwater crustacean Daphnia magna. D. magna was exposed to algal food (Pseudokirchneriella subcapitata) contaminated with tetracycline for dietary uptake. Tetracycline was transferred to D. magna more through aqueous uptake than through dietary uptake. The uptake rate constant of tetracycline for D. magna was k_in,water = 0.33 ± 0.045 via the aqueous route and k_in,food = 0.16 ± 0.012 via the dietary route for 1.0 mg L⁻¹ tetracycline. Bioconcentration factors of 4.40 ± 0.91 L kg⁻¹ and 3.66 ± 0.50 L kg⁻¹ for 0.1 and 1.0 mg L⁻¹ tetracycline were found for D. magna. The biomagnification factor of 0.19 ± 0.04 indicates that magnification of tetracycline through the food web will not occur. The change in the internal concentration of the target compound was also studied for multigenerational (F1-F4) exposure. The internal concentration in D. magna showed a decreasing trend with increasing generations except for the parent generation. The bioaccumulation tendency showed a biphasic change in multigenerational exposure.

In der Schweiz findet ein rascher Wandel von Landschaft und Landschaftsnutzung statt, die Bevölkerung nimmt stark zu und die Wirtschaftsaktivitäten wachsen. Dadurch akzentuieren sich Nutzungskonflikte im Wassersektor: Wo einst verschiedene Nutzergruppen unabhängig voneinander agieren konnten, überlagern sich die verschiedenen Ansprüche immer stärker. Zugleich ändern sich die Rahmenbedingungen der Wasserbewirtschaftung durch den Klimawandel.

This report describes how water and aquatic ecosystems in Switzerland are presently being utilised. It also documents present and – as far as foreseeable – future conflicts and potential synergies resulting from the different uses. The analysis is based wherever possible on knowledge gained by NRP 61 research projects, yet also draws on insights of other research projects, official reports and publications. The report hence lays out the current state of knowledge on water utilisation in Switzerland. To identify the relevant synergies and conflicts, all important demands on water and aquatic ecosystems have been examined. This includes activities that do not originally intend to make use of water or water bodies, but do have an impact on their condition and hence on other water users. The impact of the various activities on water and aquatic ecosystems was analysed on the basis of literature research and interviews with experts, and framed along the four dimensions water quantity, water quality, hydromorphology and land-use (chapters A to D). The results are summarised in four utilization matrices showing how the various activities (potentially) impact other uses. These matrices epitomise the essence of chapters A to D, in which the impact of different user demands is explored in detail.

This report describes how water and aquatic ecosystems in Switzerland are presently being utilised. It also documents present and – as far as foreseeable – future conflicts and potential synergies resulting from the different uses. The analysis is based wherever possible on knowledge gained by NRP 61 research projects, yet also draws on insights of other research projects, official reports and publications. The report hence lays out the current state of knowledge on water utilisation in Switzerland. To identify the relevant synergies and conflicts, all important demands on water and aquatic ecosystems have been examined. This includes activities that do not originally intend to make use of water or water bodies, but do have an impact on their condition and hence on other water users. The impact of the various activities on water and aquatic ecosystems was analysed on the basis of literature research and interviews with experts, and framed along the four dimensions water quantity, water quality, hydromorphology and land-use (chapters A to D). The results are summarised in four utilization matrices showing how the various activities (potentially) impact other uses. These matrices epitomise the essence of chapters A to D, in which the impact of different user demands is explored in detail.

Die Siedlungsfläche in der Schweiz hat in den vergangenen Jahrzehnten deutlich zugenommen. Laut Arealstatistik ist sie zwischen der letzten Erhebung von 1992/97 (BFS Arealstatistik 1992/97) und der aktuellen Erhebung von 2004/2009 (BFS Arealstatistik 2004/09) um 58'422 ha gewachsen, hauptsächlich auf Kosten der landwirtschaftlichen Nutzfläche (minus 55'557 ha ohne Berücksichtigung aufgegebener Alpflächen).

Determining optimal ozone doses for organic micropollutant elimination during wastewater ozonation is challenged by the presence of a large number of structurally diverse micropollutants for varying wastewater matrice compositions. A chemical kinetics approach based on ozone and hydroxyl radical (·OH) rate constant and measurements of ozone and ·OH exposures is proposed to predict the micropollutant elimination efficiency. To further test and validate the chemical kinetics approach, the elimination efficiency of 25 micropollutants present in a hospital wastewater effluent from a pilot-scale membrane bioreactor (MBR) were determined at pH 7.0 and 8.5 in bench-scale experiments with ozone alone and ozone combined with H₂O₂ as a function of DOC-normalized specific ozone doses (gO₃/gDOC). Furthermore, ozone and ·OH exposures, ·OH yields, and ·OH consumption rates were determined. Consistent eliminations as a function of gO₃/gDOC were observed for micropollutants with similar ozone and OH rate constants. They could be classified into five groups having characteristic elimination patterns. By increasing the pH from 7.0 to 8.5, the elimination levels increased for the amine-containing micropollutants due to the increased apparent second-order ozone rate constants while decreased for most micropollutants due to the diminished ozone or ·OH exposures. Increased ·OH quenching by effluent organic matter and carbonate with increasing pH was responsible for the lower ·OH exposures. Upon H₂O₂ addition, the elimination levels of the micropollutants slightly increased at pH 7 (<8%) while decreased considerably at pH 8.5 (up to 31%). The elimination efficiencies of the selected micropollutants could be predicted based on their ozone and ·OH rate constants (predicted or taken from literature) and the determined ozone and ·OH exposures. Reasonable agreements between the measured and predicted elimination levels were found, demonstrating that the proposed chemical kinetics method can be used for a generalized prediction of micropollutant elimination during wastewater ozonation. Out of 67 analyzed micropollutants, 56 were present in the tested hospital wastewater effluent. Two-thirds of the present micropollutants were found to be ozone-reactive and efficiently eliminated at low ozone doses (e.g., >80% for gO₃/gDOC = 0.5).

Bioconcentration and transformation of the potent and persistent xeno-estrogen 17α-ethinylestradiol (EE2) by organisms at the basis of the food web have received only little research attention. In this study, uptake, elimination, and biotransformation of radiolabeled EE2 (¹⁴C-EE2) by the freshwater green alga Desmodesmus subspicatus were investigated. The alga highly incorporated radioactivity following ¹⁴C-EE2 exposure. Up to 68% of the test compound was removed from the medium by D. subspicatus within a rather short time period (72 h C_algae/C_water: 2200 L/kg wet weight). When the algae were transported to clear medium, a two-stage release pattern was observed with an initially quick elimination phase following slower clearance afterward. Interestingly, D. subspicatus brominated EE2 when bromide was available in the medium, a transformation process demonstrated to occur abiotically but not by algae. The consequence of the presence of more hydrophobic mono- and dibrominated EE2 in the environment remains to be further investigated, as these products were shown to have a lower estrogenic potency but are expected to have a higher bioaccumulation potential and to be more toxic than the mother compound.

Pyrethroids and organophosphates are among the most toxic insecticides for aquatic organisms, leading to annual-average environmental quality standards (AA-EQS) in the picogram per liter range in surface waters. For monitoring purposes, it is therefore crucial to develop very sensitive analytical methods. Until now, it is very difficult to reach detection limits at or below given AA-EQSs. Here, we present a passive sampling method using silicone rubber (SR) sheets for the sampling of ten pyrethroids and two organophosphates in surface waters. An analytical method was developed, optimized and validated for the extraction of the insecticides from the SR sheets by accelerated solvent extraction followed by clean-up on C18 and silica gel and detection with GC–MS/MS in positive ionization mode. Good precision (<20%) and absolute recovery (>50%) was observed for all substances, accuracy was between 66% and 139%. Limits of detection between 6 and 200 pg/L were achieved for all substances in surface waters using average sampling rates for PCBs and PAHs. The lack of substance-specific sampling rates and missing performance reference compounds led to an uncertainty in the concentration estimation of factor three in both directions. In a large field study, comprising 40 environmental samples from nine Swiss rivers, eight out of 12 substances were detected (most frequently: chlorpyrifos, cypermethrin). Most of the estimated organophosphate concentrations were between 0.1 and 1 ng/L, most pyrethroid detections below 0.1 ng/L. Four substances (chlorpyrifos-methyl, cypermethrin, deltamethrin and lambda-cyhalothrin) showed exceedances of their respective AA-EQS in multiple samples, also when the uncertainties in the concentration estimation were considered. As pyrethroid and organophosphate detection by SR passive sampling is very practicable and allows sensitive analysis, it has the potential to become a new tool in the monitoring of non-polar pesticides.

A comprehensive assessment of pesticides in surface waters is challenging due to the large number of potential contaminants. Most scientific studies and routine monitoring programs include only 15–40 pesticides, which leads to error-prone interpretations. In the present study, an extensive analytical screening was carried out using liquid chromatography–high-resolution mass spectrometry, covering 86% of all polar organic pesticides sold in Switzerland and applied to agricultural or urban land (in total 249 compounds), plus 134 transformation products; each of which could be quantified in the low ng/L range. Five medium-sized rivers, containing large areas of diverse crops and urban settlements within the respective catchments, were sampled between March and July 2012. More than 100 parent compounds and 40 transformation products were detected in total, between 30 and 50 parent compounds in each two-week composite sample in concentrations up to 1500 ng/L. The sum of pesticide concentrations was above 1000 ng/L in 78% of samples. The chronic environmental quality standard was exceeded for 19 single substances; using a mixture toxicity approach, exceedances occurred over the whole measurement period in all rivers. With scenario calculations including only 30–40 frequently measured pesticides, the number of detected substances and the mixture toxicity would be underestimated on average by a factor of 2. Thus, selecting a subset of substances to assess the surface water quality may be sufficient, but a comprehensive screening yields substantially more confidence.

Comprehensive two-dimensional gas chromatography (GC × GC) is effective for separating and quantifying nonpolar organic chemicals in complex mixtures. Here we present a model to estimate 11 environmental partitioning properties for nonpolar analytes based on GC × GC chromatogram retention time information. The considered partitioning properties span several phases including pure liquid, air, water, octanol, hexadecane, particle natural organic matter, dissolved organic matter, and organism lipids. The model training set and test sets are based on a literature compilation of 648 individual experimental partitioning property data. For a test set of 50 nonpolar environmental contaminants, predicted partition coefficients exhibit root-mean-squared errors ranging from 0.19 to 0.48 log unit, outperforming Abraham-type solvation models for the same chemical set. The approach is applicable to nonpolar organic chemicals containing C, H, F, Cl, Br, and I, having boiling points ≤402 °C. The presented model is calibrated, easy to apply, and requires the user only to identify a small set of known analytes that adapt the model to the GC × GC instrument program. The analyst can thus map partitioning property estimates onto GC × GC chromatograms of complex mixtures. For example, analyzed nonpolar chemicals can be screened for long-range transport potential, aquatic bioaccumulation potential, arctic contamination potential, and other characteristic partitioning behaviors.

Oxygenation of aromatic rings is a frequent initial step in the biodegradation of persistent contaminants, and the accompanying isotope fractionation is increasingly used to assess the extent of transformation in the environment. Here, we systematically investigated the dioxygenation of two nitroaromatic compounds (nitrobenzene and 2-nitrotoluene) by nitrobenzene dioxygenase (NBDO) to obtain insights into the factors governing its C, H, and N isotope fractionation. Experiments were carried out at different levels of biological complexity from whole bacterial cells to pure enzyme. C, H, and N isotope enrichment factors and kinetic isotope effects (KIEs) were derived from the compound-specific isotope analysis of nitroarenes, whereas C isotope fractionation was also quantified in the oxygenated reaction products. Dioxygenation of nitrobenzene to catechol and 2-nitrotoluene to 3-methylcatechol showed large C isotope enrichment factors, ϵ_C, of −4.1 ± 0.2‰ and −2.5 ± 0.2‰, respectively, and was observed consistently in the substrates and dioxygenation products. ϵ_H- and ϵ_N-values were smaller, that is −5.7 ± 1.3‰ and −1.0 ± 0.3‰, respectively. C isotope fractionation was also identical in experiments with whole bacterial cells and pure enzymes. The corresponding ¹³C-KIEs for the dioxygenation of nitrobenzene and 2-nitrotoluene were 1.025 ± 0.001 and 1.018 ± 0.001 and suggest a moderate substrate specificity. Our study illustrates that dioxygenation of nitroaromatic contaminants exhibits a large C isotope fractionation, which is not masked by substrate transport and uptake processes and larger than dioxygenation of other aromatic hydrocarbons.

The worldwide distribution and high bioaccumulation potential of pentachlorophenol (PCP) in aquatic organisms imply a high toxicological impact in aquatic systems. Firstly, our investigations show that, similar to mammalian cell lines, PCP can be metabolized to tetrachlorohydroquinone (TCHQ) in the permanent cell line derived from rainbow trout liver cells (RTL-W1). Moreover, we demonstrate that PCP as well as its metabolite TCHQ is capable of influencing the viability of these cells. Three cell viability assays were performed to assess possible cellular targets of these substances. Thus, the cytotoxicity of the PCP-derivative TCHQ was shown for the first time in a fish cell line. Further investigations revealed the involvement of ROS in the cytotoxicity of PCP and its metabolite TCHQ. The observation of oxidative stress provides a plausible explanation for the increased cytotoxicity at higher concentrations especially for PCP and implies possible mechanisms underlying these observations. In addition, antioxidants such as ascorbic acid and quercetin modulate the detrimental effects of PCP and TCHQ whereby both compounds exacerbate the cytotoxic effects of high PCP and TCHQ concentrations.

Twenty percent of the water run-off from China’s land surface drains into the Yangtze River and carries the sewage of approximately 400 million people out to sea. The lower stretch of the Yangtze therefore offers the opportunity to assess the pollutant discharge of a huge population. To establish a comprehensive assessment of micropollutants, river water samples were collected monthly from May 2009 to June 2010 along a cross-section at the lowermost hydrological station of the Yangtze River not influenced by the tide (Datong Station, Anhui province). Following a prescreening of 268 target compounds, we examined the occurrence, seasonal variation, and annual loads of 117 organic micropollutants, including 51 pesticides, 43 pharmaceuticals, 7 household and industrial chemicals, and 16 polycyclic aromatic hydrocarbons (PAHs). During the 14-month study, the maximum concentrations of particulate PAHs (1–5 μg/g), pesticides (11–284 ng/L), pharmaceuticals (5–224 ng/L), and household and industrial chemicals (4–430 ng/L) were generally lower than in other Chinese rivers due to the dilution caused of the Yangtze River’s average water discharge of approximately 30,000 m³/s. The loads of most pesticides, anti-infectives, and PAHs were higher in the wet season compared to the dry season, which was attributed to the increased agricultural application of chemicals in the summer, an elevated water discharge through the sewer systems and wastewater treatment plants (WWTP) as a result of high hydraulic loads and the related lower treatment efficiency, and seasonally increased deposition from the atmosphere and runoff from the catchment. The estimated annual load of PAHs in the river accounted for some 4% of the total emission of PAHs in the whole Yangtze Basin. Furthermore, by using sucralose as a tracer for domestic wastewater, we estimate a daily disposal of approximately 47 million m³ of sewage into the river, corresponding to 1.8% of its average hydraulic load. In summary, the annual amounts flushed by the Yangtze River into the East China Sea were 2.9 × 10⁶ tons of dissolved and particulate organic carbon (DOC and POC), 369 tons of PAHs, 98 tons of pesticides, 152 tons of pharmaceuticals, and 273 tons of household and industrial chemicals. While the concentrations seem comparably moderate, the pollutant loads are considerable and pose an increasing burden to the health of the marine coastal ecosystem.

Anthropogenic contamination of surface waters in Asia is on the increase. While polar organic contaminants are gradually recognized for their impacts on aquatic ecosystems in the Western World, less is known about the situation in Asia. In developing countries like China, water resources are particularly vulnerable. We investigated the occurrence, elimination, and per capita loads of a wide range of pharmaceuticals, household chemicals and pesticides in five Beijing WWTPs representative for megacities in China, and compare the efficiency of different treatment processes. Based on initial screening for 268 micropollutants using high-resolution mass spectrometry, 33 compounds were examined in detail. Pollutant concentrations in raw wastewater ranged from <0.02 μg L⁻¹ for pesticides to >20 μg L⁻¹ for caffeine and the contrast agent iopromide. Concentrations in the WWTP effluents were generally <1 μg L⁻¹, except for some pharmaceuticals, iopromide (1.2–18 μg L⁻¹), caffeine (0.025–2.3 μg L⁻¹), and the artificial sweetener sucralose (2.7–3.5 μg L⁻¹). Elimination efficiencies varied greatly from <1% to close to 100%, with macrolides, some sulfonamides, metronidazole, iopromide, and 4-acetamidoantipyrine being the most persistent compounds. Total per capita loads of the investigated micropollutants were lower than in communal wastewater of Europe, amounting to 7.9–12.2 and 2.0–6.5 g d⁻¹ 1000 inhabitants⁻¹ in the influents and effluents, respectively, with an average release of ∼100 kg d⁻¹ by the 11.4 million people and 2.3 million m³ of wastewater treated per day. Since the wastewater effluents are often used for agricultural irrigation, residual organic pollutants pose a threat to food safety, the development of antibacterial resistance, and combined effects of micropollutants in the aquatic environment.

There are worldwide approximately 4.3 million coffee (Coffea arabica) producing smallholders generating a large share of tropical developing countries' gross domestic product, notably in Central America. Their livelihoods and coffee production are facing major challenges due to projected climate change, requiring adaptation decisions that may range from changes in management practices to changes in crops or migration. Since management practices such as shade use and reforestation influence both climate vulnerability and carbon stocks in coffee, there may be synergies between climate change adaptation and mitigation that could make it advantageous to jointly pursue both objectives. In some cases, carbon accounting for mitigation actions might even be used to incentivize and subsidize adaptation actions. To assess potential synergies between climate change mitigation and adaptation in smallholder coffee production systems, we quantified (i) the potential of changes in coffee production and processing practices as well as other livelihood activities to reduce net greenhouse gas emissions, (ii) coffee farmers' climate change vulnerability and need for adaptation, including the possibility of carbon markets subsidizing adaptation. We worked with smallholder organic coffee farmers in Northern Nicaragua, using workshops, interviews, farm visits and the Cool Farm Tool software to calculate greenhouse gas balances of coffee farms. From the 12 activities found to be relevant for adaptation, two showed strong and five showed modest synergies with mitigation. Afforestation of degraded areas with coffee agroforestry systems and boundary tree plantings resulted in the highest synergies between adaptation and mitigation. Financing possibilities for joint adaptation-mitigation activities could arise through carbon offsetting, carbon insetting, and carbon footprint reductions. Non-monetary benefits such as technical assistance and capacity building could be effective in promoting such synergies at low transaction costs.

Im Rahmen der Thematischen Synthese „Bewirtschaftung der Wasserressourcen unter steigendem Nutzungsdruck“ (Thematische Synthese 2 (TS 2)) des Nationalen Forschungsprogramms 61 „Nachhaltige Wassernutzung“ wurden Nutzungsüberlagerungen im Wasserbereich der Schweiz und die sich daraus ergebenden Konflikte und Synergien systematisch untersucht. Zu diesem Zweck wurden verschiedenste GIS-Datensätze zusammengetragen, miteinander verschnitten und z.T. neu dargestellt. Im Folgenden sind die im Bericht verwendeten GIS-Karten (Tab. 1) mitsamt Bildlegenden nochmals wiedergegeben und mit ihren Datengrundlagen und Auswertungen methodisch beschrieben. In Tabelle 2 sind weitere Karten aufgeführt, auf welche im Bericht verwiesen wird.

We examined the influence of land-use, habitat, and water quality on the spatial distribution of aquatic macroinvertebrates in two human-dominated catchments in the Swiss Plateau (Gürbe, Mönchaltorfer Aa). Land-use in the Gürbe catchment was dominated by agriculture, whereas urban land-use was more common in the Mönchaltorfer Aa. Study sites in each catchment were characterized using measures of local habitat conditions, water quality parameters including water temperature, and organic matter resources. A strong longitudinal gradient in temperature, conductivity and nitrogen was evident among sites in the Gürbe catchment, although sites on a main tributary had a strong agricultural signature and deviated from this pattern. Percentage agricultural land-use in the Gürbe was strongly correlated with algal biomass and the water quality PCA axes associated with conductivity, nitrogen (axis-1) and temperature (axis-3). Spatial grouping of sites by water quality was less evident in the Mönchaltorfer Aa, except for a strong signal by wastewater treatment plant effluents and partial differences between upper and lower basin sites. Percentage forest and agricultural land-use in the Mönchaltorfer Aa were correlated with water quality PCA axis-2, being associated with phosphorus and temperature. Macroinvertebrate densities, taxonomic richness, and axis-1 from a non-metric multidimensional scaling analysis (NMDS) of taxonomic composition were significantly correlated with water quality PCA axis-1 in the Gürbe catchment. Here, macroinvertebrate densities and NMDS axis-1 scores based on taxon relative abundances and densities were correlated with land-use features. Spatial distances between sites also were related to site differences in macroinvertebrates, reflecting the strong longitudinal environmental gradient in the Gürbe. Taxonomic differences between water quality PCA site groups were less pronounced in the Mönchaltorfer Aa, although differences were significant for trichopterans, ephemeropterans, chironomids, gastropods and coleopterans. Here, NMDS axis-1 based on taxon relative abundances and densities was correlated with forest land-use. Spatial distances between sites were not evident in macroinvertebrate site differences, reflecting the less pronounced spatial and longitudinal patterns in environmental attributes in this catchment. Our results support the hypothesis that spatial distributions of macroinvertebrates are related to spatial relationships among environmental attributes like land-use, habitat, and water quality in human-dominated catchments that depend on river network complexity, a habitat-filtering template in line with ecological niche theory.

River restoration can enhance river dynamics, environmental heterogeneity and biodiversity, but the underlying processes governing the dynamic changes need to be understood to ensure that restoration projects meet their goals, and adverse effects are prevented. In particular, we need to comprehend how hydromorphological variability quantitatively relates to ecosystem functioning and services, biodiversity as well as ground- and surface water quality in restored river corridors. This involves (i) physical processes and structural properties, determining erosion and sedimentation, as well as solute and heat transport behavior in surface water and within the subsurface; (ii) biogeochemical processes and characteristics, including the turnover of nutrients and natural water constituents; and (iii) ecological processes and indicators related to biodiversity and ecological functioning. All these aspects are interlinked, requiring an interdisciplinary investigation approach. Here, we present an overview of the recently completed RECORD (REstored CORridor Dynamics) project in which we combined physical, chemical, and biological observations with modeling at a restored river corridor of the perialpine Thur River in Switzerland. Our results show that river restoration, beyond inducing morphologic changes that reshape the river bed and banks, triggered complex spatial patterns of bank infiltration, and affected habitat type, biotic communities and biogeochemical processes. We adopted an interdisciplinary approach of monitoring the continuing changes due to restoration measures to address the following questions: How stable is the morphological variability established by restoration? Does morphological variability guarantee an improvement in biodiversity? How does morphological variability affect biogeochemical transformations in the river corridor? What are some potential adverse effects of river restoration? How is river restoration influenced by catchment-scale hydraulics and which feedbacks exist on the large scale? Beyond summarizing the major results of individual studies within the project, we show that these overarching questions could only be addressed in an interdisciplinary framework.

The second Critical Assessment of Small Molecule Identification (CASMI) contest took place in 2013. A joint team from the Swiss Federal Institute of Aquatic Science and Technology (Eawag) and Leibniz Institute of Plant Biochemistry (IPB) participated in CASMI 2013 with an automatic workflow-style entry. MOLGEN-MS/MS was used for Category 1, molecular formula calculation, restricted by the information given for each challenge. MetFrag and MetFusion were used for Category 2, structure identification, retrieving candidates from the compound databases KEGG, PubChem and ChemSpider and joining these lists pre-submission. The results from Category 1 were used to guide whether formula or exact mass searches were performed for Category 2. The Category 2 results were impressive considering the database size and automated regime used, although these could not compete with the manual approach of the contest winner. The Category 1 results were affected by large m/z and ppm values in the challenge data, where strategies beyond pure enumeration from other participants were more successful. However, the combination used for the CASMI 2013 entries was extremely useful for developing decision-making criteria for automatic, high throughput general unknown (non-target) identification and for future contests.

Wastewater effluents contain a multitude of organic contaminants and transformation products, which cannot be captured by target analysis alone. High accuracy, high resolution mass spectrometric data were explored with novel untargeted data processing approaches (enviMass, nontarget, and RMassBank) to complement an extensive target analysis in initial "all in one" measurements. On average 1.2% of the detected peaks from 10 Swiss wastewater treatment plant samples were assigned to target compounds, with 376 reference standards available. Corrosion inhibitors, artificial sweeteners, and pharmaceuticals exhibited the highest concentrations. After blank and noise subtraction, 70% of the peaks remained and were grouped into components; 20% of these components had adduct and/or isotope information available. An intensity-based prioritization revealed that only 4 targets were among the top 30 most intense peaks (negative mode), while 15 of these peaks contained sulfur. Of the 26 nontarget peaks, 7 were tentatively identified via suspect screening for sulfur-containing surfactants and one peak was identified and confirmed as 1,3-benzothiazole-2-sulfonate, an oxidation product of a vulcanization accelerator. High accuracy, high resolution data combined with tailor-made nontarget processing methods (all available online) provided vital information for the identification of a wider range of heteroatom-containing compounds in the environment.

Bevor Flusswasser infiltriert, fliesst es durch ein ganzes Einzugsgebiet und ist Stoffeinträgen aus verschiedensten anthropogenen Quellen ausgesetzt. Neben unzähligen Chemikalien gelangen auch Krankheitserreger oder genetisches Material ins Wasser. Viele der eingetragenen Substanzen werden durch chemische Prozesse zersetzt, andere sind stabil. Deshalb kann es lange dauern, bis Reduktionsmassnahmen greifen.

Avant de s’infiltrer, l’eau des rivières traverse tout un bassin versant et subit de nombreuses pollutions d’origine anthropique. En plus des aspects chimiques, elle peut être contaminée par des germes pathogènes ou du matériel génétique. Alors que beaucoup de substances rejetées dans les cours d’eau subissent une dégradation chimique, certaines sont stables dans l’eau. Il se peut alors que les mesures prises pour réduire la pollution mettent longtemps à être suivies d’effet.

Biomethylation and volatilization of trace elements may contribute to their redistribution in the environment. However, quantification of volatile, methylated species in the environment is complicated by a lack of straightforward and field-deployable air sampling methods that preserve element speciation. This paper presents a robust and versatile gas trapping method for the simultaneous preconcentration of volatile selenium (Se), sulfur (S), and arsenic (As) species. Using HPLC-HR-ICP-MS and ESI-MS/MS analyses, we demonstrate that volatile Se and S species efficiently transform into specific non-volatile compounds during trapping, which enables the deduction of the original gaseous speciation. With minor adaptations, the presented HPLC-HR-ICP-MS method also allows for the quantification of 13 non-volatile methylated species and oxyanions of Se, S, and As in natural waters. Application of these methods in a peatland indicated that, at the selected sites, fluxes varied between 190–210 ng Se·m⁻²·d⁻¹, 90–270 ng As·m⁻²·d⁻¹, and 4–14 µg S·m⁻²·d⁻¹, and contained at least 70% methylated Se and S species. In the surface water, methylated species were particularly abundant for As (>50% of total As). Our results indicate that methylation plays a significant role in the biogeochemical cycles of these elements.

Dans un projet commun de l’Eawag, de l’OFEV et de 5 cantons (AG, SO, TG, VD et ZH), la quasi-totalité des substances actives polaires de produits biocides et phytosanitaires, soit près de 300 composés, ont été recherchées dans cinq rivières de moyenne dimension. Au total, 104 pesticides différents, en majorité des phytosanitaires, ont été détectés. Dans 78% des échantillons, la concentration cumulée de ces polluants était supérieure à 1000 ng/l. Le seuil fixé par l’OEaux et les critères de qualité environnementale n’étaient pas respectés pour, respectivement, 31 et 19 pesticides.

Fünf mittelgrosse Fliessgewasser wurden in Zusammenarbeit zwischen Eawag, BAFU und fünf Kantonen (AG, SO, TG, VD, ZH) auf möglichst alle polaren organisch-synthetischen Pflanzenschutzmittel und Biozide (ca. 300 Wirkstoffe) untersucht. lnsgesamt konnten 104 verschiedene Pestizide, hauptsachlich Pflanzenschutzmittel, nachgewiesen werden. Die Konzentrationssumme war in 78% der Proben grosser als 1000 ng/l. Die numerische Anforderung der Gewässerschutzverordnung und ökotoxikologische Qualitatskriterien wurden von 31 bzw. 19 Pestiziden überschritten.

The initial training network consortium novel tools in effect-directed analysis to support the identification and monitoring of emerging toxicants on a European scale (EDA-EMERGE) was formed in response to the seventh EU framework program call to train a new generation of young scientists (13 PhD fellows and 1 postdoctoral fellow) in the interdisciplinary techniques required to meet the major challenges in the monitoring, assessment, and management of toxic pollution in European river basins. This 4-year project is of particular relevance considering the multidisciplinary analytical chemistry and biology skills required to investigate the enormous complexity of contamination, effects, and cause-effect relationships. By integrating innovative mode-of-action-based biodiagnostic tools including in vitro and in vivo tests, transgenic organisms, and 'omics' techniques with powerful fractionation and cutting edge, analytical, and computational structure elucidation tools, powerful new EDA approaches are being developed for the identification of toxicants in European surface and drinking waters. Innovative method development by young researchers at major European universities, research centers, and private companies has been closely interlinked with a joint European demonstration program, higher-tier EDA, and specialized training courses and secondments. Using a simplified protocol based on existing EDA tools, EDA-EMERGE fellows are also being trained to organize and run international and interdisciplinary sampling and monitoring campaigns within selected European river basin sites. Strong networking between academia, the private sector, and leading regulators in the field of river basin management and pollution management ensures the relevance of the research for practice and excellent employment opportunities for the fellows. Additionally, an internationally composed advisory board has been tasked to introduce new perspectives on monitoring, assessment, and management of emerging pollutants within and outside of Europe. The combination of cutting edge science with specialized training in complimentary soft skills is being offered with a strong emphasis on commercial exploitation and media competence which further enhances the employability of the fellows in research, academia, and beyond.

Amino acids (AAs) comprise a large fraction of organic nitrogen (N) in plankton and sedimenting matter. Aquatic studies of organic N compounds in general and of AAs in particular, mostly concentrate on marine environments. In order to study the cycling and fate of organic N and AAs in lakes, we measured the N isotopic composition (δ¹⁵N) of bulk organic matter (OM) and of single hydrolysable AAs in sediment trap and sediment samples from two Swiss lakes with contrasting trophic state: Lake Brienz, an oligotrophic lake with an oxic water column, and Lake Zug a eutrophic, meromictic lake. We also measured the N isotopic composition of water column nitrate, the likely inorganic N source during biosynthesis in both lakes. The δ¹⁵N–AA patterns found for the sediment trap material were consistent with published δ¹⁵N–AA data for marine plankton. The AA composition and primary δ¹⁵N–AA signatures are preserved until burial in the sediments. During early sedimentary diagenesis, the δ¹⁵N values of single AAs appear to increase, exceeding those of the bulk OM. This increase in δ¹⁵N–AA is paralleled by a decreased contribution of AAs to the total OM pool with progressed degradation, suggesting preferential AA degradation associated with a significant N isotope fractionation. Indicators for trophic level based on δ¹⁵N–AAs were determined, for the first time in lacustrine systems. In our samples, the trophic AAs were generally enriched in ¹⁵N compared to source AAs and higher trophic δ¹⁵N–AA values in Lake Zug were consistent with a higher trophic level of the bulk biomass compared to Lake Brienz. Especially the difference between average trophic δ¹⁵N–AAs and average source δ¹⁵N–AAs was sensitive to the trophic states of the two lakes. A proxy for total heterotrophic AA re-synthesis (ΣV), which is strongly associated with heterotrophic microbial reworking of the OM, was calculated based on δ¹⁵N values of trophic AAs. Higher ΣV in Lake Brienz indicate enhanced heterotrophic bacterial reworking of AAs under oligotrophic conditions. Despite changes in the δ¹⁵N–AA values within the sediments, the proxies based on these values were consistent over the studied sediment profile, indicating the preservation of trophic signatures; therefore, our results underscore that δ¹⁵N–AA analysis of sedimentary records represents a promising tool to assess trophic levels and bacterial re-synthesis in lakes.

Organic contaminants detected in sediments from Lake Greifensee and other compounds falling in the log Dow range from 1 to 7 were selected to study the bioconcentration of organic contaminants in sediments in Daphnia resting eggs (ephippia). Our results show that octocrylene, tonalide, triclocarban, and other personal care products, along with pesticides and biocides can accumulate in ephippia with log BCF values up to 3. Data on the uptake and depuration kinetics show a better fit toward a two compartment organism model over a single compartment model due to the differences in ephippial egg content in the environment. The obtained BCFs correlate with hydrophobicity for neutral compounds. Independence between BCF and hydrophobicity was observed for partially ionized compounds with log D_ow values around 1. Internal concentrations in ephippia in the environment were predicted based on sediment concentrations using the equilibrium partitioning model and calculated BCFs. Estimated internal concentration values ranged between 1 and 68,000 µg/kg_lip with triclocarban having the highest internal concentrations followed by tonalide and triclosan. The outcomes indicate that contaminants can be taken up by ephippia from the water column or the pore water in the sediment and might influence fitness and sexual reproduction in the aquatic key species of the genus Daphnia.

We developed a multiresidue method for the target and suspect screening of more than 180 pharmaceuticals, personal care products, pesticides, biocides, additives, corrosion inhibitors, musk fragrances, UV light stabilizers, and industrial chemicals in sediments. Sediment samples were freeze-dried, extracted by pressurized liquid extraction, and cleaned up by liquid–liquid partitioning. The quantification and identification of target compounds with a broad range of physicochemical properties (log K_ow 0–12) was carried out by liquid chromatography followed by electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) coupled to high resolution Orbitrap mass spectrometry (HRMS/MS). The overall method average recoveries and precision are 103% and 9% (RSD), respectively. The method detection limits range from 0.010 to 4 ng/g_dw, while limits of quantification range from 0.030 to 14 ng/g_dw. The use of APPI as an alternative ionization source helped to distinguish two isomeric musk fragrances by means of different ionization behavior. The method was demonstrated on sediment cores from Lake Greifensee located in northeastern Switzerland. The results show that biocides, musk fragrances, and other personal care products were the most frequently detected compounds with concentrations ranging from pg/g_dw to ng/g_dw, whereas none of the targeted pharmaceuticals were found. The concentrations of many urban contaminants originating from wastewater correlate with the highest phosphorus input into the lake as a proxy for treatment efficiency. HRMS enabled a retrospective analysis of the full-scan data acquisition allowing the detection of suspected compounds like quaternary ammonium surfactants, the biocide triclocarban, and the tentative identification of further compounds without reference standards, among others transformation products of triclosan and triclocarban.

Hydrodynamic models are useful tools for urban water management. Unfortunately, it is still challenging to obtain accurate results and plausible uncertainty estimates when using these models. In particular, with the currently applied statistical techniques, flow predictions are usually overconfident and biased. In this study, we present a flexible and relatively efficient methodology (i) to obtain more reliable hydrological simulations in terms of coverage of validation data by the uncertainty bands and (ii) to separate prediction uncertainty into its components. Our approach acknowledges that urban drainage predictions are biased. This is mostly due to input errors and structural deficits of the model. We address this issue by describing model bias in a Bayesian framework. The bias becomes an autoregressive term additional to white measurement noise, the only error type accounted for in traditional uncertainty analysis. To allow for bigger discrepancies during wet weather, we make the variance of bias dependent on the input (rainfall) or/and output (runoff) of the system. Specifically, we present a structured approach to select, among five variants, the optimal bias description for a given urban or natural case study. We tested the methodology in a small monitored stormwater system described with a parsimonious model. Our results clearly show that flow simulations are much more reliable when bias is accounted for than when it is neglected. Furthermore, our probabilistic predictions can discriminate between three uncertainty contributions: parametric uncertainty, bias, and measurement errors. In our case study, the best performing bias description is the output-dependent bias using a log-sinh transformation of data and model results. The limitations of the framework presented are some ambiguity due to the subjective choice of priors for bias parameters and its inability to address the causes of model discrepancies. Further research should focus on quantifying and reducing the causes of bias by improving the model structure and propagating input uncertainty.

Hydrodynamische Kanalnetzmodelle sind für die Entwässerungsplanung unersetzlich.Obwohl sie den komplexen Niederschlags-Abfluss Prozess niemals exakt abbilden können, liefern sie oft akzeptable Ergebnisse. Es ist jedoch schwierig, plausible Schätzungen der Unsicherheit von Kanalnetzberechnungen zu erhalten, da die gängigen statistischen Verfahren auf sehr starken Annahmen über die Fehlerverteilung beruhen, wie z.B. unabhängige, und identisch verteilte Zufallseffekte, welche praktisch nie erfüllt sind. In diesem Artikel stellen wir deshalb eine Methode vor, um i) zuverlässigere Schätzungen der Unsicherheit von Kanalnetzsimulationen zu berechnen und ii) die Vorhersageunsicherheit in einzelne Komponenten zu trennen. Zu diesem Zweck werden neben dem deterministischen Modell und zufälligen Messfehlern auch systematische Modellabweichungen berücksichtigt. Diese systematischen Modellabweichungen werden durch einen autoregressiven Zufallsprozess beschrieben und erfassen die Effekte von Unsicherheiten in den Eingangsdaten und der Modellstruktur. Zur Kalibration wird Bayessche Parameterschätzung verwendet. Wir zeigen an einem Fallbeispiel, dass die Berücksichtigung der Modellabweichung die Zuverlässigkeit der Berechnungsergebnisse stark verbessert. Ausserdem wird deutlich, dass systematische Modellabweichungen die Vorhersageunsicherheit dominieren und weit grösser sind, als Unsicherheit in den Modellparametern oder Messfehler. Abgesehen von den langen Rechenzeiten ergeben sich gewisse Limitierungen aus der subjektiven Formulierung des Vorwissens über die Parameter des Fehlermodells. Die statistische Berücksichtigung von systematischen Modellabweichungen liefert jedoch eine zuverlässige Schätzungen der Unsicherheit als herkömmliche Methoden und scheint daher für Kanalnetzsimulationen sehr interessant.

Zukünftige, von regionalen Klimamodellen vorhergesagte Änderungen der Niederschlagseigenschaften müssen zuerst in die für die Siedlungsentwässerung relevanten räumliche und zeitliche Skalen übertragen werden. Dazu verwenden wir ,statistisches Downscaling‘, um synthetische Punktregenserien zu generieren. Diese können dann zur hydraulischen Analyse und Bemessung von Siedlungsentwässerungssystemen herangezogen werden. Wir analysierten damit den Einfluss des Klimawandels auf die hydraulische Leistungsfähigkeit eines ausgewählten Entwässerungssystems. Spezielles Augenmerk wurde dabei auf Unsicherheiten gelegt, welche (i) in der natürlichen Variabilität des Klimas und (ii) der Unsicherheit der Klimamodelle begründet sind. Die Analyse zeigt auf, dass die Leistungsfähigkeit von Entwässerungssystemen sowohl unter heutigem als auch zukünftigem Klima stark schwanken kann. Die Anteile von Schächten an denen das angewandte Bemessungskriterium nicht erfüllt wird, variiert zwischen 1,3 und 7,4 % (heutiges Klima) und 1,3 und 15,8 % (zukünftiges Klima). Damit zeigt sich eine Tendenz zu einer verschlechterten hydraulischen Leistungsfähigkeit unter zukünftigem Klima.

Removal of organic micropollutants in a hybrid biofilm-activated sludge process was investigated through batch experiments, modeling, and full-scale measurements. Batch experiments with carriers and activated sludge from the same full-scale reactor were performed to assess the micropollutant removal rates of the carrier biofilm under oxic conditions and the sludge under oxic and anoxic conditions. Clear differences in the micropollutant removal kinetics of the attached and suspended growth were demonstrated, often with considerably higher removal rates for the biofilm compared to the sludge. For several micropollutants, the removal rates were also affected by the redox conditions, i.e. oxic and anoxic. Removal rates obtained from the batch experiments were used to model the micropollutant removal in the full-scale process. The results from the model and plant measurements showed that the removal efficiency of the process can be predicted with acceptable accuracy (±25%) for most of the modeled micropollutants. Furthermore, the model estimations indicate that the attached growth in hybrid biofilm-activated sludge processes can contribute significantly to the removal of individual compounds, such as diclofenac.

The benefits of global pesticide use come at the cost of their widespread occurrence in the environment. An array of abiotic and biotic transformations effectively removes pesticides from the environment, but may give rise to potentially hazardous transformation products. Despite a large body of pesticide degradation data from regulatory testing and decades of pesticide research, it remains difficult to anticipate the extent and pathways of pesticide degradation under specific field conditions. Here, we review the major scientific challenges in doing so and discuss emerging opportunities to identify pesticide degradation processes in the field.

Many environmental mutagens, including polyaromatic compounds are present in surface waters, often in complex mixtures and at low concentrations. The present study provides and applies a novel, integrated approach to isolate polyaromatic mutagens in river water using a sample from the River Elbe. The sample was taken downstream of industrial discharges using blue rayon (BR) as a passive sampler that selectively adsorbs polyaromatic compounds and was subjected to effect-directed fractionation in order to characterise the compounds causing the detected effect(s). The procedure relies on three complementary fractionation steps, the Ames fluctuation assay with strains TA98, YG1024 and YG1041 with and without S9 activation and analytical screening. Several mutagenic fractions were isolated by combining mutagenicity testing with fractionation. The enhanced mutagenicity in the nitroreductase and/or O-acetyltransferase overexpressing strains YG1024 and YG1041 strains suggested amino- and/or nitro-compounds causing mutagenicity in several fractions. Analytical screening of mutagenic fractions with LC-HRMS/MS provided a list of molecular formulas typically containing one to ten nitrogen and at least two oxygen atoms supporting the presence of amino and nitro-compounds in the mutagenic fractions.

Pesticides applied onto agricultural fields are frequently found in adjacent rivers. To what extent and along which pathways they are transported is influenced by intrinsic pesticide properties such as sorption and degradation. In the environment, incomplete degradation of pesticides leads to the formation of transformation products (TPs), which may differ from the parent compounds regarding their intrinsic fate characteristics. Thus, the export processes of TPs in catchments and streams may also be different. In order to test this hypothesis, we extended a distributed hydrological model by the fate and behaviour of pesticides and transformation products and applied it to a small, well-monitored headwater catchment in Switzerland. The successful model evaluation of three pesticides and their TPs at three sampling locations in the catchment enabled us to estimate the quantity of contributing processes for pollutant export. Since all TPs were more mobile than their parent compounds (PCs), they exhibited larger fractions of export via subsurface pathways. However, besides freshly applied pesticides, subsurface export was found to be influenced by residues of former applications. Export along preferential flow pathways was less dependent on substance fate characteristics than soil matrix export, but total soil water flow to tile drains increased more due to preferential flow for stronger sorbing substances. Our results indicate that runoff generation by matrix flow to tile drains gained importance towards the end of the modelling period whereas the contributions from fast surface runoff and preferential flow decreased. Accordingly, TPs were to a large extent exported under different hydrological conditions than their PCs, due to their delayed formation and longer half-lives. Thus, not only their different intrinsic characteristics but also their delayed formation could be responsible for the fact that TPs generally took different pathways than their PCs. We suggest that these results should be considered in risk assessment for the export of agricultural chemicals to adjacent rivers and that models should be extended to include both PCs and TPs.

Structural Fe in clay minerals is an important redox-active species in many pristine and contaminated environments as well as in engineered systems. Understanding the extent and kinetics of redox reactions involving Fe-bearing clay minerals has been challenging due to the inability to relate structural Fe²⁺/Fe_total fractions to fundamental redox properties, such as reduction potentials (E_H). Here, we overcame this challenge by using mediated electrochemical reduction (MER) and oxidation (MEO) to characterize the fraction of redox-active structural Fe (Fe²⁺/Fe_total) in smectites over a wide range of applied E_H-values (−0.6 V to +0.6 V). We examined Fe²⁺/Fe_total – E_H relationships of four natural Fe-bearing smectites (SWy-2, SWa-1, NAu-1, NAu-2) in their native, reduced, and reoxidized states and compared our measurements with spectroscopic observations and a suite of mineralogical properties. All smectites exhibited unique Fe²⁺/Fe_total – E_H relationships, were redox active over wide E_H ranges, and underwent irreversible electron transfer induced structural changes that were observable with X-ray absorption spectroscopy. Variations among the smectite Fe²⁺/Fe_total – E_H relationships correlated well with both bulk and molecular-scale properties, including Fe_total content, layer charge, and quadrupole splitting values, suggesting that multiple structural parameters determined the redox properties of smectites. The Fe²⁺/Fe_total – E_H relationships developed for these four commonly studied clay minerals may be applied to future studies interested in relating the extent of structural Fe reduction or oxidation to E_H-values.

Quantum chemical implicit solvent models are used widely to estimate aqueous redox potentials. We compared the accuracy of several popular implicit solvent models (SM8, SMD, C-PCM, IEF-PCM, and COSMO-RS) for the prediction of aqueous single electron oxidation potentials of a diverse test set of neutral organic compounds for which accurate experimental oxidation potential and gas-phase ionization energy data are available. Using a thermodynamic cycle, we decomposed the free energy of oxidation into contributions arising from the gas-phase adiabatic ionization energy, the solvation free energy of the closed-shell neutral species, and the solvation free energy of the radical cation species. For aqueous oxidation potentials, implicit solvent models exhibited mean unsigned errors (MUEs) ranging from 0.27 to 0.50 V, depending on the model. The principal source of error was attributed to the computed solvation free energy of the oxidized radical cation. Based on these results, a recommended implicit solvation approach is the SMD model for the solvation free energy combined with CBS-QB3 for the gas-phase ionization energy. With this approach, the MUE in computed oxidation potentials was 0.27 V, and the MUE in solvation free energy of the charged open-shell species was 0.32 eV. This baseline assessment provides a compiled benchmark test set of vetted experimental data that may be used to judge newly developed solvation models for their ability to produce improved predictions for aqueous oxidation potentials and related properties.

Sulfonamide antibiotics form stable covalent bonds with quinone moieties in organic matter via nucleophilic addition reactions. In this work, we combined analytical electrochemistry with trace analytics to assess the catalytic role of the oxidoreductase laccase in the binding of sulfamethazine (SMZ) to Leonardite humic acid (LHA) and to four synthetic humic acids (SHAs) polymerized from low molecular weight precursors and to determine the stability of the formed bonds. In the absence of laccase, a significant portion of the added SMZ formed covalent bonds with LHA, but only a very small fraction (<0.4%) of the total quinone moieties in LHA reacted. Increasing absolute, but decreasing relative concentrations of SMZ–LHA covalent bonds with increasing initial SMZ concentration suggested that the quinone moieties in LHA covered a wide distribution in reactivity for the nucleophilic addition of SMZ. Laccase catalyzed the formation of covalent bonds by oxidizing unreactive hydroquinone moieties in LHA to reactive, electrophilic quinone moieties, of which a large fraction (5%) reacted with SMZ. Compared to LHA, the SHA showed enhanced covalent bond formation in the absence of laccase, suggesting a higher reactivity of their quinone moieties toward nucleophilic addition. This work supports that binding to soil organic matter (SOM) is an important process governing the fate, bioactivity, and extractability of sulfonamides in soils.

Eutrophication of surface waters due to diffuse phosphorus (P) losses continues to be a severe water quality problem worldwide, causing the loss of ecosystem functions of the respective water bodies. Phosphorus in runoff often originates from a small fraction of a catchment only. Targeting mitigation measures to these critical source areas (CSAs) is expected to be most efficient and cost-effective, but requires suitable tools.
Here we investigated the capability of the parsimonious Rainfall-Runoff-Phosphorus (RRP) model to identify CSAs in grassland-dominated catchments based on readily available soil and topographic data. After simultaneous calibration on runoff data from four small hilly catchments on the Swiss Plateau, the model was validated on a different catchment in the same region without further calibration. The RRP model adequately simulated the discharge and dissolved reactive P (DRP) export from the validation catchment. Sensitivity analysis showed that the model predictions were robust with respect to the classification of soils into "poorly drained" and "well drained", based on the available soil map. Comparing spatial hydrological model predictions with field data from the validation catchment provided further evidence that the assumptions underlying the model are valid and that the model adequately accounts for the dominant P export processes in the target region. Thus, the parsimonious RRP model is a valuable tool that can be used to determine CSAs. Despite the considerable predictive uncertainty regarding the spatial extent of CSAs, the RRP can provide guidance for the implementation of mitigation measures. The model helps to identify those parts of a catchment where high DRP losses are expected or can be excluded with high confidence. Legacy P was predicted to be the dominant source for DRP losses and thus, in combination with hydrologic active areas, a high risk for water quality.

A method is described for the identification of priority micropollutants (pharmaceuticals) in the aquatic environment originating from hospitals. The lack of data on the range and volume of prescribed pharmaceuticals, and on their behaviour in the environment, presented a considerable challenge to the initial selection process. The final selection of pharmaceutical substances to be included in the monitoring campaigns was based on literature data, existing priority lists, national consumption patterns and expert input from within the regions (Northwest Europe). Fifteen micropollutant compounds were identified from the diverse range of reported and prescribed pharmaceuticals in the healthcare sector:atenolol, carbamazepine, diclofenac, naproxen, lidocaine, ifosphamide, cyclophosphamide, ciprofloxacin, erythromycin, clarithromycin, sulfamethoxazole, iopromide, iopamidol, diatrizoate, and bezafibrate. Eight hospital locations in six countries were monitored for periods ranging from several weeks to one year. Samples were taken from hospital effluent (sewers) flow-proportionally and analysed by LC-MS-MS. The obtained results indicate that hospitals are significant point sources for some (especially x-ray contrast media and antibacterials) but not all pharmaceutical micropollutants. Hospital contribution to overall load in the sewers at entry to waste water treatment plants ranged from <10% for substances also used in the communities (e.g. diclofenac and atenolol), to well in excess of 50% for antibiotics and x-ray contrast media. A detailed understanding of emission pathways within the urban environment is required in order to inform related political decision making. This project demonstrated a route towards this understanding and also highlighted the difficulties and barriers that need to be overcome in the process.

A proper uncertainty assessment of rainfall-runoff predictions has always been an important objective for modelers. Several sources of uncertainty have been identified, but their representation was limited to complicated mechanistic error propagation frameworks only. The typical statistical error models used in the modeling practice still build on outdated and invalidated assumptions like the independence and homoscedasticity of model residuals and thus result in wrong uncertainty estimates. The primary reason for the popularity of the traditional faulty methods is the enormous computational requirement of full Bayesian error propagation frameworks. We introduce a statistical error model that can account for the effect of various uncertainty sources present in conceptual rainfall-runoff modeling studies and at the same time has limited computational demand. We split the model residuals into three different components: a random noise term and two bias processes with different response characteristics. The effects of the input uncertainty are simulated with a stochastic linearized rainfall-runoff model. While the description of model bias with Bayesian statistics cannot directly help to improve on the model's deficiencies, it is still beneficial to get realistic estimates on the overall predictive uncertainty and to rank the importance of different uncertainty sources. This feature is particularly important if the error sources cannot be addressed individually, but it is also relevant for the description of remaining bias when input and structural errors are considered explicitly.

The fate of polar organic micropollutants (logD_OW (pH 7) between −4.2 and +3.5) during riverbank filtration (RBF) at the river Thur was studied using both spatiotemporally resolved sampling and single-well push–pull tests (PPT), followed by LC-MS/MS analysis. The Thur is a dynamic prealpine river with an alluvial sandy-gravel aquifer, which is characterized by short groundwater travel times (a few days) from surface water infiltration to groundwater extraction. The spatiotemporal sampling allowed tracing concentration dynamics in the river and the groundwater and revealed persistence for the drug carbamazepine, while the herbicide MCPA (2-methyl-4-chloro-phenoxyacetic acid) and the drug 4-acetamidoantipyrine were very quickly degraded under the prevalent aerobic conditions. The corrosion inhibitor 1H-benzotriazole was degraded slightly, particularly in a transect influenced by river restoration measures. For the first time in situ first-order degradation rate constants for three pesticides and two pharmaceuticals were determined by PPTs, which confirmed the results of the spatiotemporal sampling. Atenolol was transformed almost completely to atenolol acid. Rate constants of 0.1–1.3 h^–1 for MCPA, 2,4-D, mecoprop, atenolol, and diclofenac, corresponding to half-lives of 0.6–6.3 h, demonstrated the great potential of RBF systems to degrade organic micropollutants and simultaneously the applicability of PPTs for micropollutants in such dynamic systems.

The inhibition of acetylcholinesterase (AChE) activity and energy allocation in the freshwater organism Daphnia magna exposed to carbaryl and potential recovery from the effects was examined. The binding of carbaryl-AChE was characterized through in vitro assays. To evaluate the recovery from inhibition and the alteration in energy budget, in vivo exposure and recovery regime tests were conducted. In comparison to diazoxon, the active metabolite of the insecticide diazinon, the stability of enzyme–carbaryl complex was fifteen times lower and the reactivity toward the active site was two times lower, resulting in approximately 30 times lower overall inhibition rate than for diazoxon. The in vitro reactivation rate constant of the inhibited enzyme and the in vivo recovery rate constant of AChE activity were 1.9 h⁻¹ and 0.12 h⁻¹ for carbaryl, respectively, which are much higher than the corresponding rate constants for diazoxon. The lower AChE inhibition and greater reactivation/recovery rates are in accordance with the lower toxicity of carbaryl compared to diazinon. Carbaryl exposure also altered the profile of the energy reserve: the decrease in lipid and glycogen and the increase in protein content resulted in the reduction of the total energy budget by about 45 mJ/g_ww. This corresponds to 26 percent of the available energy, which might allocate for external stressors. The mechanistic model of AChE inhibition is helpful to get an insight into (eco-)toxicological effects of AChE inhibitors on freshwater crustaceans under environmentally realistic conditions.

Exposure and depuration experiments for Gammarus pulex and Daphnia magna were conducted to quantitatively analyze biotransformation products (BTPs) of organic micropollutants (tramadol, irgarol, and terbutryn). Quantification for BTPs without available standards was performed using an estimation method based on physicochemical properties. Time-series of internal concentrations of micropollutants and BTPs were used to estimate the toxicokinetic rates describing uptake, elimination, and biotransformation processes. Bioaccumulation factors (BAF) for the parents and retention potential factors (RPF), representing the ratio of the internal amount of BTPs to the parent at steady state, were calculated. Nonlinear correlation of excretion rates with hydrophobicity indicates that BTPs with lower hydrophobicity are not always excreted faster than the parent compound. For irgarol, G.pulex showed comparable elimination, but greater uptake and BAF/RPF values than D.magna. Further, G. pulex had a whole set of secondary transformations that D. magna lacked. Tramadol was transformed more and faster than irgarol and there were large differences in toxicokinetic rates for the structurally similar compounds irgarol and terbutryn. Thus, predictability of toxicokinetics across species and compounds needs to consider biotransformation and may be more challenging than previously thought because we found large differences in closely related species and similar chemical structures.

So far, there is limited information on biotransformation mechanisms and products of polar contaminants in freshwater crustaceans. In the present study, metabolites of biocides and pharmaceuticals formed in Gammarus pulex and Daphnia magna were identified using liquid chromatography–high resolution mass spectrometry. Different confidence levels were assigned to the identification of metabolites without reference standards using a framework based on the background evidence used for structure elucidation. Twenty-five metabolites were tentatively identified for irgarol, terbutryn, tramadol, and venlafaxine in G. pulex (21 via oxidation and 4 via conjugation reactions) and 11 metabolites in D. magna (7 via oxidation and 4 via conjugation reactions), while no evidence of metabolites for clarithromycin and valsartan was found. Of the 360 metabolites predicted for the four parent compounds using pathway prediction systems and expert knowledge, 23 products were true positives, while 2 identified metabolites were unexpected products. Observed oxidative reactions included N- and O-demethylation, hydroxylation, and N-oxidation. Glutathione conjugation of selected biocides followed by subsequent reactions forming cysteine conjugates was described for the first time in freshwater invertebrates.

The occurrence and persistence of pharmacologically active compounds in the environment has been an increasingly important issue. The objectives of this study were to investigate the decomposition of aqueous antimicrobial compounds using activated sludge, γ-irradiation, and UV treatment, and to evaluate the toxicity towards green algae, Pseudokirchneriella subcapitata, before and after treatment. Tetracycline (TCN), lincomycin (LMC) and sulfamethazine (SMZ) were used as target compounds. Gamma (γ)-irradiation showed the highest removal efficiency for all target compounds, while UV and activated sludge treatment showed compound-dependent removal efficiencies. TCN and SMZ were well degraded by all three treatment methods. However, LMC showed extremely low removal efficiency for UV and activated sludge treatments. Overall, the algal toxicity after degradation processes was significantly decreased, and was closely correlated to removal efficiency. However, in the case of γ-irradiated TCN, UV and activated sludge treated LMC as well as sludge treated SMZ, the observed toxicity was higher than expected, which indicates the substantial generation of byproducts or transformed compounds of a greater toxicity in the treated sample. Consequently, γ-radiation treatment could be an effective method for removal of recalcitrant compounds such as antibiotics.

Due to concerns about ecotoxicological effects of pharmaceuticals and other micropollutants released from wastewater treatment plants, activated carbon adsorption is one of the few processes to effectively reduce the concentrations of micropollutants in wastewater. Although aimed mainly at apolar compounds, polar compounds are also simultaneously removed to a certain extent, which has rarely been studied before. In this study, adsorption isotherm and batch kinetic data were collected with two powdered activated carbons (PACs) to assess the removal of the polar pharmaceuticals 5-fluorouracil (5-Fu) and cytarabine (CytR) from ultrapure water and wastewater treatment plant effluent. At pH 7.8, single-solute adsorption isotherm data for the weak acid 5-Fu and the weak base CytR showed that their adsorption capacities were about 1 order of magnitude lower than those of the less polar endocrine disrupting chemicals bisphenol A (BPA) and 17-α-ethinylestradiol (EE2). To remove 90 % of the adsorbate from a single-solute solution 14, 18, 70, and 87 mg L⁻¹ of HOK Super is required for EE2, BPA, CytR, and 5-Fu, respectively. Effects of solution pH, ionic strength, temperature, and effluent organic matter (EfOM) on 5-Fu and CytR adsorption were evaluated for one PAC. Among the studied factors, the presence of EfOM had the highest effect, due to a strong competition on 5-Fu and CytR adsorption. Adsorption isotherm and kinetic data and their modeling with a homogeneous surface diffusion model showed that removal percentage in the presence of EfOM was independent on the initial concentration of the ionizable compounds 5-Fu and CytR. These results are similar to neutral organic compounds in the presence of natural organic matter. Overall, results showed that PAC doses sufficient to remove >90 % of apolar adsorbates were able to remove no more than 50 % of the polar adsorbates 5-Fu and CytR and that the contact time is a critical parameter.

A pilot-scale hospital wastewater treatment plant consisting of a primary clarifier, membrane bioreactor, and five post-treatment technologies including ozone (O₃), O₃/H₂O₂, powdered activated carbon (PAC), and low pressure UV light with and without TiO₂ was operated to test the elimination efficiencies for 56 micropollutants. The extent of the elimination of the selected micropollutants (pharmaceuticals, metabolites and industrial chemicals) was successfully correlated to physical-chemical properties or molecular structure. By mass loading, 95% of all measured micropollutants in the biologically treated hospital wastewater feeding the post-treatments consisted of iodinated contrast media (ICM). The elimination of ICM by the tested post-treatment technologies was 50–65% when using 1.08 g O₃/gDOC, 23 mg/L PAC, or a UV dose of 2400 J/m² (254 nm). For the total load of analyzed pharmaceuticals and metabolites excluding ICM the elimination by ozonation, PAC, and UV at the same conditions was 90%, 86%, and 33%, respectively. Thus, the majority of analyzed substances can be efficiently eliminated by ozonation (which also provides disinfection) or PAC (which provides micropollutants removal, not only transformation). Some micropollutants recalcitrant to those two post-treatments, such as the ICM diatrizoate, can be substantially removed only by high doses of UV (96% at 7200 J/m²). The tested combined treatments (O₃/H₂O₂ and UV/TiO₂) did not improve the elimination compared to the single treatments (O₃ and UV).

This paper details the MOLGEN entries for the 2012 CASMI contest for small molecule identification to demonstrate structure elucidation using structure generation approaches. Different MOLGEN programs were used for different categories, including MOLGEN–MS/MS for Category 1, MOLGEN 3.5 and 5.0 for Category 2 and MOLGEN–MS for Categories 3 and 4. A greater focus is given to Categories 1 and 2, as most CASMI participants entered these categories. The settings used and the reasons behind them are described in detail, while various evaluations are used to put these results into perspective. As one author was also an organiser of CASMI, these submissions were not part of the official CASMI competition, but this paper provides an insight into how unknown identification could be performed using structure generation approaches. The approaches are semi-automated (category dependent) and benefit greatly from user experience. Thus, the results presented and discussed here may be better than those an inexperienced user could obtain with MOLGEN programs.

Urban wastewater treatment plants (UWTPs) are among the main sources of antibiotics' release into various compartments of the environment worldwide. The aim of the present paper is to critically review the fate and removal of various antibiotics in wastewater treatment, focusing on different processes (i.e. biological processes, advanced treatment technologies and disinfection) in view of the current concerns related to the induction of toxic effects in aquatic and terrestrial organisms, and the occurrence of antibiotics that may promote the selection of antibiotic resistance genes and bacteria, as reported in the literature. Where available, estimations of the removal of antibiotics are provided along with the main treatment steps. The removal efficiency during wastewater treatment processes varies and is mainly dependent on a combination of antibiotics' physicochemical properties and the operating conditions of the treatment systems. As a result, the application of alternative techniques including membrane processes, activated carbon adsorption, advanced oxidation processes (AOPs), and combinations of them, which may lead to higher removals, may be necessary before the final disposal of the effluents or their reuse for irrigation or groundwater recharge.

Polar organic micropollutants (MPs) can have ecotoxicological effects on aquatic ecosystems and their occurrence in drinking water is a threat to public health. An extensive exposure assessment of MPs in large river and lake catchments is a necessary but challenging proposition for researchers and regulators. To get a complete picture of MP exposure in a large catchment, we employed a novel integrated strategy including MP measurement in the international catchment of Lake Constance and mass-flux modeling. A comprehensive screening of 252 MPs in the lake water by high-resolution mass spectrometry was used to identify the most commonly present MPs for the study site. It was found that the wastewater borne MPs diclofenac, carbamazepine, sulfamethoxazole, acesulfame, sucralose, benzotriazole, and methylbenzotriazole accounted for the most frequent and prominent findings. The concentration pattern of these compounds in the catchment was calculated based on regionalized inputs from wastewater treatment plants (WWTPs) and substance specific elimination rates. In 52, 8, and 3 of the 112 investigated river locations the concentration exceeded the predicted no-effect levels for diclofenac, sulfamethoxazole and carbamazepine, respectively. By coupling the catchment and lake model the effect of future trends in usage as well as possible mitigation options were evaluated for the tributaries and the lake. The upgrade of the major WWTPs in the catchment with a postozonation step would lead to a load reduction between 32% and 52% for all substances except for sucralose (10%).

In this study, the efficiency of a suspect screening strategy using liquid chromatography-high resolution mass spectrometry (LC-HRMS) without the prior purchase of reference standards was systematically optimized and evaluated for assessing the exposure of rarely investigated pesticides and their transformation products (TPs) in 76 surface water samples. Water-soluble and readily ionizable (electrospray ionization) substances, 185 in total, were selected from a list of all insecticides and fungicides registered in Switzerland and their major TPs. Initially, a solid phase extraction-LC-HRMS method was established using 45 known, persistent, and high sales volume pesticides. Seventy percent of these target substances had limit of quantitation (LOQ) < 5 ng L^–1. This compound set was then used to develop and optimize a HRMS suspect screening method using only the exact mass as a priori information. Thresholds for blank subtraction, peak area, peak shape, signal-to-noise, and isotopic pattern were applied to automatically filter the initially picked peaks. The success rate was 70%; false negatives mainly resulted from low intense peaks. The optimized approach was applied to the remaining 140 substances. Nineteen additional substances were detected in environmental samples, two TPs for the first time in the environment. Sixteen substances were confirmed with reference standards purchased subsequently, while three TP standards could be obtained from industry or other laboratories. Overall, this screening approach was fast and very successful and can easily be expanded to other micropollutant classes for which reference standards are not readily accessible such as TPs of household chemicals.

The effects of sulfathiazole (STA) on Escherichia coli with glucose as a growth substrate was investigated to elucidate the effect-based reaction of sulfonamides in bacteria and to identify biomarkers for bacterial uptake and effect. The predominant metabolite was identified as pterine-sulfathiazole by LC-high resolution mass spectrometry. The formation of pterine-sulfathiazole per cell was constant and independent of the extracellular STA concentrations, as they exceeded the modeled half-saturation concentration of 0.011 μmol L⁻¹. The concentration of the dihydrofolic acid precursor para-aminobenzoic acid (pABA) increased with growth and with concentrations of the competitor STA. This increase was counteracted for higher STA concentrations by growth inhibition as verified by model simulation of pABA dynamics. The EC value for the inhibition of pABA increase was 6.9 ± 0.7 μmol L⁻¹ STA, which is similar to that calculated from optical density dynamics indicating that pABA is a direct biomarker for the SA effect.

Die Überwachungsstationen des Rheins haben die Aufgabe, Trends in der Gewässerqualität aufzuzeigen und Fehleinleitungen aufzudecken. Zentrales Element der Überwachung an der Station in Weil ist eine umfangreiche tägliche Analytik auf organische Spurenstoffe. Mit Einführung der hochauflösenden Massenspektrometrie konnte die Analytik relevanter polarer Substanzen massiv ausgebaut werden. Gleichzeitig besteht künftig die Möglichkeit, unbekannte Substanzen aufzuspüren und zu identifizieren.

The Critical Assessment of Small Molecule Identification, or CASMI, contest was founded in 2012 to provide scientists with a common open dataset to evaluate their identification methods. In this article, the challenges and solutions for the inaugural CASMI 2012 are presented. The contest was split into four categories corresponding with tasks to determine molecular formula and molecular structure, each from two measurement types, liquid chromatography-high resolution mass spectrometry (LC-HRMS), where preference was given to high mass accuracy data, and gas chromatography-electron impact-mass spectrometry (GC-MS), i.e., unit accuracy data. These challenges were obtained from plant material, environmental samples and reference standards. It was surprisingly difficult to obtain data suitable for a contest, especially for GC-MS data where existing databases are very large. The level of difficulty of the challenges is thus quite varied. In this article, the challenges and the answers are discussed, and recommendations for challenge selection in subsequent CASMI contests are given.

The Critical Assessment of Small Molecule Identification (CASMI) Contest was founded in 2012 to provide scientists with a common open dataset to evaluate their identification methods. In this review, we summarize the submissions, evaluate procedures and discuss the results. We received five submissions (three external, two internal) for LC–MS Category 1 (best molecular formula) and six submissions (three external, three internal) for LC–MS Category 2 (best molecular structure). No external submissions were received for the GC–MS Categories 3 and 4. The team of Dunn et al. from Birmingham had the most answers in the 1^st place for Category 1, while Category 2 was won by H. Oberacher. Despite the low number of participants, the external and internal submissions cover a broad range of identification strategies, including expert knowledge, database searching, automated methods and structure generation. The results of Category 1 show that complementing automated strategies with (manual) expert knowledge was the most successful approach, while no automated method could compete with the power of spectral searching for Category 2—if the challenge was present in a spectral library. Every participant topped at least one challenge, showing that different approaches are still necessary for interpretation diversity.

HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br₂, BrOCl, and Br₂O can also serve as brominating agents of the herbicide dimethenamid in solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration ([HOBr]_T), [Cl^–], and [FAC]_o) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in [HOBr]_T ranged from 1.09 (±0.17) to 1.67 (±0.16), reaching a maximum near the pK_a of HOBr. This complex dependence on [HOBr]_T implicates Br₂O as an active brominating agent. That bromination rates increased with increasing [Cl^–], [FAC]_o (at constant [HOBr]_T), and excess bromide (where [Br^–]_o>[FAC]_o) implicate BrCl, BrOCl, and Br₂, respectively, as brominating agents. As equilibrium constants for the formation of Br₂O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr Br₂O < BrOCl ≈ Br₂ < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.

Compound-specific isotope analysis (CSIA) is an important tool for the identification of contaminant sources and transformation pathways, but it is rarely applied to emerging aquatic micropollutants owing to a series of instrumental challenges. Using four different benzotriazole corrosion inhibitors and its derivatives as examples, we obtained evidence that formation of organometallic complexes of benzotriazoles with parts of the instrumentation impedes isotope analysis. Therefore, we propose two strategies for accurate δ¹³C and δ¹⁵N measurements of polar organic micropollutants by gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). Our first approach avoids metallic components and uses a Ni/Pt reactor for benzotriazole combustion while the second is based on the coupling of online methylation to the established GC/IRMS setup. Method detection limits for on-column injection of benzotriazole, as well as its 1-CH_3^–, 4-CH_3^–, and 5-CH_3^– substituted species were 0.1–0.3 and 0.1–1.0 mM for δ¹³C- and δ¹⁵N analysis, respectively, corresponding to injected masses of 0.7–1.8 nmol C and 0.4–3.0 nmol N, respectively. The Ni/Pt reactor showed good precision and was very long-lived (>1,000 successful measurements). Coupling isotopic analysis to offline solid-phase extraction enabled benzotriazole-CSIA in tap water, wastewater treatment effluent, activated sludge, and in commercial dishwashing products. A comparison of δ¹³C and δ¹⁵N values from different benzotriazoles and benzotriazole derivatives, both from commercial standards and in dishwashing detergents, reveals the potential application of the proposed method for source apportionment.

The aim of this study was to provide an ex ante assessment of the sustainability of genetically modified (GM) crops under the agricultural conditions prevailing in Switzerland. The study addressed the gaps in our knowledge relating to (1) the agronomic risks/benefits in production systems under Swiss conditions (at field and rotation/orchard level), (2) the economic and socio-economic impacts associated with altered farming systems, and (3) the agro-ecological risks/benefits of GM crops (at field and rotation/orchard level). The study was based on an inventory of GM crops and traits which may be available in the next decade, and on realistic scenarios of novel agricultural practices associated with the use of GM crops in conventional, integrated, and organic farming systems in Switzerland. The technology impact assessment was conducted using an adapted version of the matrix for "comparative assessment of risks and benefits for novel agricultural systems" developed for the UK. Parameter settings were based on information from literature sources and expert workshops. In a tiered approach, sustainability criteria were defined, an inventory of potentially available, suitable GM crops was drawn up, and scenarios of baseline and novel farming systems with GM crops were developed and subsequently submitted to economic, socio-economic, and agro-ecological assessments. The project had several system boundaries, which influenced the outcomes. It was limited to the main agricultural crops used for food and feed production and focused on traits that are relevant at the field level and are likely to be commercially available within a decade from the start of the project. The study assumed that there would be no statutory restrictions on growing GM crops in all farming systems and that they would be eligible for direct payments in the same way as non-GM crops. Costs for co-existence measures were explicitly excluded and it was assumed that GM foods could be marketed in the same way as non-GM foods at equal farm gate prices. The following model GM crops were selected for this study: (1) GM maize varieties with herbicide tolerance (HT), and with resistance to the European corn borer (Ostrinia nubilalis) and the corn rootworm (Diabrotica virgifera); (2) HT wheat; (3) GM potato varieties with resistance to late blight (Phytophthora infestans), to the nematode Globodera spp., and to the Colorado beetle (Leptinotarsa decemlineata); (4) HT sugar beet with resistance to "rhizomania" (beet necrotic yellow vein virus; BNYVV); (5) apples with traditionally bred or GM resistance to scab (Venturia inaequalis), and GM apples with stacked resistance to scab and fire blight (Erwinia amylovora). Scenarios for arable rotations and apple orchards were developed on the basis of the model crops selected. The impact assessments were conducted for the entire model rotations/orchards in order to explore cumulative effects as well as effects that depend on the farming systems (organic, integrated, and conventional). In arable cropping systems, herbicide tolerance had the most significant impact on agronomic practices in integrated and conventional farming systems. HT crops enable altered soil and weed management strategies. While no-till soil management benefited soil conservation, the highly efficient weed control reduced biodiversity. These effects accumulated over time due to the high proportion of HT crops in the integrated and conventional model rotations. In organic production systems, the effects were less pronounced, mainly due to non-use of herbicides. Traits affecting resistance to pests and diseases had a minor impact on the overall performance of the systems, mainly due to the availability of alternative crop protection tools or traditionally bred varieties. The use of GM crops had only a minor effect on the overall profitability of the arable crop rotations. In apple production systems, scab and fire blight resistance had a positive impact on natural resources as well as on local ecology due to the reduced need for spray passages and pesticide use. In integrated apple production, disease resistance increased profitability slightly, whereas in the organic scenario, both scab and fire blight resistance increased the profitability of the systems substantially. In conclusion, the ecological and socio-economic impacts identified in this study were highly context sensitive and were associated mainly with altered production systems rather than with the GM crops per se.

Die stoffliche Gewässerqualität hängt erheblich von der Landnutzung im Einzugsgebiet eines Gewässers ab. Mit einem neu erstellten Geo-Datensatz, der erstmals auch die Charakterisierung kleiner Fliessgewässer ermöglichte, wurde die Landnutzung entlang des Schweizer Gewässernetzes analysiert. In grosse Teile des Gewässernetzes, insbesondere in kleine Gewässer, können ausschliesslich Stoffe aus verschiedenen diffusen Quellen eingetragen werden.

High accuracy, high resolution tandem mass spectrometry (MS/MS) is becoming more common in analytical applications, yet databases of these spectra remain limited. Databases require good quality spectra with sufficient compound information, but processing, calibration, noise reduction and retrieval of compound information are time-consuming tasks that prevent many contributions. We present a comprehensive workflow for the automatic processing of MS/MS using formula annotation for recalibration and cleanup to generate high quality spectra of standard compounds for upload to MassBank (www.massbank.jp). Compound information is retrieved via Internet services. Reference standards of 70 pesticides were measured at various collision energies on an LTQ-Orbitrap XL to develop and evaluate the workflow. A total of 944 resulting spectra are now available on MassBank. Evidence of nitrogen adduct formation during MS/MS fragmentation processes was found, highlighting the benefits high accuracy MS/MS offers for spectral interpretation. A database of recalibrated, cleaned-up spectra resulted in the most correct spectra ranked in first place, regardless of whether the search spectra were recalibrated or not, whereas the average rank of the correct molecular formula was improved from 2.55 (uncalibrated) to 1.53 when using recalibrated MS/MS data. The workflow is available as an R package RMassBank capable of generating MassBank records from raw MS and MS/MS data and can be adjusted to process data acquired with different settings and instruments. This workflow is a vital step towards addressing the need for more high quality, high accuracy MS/MS spectra in spectral databases and provides important information for spectral interpretation.

In many situations, weak interactions between radicals and their environment potentially influence their properties and reactivity. We computed benchmark binding energies of 12 binary complexes involving radicals, using basis set extrapolated coupled cluster theory with up to CCSDT(Q) excitations plus corrections for core correlation and relativistic effects. The set was comprised of both electron-rich and electron-poor small radicals which were either neutral or positively charged. The radicals were complexed with the closed-shell polar (model) solvent molecules H₂O and HF. On the basis of these accurate ab initio binding energies, we assess the performance of many modern DFT functionals for these radical-solvent molecule interactions. Radical hydrogen bonded complexes are well-described by most DFT methods, but two-center–three-electron interactions are at least slightly overbound by most functionals evaluated here, including range-separated functionals. No such systematic error was found for electron-rich metal–water complexes. None of the functionals tested yield chemical accuracy for all types of complexes.

Solvated radicals play an important role in many areas of chemistry, but to date, the nature of their interactions with polar solvent molecules lacks chemical interpretation. We present a computational quantum chemical analysis of the binding motives of binary complexes involving electron-poor and electron-rich radicals bound to water and hydrogen fluoride, considered here as model polar solvent molecules. By comparing the binding strengths of several open-shell and closed-shell complexes, in combination with natural localized molecular orbital analysis, we show that open-shell complexes can exhibit additional donor–acceptor interactions relative to analogous closed-shell systems. This may explain the unexpectedly large binding energies observed in some open-shell complexes. These exploratory results show that specific interactions in open-shell systems deserve more attention, and they imply that the quantum mechanical description of explicit solvent molecules needs to be considered carefully when designing simulation protocols for solvated radicals.

Sulfonamide antibiotics are an important class of organic micropollutants in the aquatic environment. For several, sulfur dioxide extrusion products have been previously reported upon photochemical or dark oxidation. Using quantum chemical modeling calculations and transient absorption spectroscopy, it is shown that single-electron oxidation from sulfadiazine produces the corresponding aniline radical cation. Density functional theory calculations indicate that this intermediate can exist in four protonation states. One species exhibits a low barrier for an intramolecular nucleophilic attack at the para position of the oxidized aniline ring, in which a pyrimidine nitrogen acts as a nucleophile. This attack can lead to a rearranged structure, which exhibits the same connectivity as the SO₂-extruded oxidation product that was previously observed in the aquatic environment and characterized by NMR spectroscopy. We report a detailed reaction mechanism for this intramolecular aromatic nucleophilic substitution, and we discuss the possibility of this reaction pathway for other sulfonamide drugs.

The Chemcatcher passive sampler, which uses Empore™ disks as sampling phase, is frequently used to monitor polar organic chemicals in river water and effluents. Uptake kinetics need to be quantified to calculate time-weighted average concentrations from Chemcatcher field deployments. Information on release kinetics is needed if performance reference compounds (PRCs) are used to quantify the influence of environmental conditions on the uptake. In a series of uptake and elimination experiments, we used Empore™ SDB disks (poly(styrenedivinylbenzene) copolymer modified with sulfonic acid groups) as a sampling phase and 22 compounds with a logK_ow (octanol–water partitioning coefficient) range from −2.6 to 3.8. Uptake experiments were conducted in river water or tap water and lasted up to 25 days. Only 1 of 22 compounds (sulfamethoxazole) approached equilibrium in the uptake trials. Other compounds showed continuing non-linear uptake, even after 25 days. All compounds could be released from SDB disks, and desorption was proportionally higher in disks loaded for shorter periods. Desorption showed two-phase characteristics, and desorption was proportionally higher for passively sorbed compounds compared to actively loaded compounds (active loading was performed by pulling spiked river water over SDB disks using vacuum). We hypothesise that the two-phase kinetics and better retention of actively loaded compounds—and compounds loaded for a longer period—may be caused by slow diffusion of chemicals within the polymer. As sorption and desorption did not show isotropic kinetics, it is not possible to develop robust PRCs for adsorbent material like SDB disks.

Oxidation of aromatic rings and its alkyl substituents are often competing initial steps of organic pollutant transformation. The use of compound-specific isotope analysis (CSIA) to distinguish between these two pathways quantitatively, however, can be hampered by large H isotope fractionation that precludes calculation of apparent ²H-kinetic isotope effects (KIE) as well as the process identification in multi-element isotope fractionation analysis. Here, we investigated the C and H isotope fractionation associated with the transformation of toluene, nitrobenzene, and four substituted nitrotoluenes by permanganate, MnO₄^–, to propose a refined evaluation procedure for the quantitative distinction of CH₃-group oxidation and dioxygenation. On the basis of batch experiments, an isotopomer-specific kinetic model, and density functional theory (DFT) calculations, we successfully derived the large apparent ²H-KIE of 4.033 ± 0.20 for the CH₃-group oxidation of toluene from H isotope fractionation exceeding >1300‰ as well as the corresponding ¹³C-KIE (1.0324 ± 0.0011). Experiment and theory also agreed well for the dioxygenation of nitrobenzene, which was associated with ²H- and ¹³C-KIEs of 0.9410 ± 0.0030 (0.9228 obtained by DFT) and 1.0289 ± 0.0003 (1.025). Consistent branching ratios for the competing CH₃-group oxidation and dioxygenation of nitrotoluenes by MnO₄^– were obtained from the combined modeling of concentration as well as C and H isotope signature trends. Our approach offers improved estimates for the identification of contaminant microbial and abiotic oxidation pathways by CSIA.

Assessing the fate of nitroaromatic explosives in the subsurface is challenging because contaminants are present in different phases (e.g., bound to soil or sediment matrix or as solid-phase residues) and transformation takes place via several potentially competing pathways over time-scales of decades. We developed a procedure for compound-specific analysis of stable C, N, and H isotopes in nitroaromatic compounds (NACs) and characterized biodegradation of 2,4,6-trinitrotoluene (TNT) and two dinitrotoluene isomers (2,4-DNT and 2,6-DNT) in subsurface material of a contaminated site. The type and relative contribution of reductive and oxidative pathways to the degradation of the three contaminants was inferred from the combined evaluation of C, N, and H isotope fractionation. Indicative trends of Δδ¹⁵N vs Δδ¹³C and Δδ²H vs Δδ¹³C were obtained from laboratory model systems for biodegradation pathways initiated via (i) dioxygenation, (ii) reduction, and (iii) CH₃-group oxidation. The combined evaluation of NAC isotope fractionation in subsurface materials and in laboratory experiments suggests that in the field, 86–89% of 2,4-DNT transformation was due to dioxygenation while TNT was mostly reduced and 2,6-DNT reacted via a combination of reduction and CH₃-group oxidation. Based on historic information on site operation, our data imply biodegradation of 2,4-DNT with half-lives of up to 9–17 years compared to 18–34 years for cometabolic transformation of TNT and 2,6-DNT.

Monooxygenation is an important route of nitroaromatic compound (NAC) biodegradation and it is widely found for cometabolic transformations of NACs and other aromatic pollutants. We investigated the C and N isotope fractionation of nitrophenol monooxygenation to complement the characterization of NAC (bio)degradation pathways by compound-specific isotope analysis (CSIA). Because of the large diversity of enzymes catalyzing monooxygenations, we studied the combined C and N isotope fractionation and the corresponding ¹³C- and ¹⁵N-apparent kinetic isotope effects (AKIEs) of four nitrophenol-biodegrading microorganisms (Bacillus spharericus JS905, Pseudomonas sp. 1A, Arthrobacter sp. JS443, Pseudomonas putida B2) in the pH range 6.1–8.6 with resting cells and crude cell extracts. While the extent of C and N isotope fractionation and the AKIE-values varied considerably for the different organisms, the correlated C and N isotope signatures (δ¹⁵N vs δ¹³C) revealed trends, indicative of two distinct monooxygenation pathways involving hydroxy-1,4-benzoquinone or 1,2- and 1,4-benzoquinone intermediates, respectively. The distinction was possible based on larger secondary ¹⁵N-AKIEs associated with the benzoquinone pathway. Isotope fractionation was neither masked substantially by nitrophenol speciation nor transport across cell membranes. Only when 4-nitrophenol was biodegraded by Pseudomonas sp. 1A did isotope fractionation become negligible, presumably due to rate-limiting substrate binding steps pertinent to the catalytic cycle of flavin-dependent monooxygenases.

Micropollutants (MP) are only partly removed from municipal wastewater by nutrient removal plants and are seen increasingly as a threat to aquatic ecosystems and to the safety of drinking water resources. The addition of powder activated carbon (PAC) is a promising technology to complement municipal nutrient removal plants in order to achieve a significant reduction of MPs and ecotoxicity in receiving waters. This paper presents the salient outcomes of pilot- and full-scale applications of PAC addition in different flow schemes for micropollutant removal in municipal wastewater treatment plants (WWTPs). The sorption efficiency of PAC is reduced with increasing dissolved organic carbon (DOC). Adequate treatment of secondary effluent with 5–10 g DOC m⁻³ requires 10–20 g PAC m⁻³ of effluent. Counter-current use of PAC by recycling waste PAC from post-treatment in a contact tank with an additional clarifier to the biology tank improved the overall MP removal by 10 to 50% compared with effluent PAC application alone. A dosage of 15 g PAC m⁻³ to a full-scale flocculation sand filtration system and recycling the backwash water to the biology tank showed similar MP elimination. Due to an adequate mixing regime and the addition of adapted flocculants, a good retention of the fine fraction of the PAC in the deep-bed filter were observed (1–3 g TSS m⁻³; TSS: total suspended solids). With double use of PAC, only half of the PAC was required to reach MP removal efficiencies similar to the direct single dosage of PAC to the biology tank. Overall, the application of PAC in WWTPs seems to be an adequate and feasible technology for efficient MP elimination (>80%) from wastewater comparable with post ozonation.

Control of the N-glycosylase reaction by the DNA repair enzyme, MutY, entails the organization of solvent molecules. Classical molecular dynamics and QM/MM simulations were used to investigate the solvent and environment effects contributing to catalysis. Our findings suggest that the entire reaction is an energetically neutral process, in which the first step is rate determining, requiring protonation of adenine (N₇) to initiate cleavage, and the second step is strongly exothermic, involving hydrolysis of an oxacarbenium ion intermediate. Although water molecules are catalytically active in both steps, the first step requires an entirely different level of solvent organization compared to the second. Needed to secure protonation at N₇, a long-term solvation pattern is established which facilitates the involvement of three out of the five structured water molecules in the active site. This persistent arrangement coordinates the catalytically active water molecules into prime positions to assist the proton transfer: (i) a water molecule frequently bridges the catalytic residues and (ii) the bridging water molecule is assisted by 1–2 other ‘supporting’ water molecules. To maintain this configuration, MutY, surprisingly, uses hydrophobic residues in combination with hydrophilic residues to tune the microenvironment into a ‘water trap’. Hydrophilic residues prolong solvent residence times by maintaining hydrogen-bonding networks, whereas the hydrophobic residues constrain the positioning of the catalytic water molecules that assist the proton-transfer event. In this way, the enzyme uses both entropic and enthalpic considerations to guide the water-assisted reaction.

The discovery of oiled and non-oiled honeycomb material in the Gulf of Mexico surface waters and along coastal beaches shortly after the explosion of Deepwater Horizon sparked debate about its origin and the oil covering it. We show that the unknown pieces of oiled and non-oiled honeycomb material collected in the Gulf of Mexico were pieces of the riser pipe buoyancy module of Deepwater Horizon. Biomarker ratios confirmed that the oil had originated from the Macondo oil well and had undergone significant weathering. Using the National Oceanic and Atmospheric Administration's records of the oil spill trajectory at the sea surface, we show that the honeycomb material preceded the front edge of the uncertainty of the oil slick trajectory by several kilometers. We conclude that the observation of debris fields deriving from damaged marine materials may be incorporated into emergency response efforts and forecasting of coastal impacts during future offshore oil spills, and ground truthing predicative models.

Anthropogenic coal fly ash (FA) aerosol may represent a significant source of bioavailable iron in the open ocean. Few measurements have been made that compare the solubility of atmospheric iron from anthropogenic aerosols and other sources. We report here an investigation of iron dissolution for three FA samples in acidic aqueous solutions and compare the solubilities with that of Arizona test dust (AZTD), a reference material for mineral dust. The effects of pH, simulated cloud processing, and solar radiation on iron solubility have been explored. Similar to previously reported results on mineral dust, iron in aluminosilicate phases provides the predominant component of dissolved iron. Iron solubility of FA is substantially higher than of the crystalline minerals comprising AZTD. Simulated atmospheric processing elevates iron solubility due to significant changes in the morphology of aluminosilicate glass, a dominant material in FA particles. Iron is continuously released into the aqueous solution as FA particles break up into smaller fragments. These results suggest that the assessment of dissolved atmospheric iron deposition fluxes and their effect on the biogeochemistry at the ocean surface should be constrained by the source, environmental pH, iron speciation, and solar radiation.

During rain events, herbicides can be transported from their point of application to surface waters, where they may harm aquatic organisms. Since the spatial pattern of mobilisation and transport is heterogeneous, the contributions of different fields to the herbicide load in the stream may vary considerably within one catchment. Therefore, the prediction of contributing areas could help to target mitigation measures efficiently to those locations where they reduce herbicide pollution the most.
Such spatial predictions require sufficient insight into the underlying transport processes. To improve the understanding of the process chain of herbicide mobilisation on the field and the subsequent transport through the catchment to the stream, we performed a controlled herbicide application on corn fields in a small agricultural catchment (ca. 1 km²) with intensive crop production in the Swiss Plateau. Water samples were collected at different locations in the catchment (overland flow, tile drains and open channel) for two months after application in 2009, with a high temporal resolution during rain events. We also analysed soil samples from the experimental fields and measured discharge, groundwater level, soil moisture and the occurrence of overland flow at several locations. Several rain events with varying intensities and magnitudes occurred during the study period. Overland flow and erosion were frequently observed in the entire catchment. Infiltration excess and saturation excess overland flow were both observed. However, the main herbicide loss event was dominated by infiltration excess.
Despite the frequent and wide-spread occurrence of overland flow, most of this water did not reach the channel directly, but was retained in small depressions in the catchment. From there, it reached the stream via macropores and tile drains. Manholes of the drainage system and storm drains for road and farmyard runoff acted as additional shortcuts to the stream.
Although fast flow processes such as overland and macropore flow reduce the influence of the herbicide's chemical properties on transport due to short travel times, sorption properties influenced the herbicide transfer from ponding overland flow to tile drains (macropore flow). However, no influence of sorption was observed during the mobilisation of the herbicides from soil to overland flow. These observations on the role of herbicide properties contradict previous findings to some degree. Furthermore, they demonstrate that valuable insight can be gained by making spatially detailed observations along the flow paths.

Compound-specific stable-isotope analysis (CSIA) has greatly facilitated assessment of sources and transformation processes of organic pollutants. Multielement isotope analysis is one of the most promising applications of CSIA because it even enables distinction of different transformation pathways. This review introduces the essential features of continuous-flow isotope-ratio mass spectrometry (IRMS) and highlights current challenges in environmental analysis as exemplified for the isotopes of nitrogen, hydrogen, chlorine, and oxygen. Strategies and recent advances to enable isotopic measurements of polar contaminants, for example pesticides or pharmaceuticals, are discussed with special emphasis on possible solutions for analysis of low concentrations of contaminants in environmental matrices. Finally, we discuss different levels of calibration and referencing and point out the urgent need for compound-specific isotope standards for gas chromatography–isotope-ratio mass spectrometry (GC–IRMS) of organic pollutants.

Water Reclamation Technologies for Safe Managed Aquifer Recharge has been developed from the RECLAIM WATER project supported by the European Commission under Thematic Priority 'Global Change and Ecosystems' of the Sixth Framework Programme. Its strategic objective is to develop hazard mitigation technologies for water reclamation providing safe and cost effective routes for managed aquifer recharge. Different treatment applications in terms of behaviour of key microbial and chemical contaminants are assessed. Engineered as well as natural treatment trains are investigated to provide guidance for sustainable MAR schemes using alternative sources such as recycled water and stormwater The technologies considered are also well suited to the needs of developing countries, which have a growing need of supplementation of freshwater resources. A broad range of international full-scale case studies enables insights into long-term system behaviour, operational aspects, and fate of a comprehensive number of compounds and contaminants, especially microbiological hazards, organic micropollutants and bulk organics. Water Reclamation Technologies for Safe Managed Aquifer Recharge presents advances in water reclamation technologies including new process combinations to treat alternative water sources to appropriate water quality levels for sustainable aquifer recharge.

Clay minerals often contain redox-active structural iron that participates in electron transfer reactions with environmental pollutants, bacteria, and biological nutrients. Measuring the redox properties of structural Fe in clay minerals using electrochemical approaches, however, has proven to be difficult due to a lack of reactivity between clay minerals and electrodes. Here, we overcome this limitation by using one-electron-transfer mediating compounds to facilitate electron transfer between structural Fe in clay minerals and a vitreous carbon working electrode in an electrochemical cell. Using this approach, the electron-accepting and -donating capacities (Q_EAC and Q_EDC) were quantified at applied potentials (E_H) of −0.60 V and +0.61 V (vs SHE), respectively, for four natural Fe-bearing smectites (i.e., SWa-1, SWy-2, NAu-1, and NAu-2) having different total Fe contents (Fe_total = 2.3 to 21.2 wt % Fe) and varied initial Fe²⁺/Fe_total states. For every SWa-1 and SWy-2 sample, all the structural Fe was redox-active over the tested E_H range, demonstrating reliable quantification of Fe content and redox state. Yet for NAu-1 and NAu-2, a significant fraction of the structural Fe was redox-inactive, which was attributed to Fe-rich smectites requiring more extreme E_H-values to achieve complete Fe reduction and/or oxidation. The Q_EAC and Q_EDC values provided here can be used as benchmarks in future studies examining the extent of reduction and oxidation of Fe-bearing smectites.

The reaction between magnetite and aqueous Fe²⁺ has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe²⁺ with magnetite (Fe₃O₄) results in the structural incorporation of Fe²⁺ and an increase in the bulk Fe²⁺ content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe²⁺, as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe²⁺ and magnetite by reacting isotopically “normal” magnetite with ⁵⁷Fe-enriched aqueous Fe²⁺. The extent of Fe atom exchange between magnetite and aqueous Fe²⁺ was significant (54–71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with ⁵⁶Fe²⁺ indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co²⁺Fe₂³⁺O₄) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.

Structural Fe in clay minerals is an important, albeit poorly characterized, redox-active phase found in many natural and engineered environments. This work develops an experimental approach to directly assess the redox properties of a natural Fe-bearing smectite (ferruginous smectite, SWa-1, 12.6 wt % Fe) with mediated electrochemical reduction (MER) and oxidation (MEO). By utilizing a suite of one-electron-transfer mediating compounds to facilitate electron transfer between structural Fe in SWa-1 and a working electrode, we show that the Fe²⁺/Fe³⁺ couple in SWa-1 is redox-active over a large range of potentials (from E_H = −0.63 V to +0.61 V vs SHE). Electrochemical and spectroscopic analyses of SWa-1 samples that were subject to reduction and re-oxidation cycling revealed both reversible and irreversible structural Fe rearrangements that altered the observed apparent standard reduction potential (E_H^Φ) of structural Fe. E_H^Φ-values vary by as much as 0.56 V between SWa-1 samples with different redox histories. The wide range of E_H-values over which SWa-1 is redox-active and redox history-dependent E_H^Φ-values underscore the importance of Fe-bearing clay minerals as redox-active phases in a wide range of redox regimes.

The mechanism of covalent bond formation of the model sulfonamide sulfathiazole (STZ) and the stronger nucleophile para-ethoxyaniline was studied in reactions with model humic acid constituents (quinones and other carbonyl compounds) in the absence and presence of laccase. As revealed by high resolution mass spectrometry, the initial bonding of STZ occurred by 1,2- and 1,4-nucleophilic additions of the aromatic amino group to quinones resulting in imine and anilinoquinone formation, respectively. Experiments using the radical scavenger tert-butyl-alcohol provided the same products and similar formation rates as those without scavenger indicating that probably not radical coupling reactions were responsible for the initial covalent bond formation. No addition with nonquinone carbonyl compounds occurred within 76 days except for a slow 1,4-addition to the β-unsaturated carbonyl 1-penten-3-one. The stability of covalent bonds against desorption and pressurized liquid extraction (PLE) was assessed. The recovery rates showed no systematic differences in STZ extractability between the two product types. This suggests that the strength of bonding is not controlled by the initial type of bond, but by the extent of subsequent incorporation of the reaction product into the formed polymer. This incorporation was monitored for ¹⁵N aniline by ¹H–¹⁵N HMBC NMR spectroscopy. The initial 1,2- and 1,4-addition bonds were replaced by stronger heterocyclic forms with increasing incubation time. These processes could also hold true for soils, and a slow nonextractable residue formation with time could be related to a slow increase of the amount of covalently bound sulfonamide and the strength of bonding.

In many areas, excessive manure application on agricultural land has led to a substantial build-up of soil phosphorus (P) stocks, increasing the risks for diffuse pollution of surface waters. Recent studies highlight the need to differentiate between runoff types for better prediction of these risks. In a factorial field-plot experiment we investigated the role of soil-P status, band-applied manure and rainfall intensity on P losses from two Swiss grassland sites. Artificial rainfall was applied on each plot first at medium intensity using a sprinkler and then at high intensity using a watering can, simulating two different runoff conditions. Under both conditions, dissolved reactive P (DRP) in runoff increased linearly with water soluble P in the soil (WSP), but the extraction coefficients differed substantially between the two phases of runoff generation. It was 0.017 kg L⁻¹ for runoff generated with the watering can (WCR), and 0.085 kg L⁻¹ for runoff generated with the sprinkler (SR). Manure application increased DRP losses, but did not override the effect of soil P status. Phosphorus losses with runoff were more sensitive to soil P status for SR than for WCR. Reducing soil-P is therefore crucial to reduce runoff-P.

Das Nationale Forschungsprogramm NFP 61 will wissenschaftlich fundierte Grundlagen zum künftigen Umgang mit Wasser bereitstellen. Es verfügt über einen Finanzrahmen von zwölf Millionen Franken und dauert ab Januar 2010 vier Jahre. Die Praxisrelevanz wird im Programm stark gewichtet. Aqua & Gas stellt an dieser Stelle jeweils ein Projekt vor. In diesem Beitrag gibt Christian Stamm von der Forschungsabteilung «Umweltchemie» der Eawag als Leiter des NFP-Projekts «Integriertes Management der Wasserqualität von Fliessgewässern» Auskunft.

The Haihe River System (HRS) drains the Chinese megacities Beijing and Tianjin, forming a large-scale irrigation system severely impacted by wastewater-borne pollution. The origin, temporal magnitudes, and annual mass fluxes of a wide range of pharmaceuticals, household chemicals, and pesticides were investigated in the HRS, which drains 70% of the wastewater discharged by 20 million people living in Beijing. Based on Chinese consumption statistics and our initial screening for 268 micropollutants using high-resolution mass spectrometry, 62 compounds were examined in space and time (2009−2010). The median concentrations ranged from 3 ng/L for metolachlor to 1100 ng/L for benzotriazole and sucralose. Concentrations of carbendazim, clarithromycin, diclofenac, and diuron exceed levels of ecotoxicological concern. Mass-flux analyses revealed that pharmaceuticals (5930 kg/year) and most household chemicals (5660 kg/year) originated from urban wastewaters, while the corrosion inhibitor benzotriazole entered the rivers through other pathways. Total pesticide residues amounted to 1550 kg/year. Per capita loads of pharmaceuticals in wastewater were lower than those in Europe, but are expected to increase in the near future. As 95% of the river water is diverted to irrigate agricultural soil, the loads of polar organic micropollutants transported with the water might pose a serious threat to food safety and groundwater quality.

The objective of this work was to improve our understanding of the quantitative predictive capabilities of metatranscriptomics. To meet this objective, we investigated whether we can predict the activity level of a specific biochemical function based on the abundance of the corresponding gene transcript within measured community metatranscriptomes. In addition, we investigated the lower limit of a microorganism's abundance that still allows detection of its transcripts within a metatranscriptome and prediction of the activity levels of the enzyme encoded by the transcript. To do this, we amended an undefined microbial community with varying fractions of an Escherichia coli strain that can catalyze a specific transformation reaction for the herbicide atrazine. We observed a linear and proportional relationship between the activity level of the transformation reaction and the abundance of its associated encoding transcript down to an E. coli cell density of 0.05% of the population.

The objective of this work was to identify relevant wastewater treatment plant (WWTP) parameters and underlying microbial processes that influence the biotransformation of a diverse set of micropollutants. To do this, we determined biotransformation rate constants for ten organic micropollutants in batch reactors seeded with activated sludge from ten diverse WWTPs. The estimated biotransformation rate constants for each compound ranged between one and four orders of magnitude among the ten WWTPs. The biotransformation rate constants were tested for statistical associations with various WWTP process parameters, amoA transcript abundance, and acetylene-inhibited monooxygenase activity. We determined that (i) ammonia removal associates with oxidative micropollutant biotransformation reaction rates; (ii) archaeal but not bacterial amoA transcripts associate with both ammonia removal and oxidative micropollutant biotransformation reaction rates; and (iii) the activity of acetylene-inhibited monooxygenases (including ammonia monooxygenase) associates with ammonia removal and the biotransformation rate of isoproturon, but does not associate with all oxidative micropollutant biotransformations. In combination, these results lead to the conclusion that ammonia removal and amoA transcript abundance can potentially be predictors of oxidative micropollutant biotransformation reactions, but that the biochemical mechanism is not necessarily linked to ammonia monooxygenase activity.

Das Schicksal organischer Mikroverunreinigungen in Böden und Gewässern ist mit herkömmlichen Methoden schwierig zu verfolgen. Die Einzelstoff-Isotopenanalyse ermöglicht es, die Isotopenzusammensetzung von Schadstoffen zu untersuchen. Damit lassen sich zum Beispiel die Herkunft von Geschirrspülmitteln nachweisen oder die Abbauwege von Sprengstoff bestimmen.

The fate of organic micropollutants in soils and natural waters is difficult to track using traditional methods. But with compound-specific isotope analysis, the isotopic composition of contaminants can be studied. This makes it possible, for example, to trace the origin of dishwasher detergents or to determine the degradation pathways of explosives.

An automated multiresidue method consisting of an online solid-phase extraction step coupled to a high performance liquid chromatography–tandem mass spectrometer (online-SPE–HPLC–MS/MS method) was developed for the determination of 88 polar organic micropollutants with a broad range of physicochemical properties (log D_OW (pH 7): −4.2 to 4.2). Based on theoretical considerations, a single mixed-bed multilayer cartridge containing four different extraction materials was composed for the automated enrichment of water samples. This allowed the simultaneous analysis of pesticides, biocides, pharmaceuticals, corrosion inhibitors, many of their transformation products, and the artificial sweetener sucralose in three matrices groundwater, surface water, and wastewater. Limits of quantification (LOQs) were in the environmentally relevant concentration range of 0.1–87 ng/L for groundwater and surface water, and 1.5–206 ng/L for wastewater. The majority of the compounds could be quantified below 10 ng/L in groundwater (82%) and surface water (80%) and below 100 ng/L in wastewater (80%). Relative recoveries were largely between 80 and 120%. Intraday and inter-day precision, expressed as relative standard deviation, were generally better than 10% and 20%, respectively. 50 isotope labeled internal standards were used for quantification and accordingly, relative recoveries as well as intraday and inter-day precision were better for compounds with corresponding internal standard. The applicability of this method was shown during a sampling campaign at a riverbank filtration site for drinking water production with travel times of up to 5 days. 36 substances of all compound classes investigated could be found in concentrations between 0.1 and 600 ng/L. The results revealed the persistence of carbamazepine and sucralose in the groundwater aquifer as well as degradation of the metamizole metabolite 4-acetamidoantipyrine.

Nutrient emission dropped significantly during the last two decades in the Danube Basin. To assess the effect of reduced nutrient loads on the trophic status of running waters, this regional study analyzed the relationships between nutrients (P and N) and suspended chlorophyll (Chl) using long-term monitoring data in Hungary. Including the upstream catchments of trans-boundary rivers, the study covered an approximate area of 400,000 km², equivalent to the half of the entire Danube catchment. Decadal median Chl was unrelated to P and N concentrations in the whole data set and weakly related to total P (TP) at natural-moderately polluted (N-MP) sites, which were distinguished from highly polluted (HP) sites by using cutoff values for chloride, chemical oxygen demand and TP. At both the N-MP sites and most of the HP sites, Chl increased with channel length. This indicated that water residence time was a more important determinant of Chl than nutrients. Nutrient concentrations showed a significant downward trend in time at half of our sites. With a nearly equal frequency, a parallel trend might or might not occur in Chl. The apparent efficiency of nutrient management was expressed as the quotient of the slopes of linear trends in Chl and nutrients. At sites within 150 km from source, this efficiency was marginal. In larger rivers, efficiency improved steeply. The highest efficiency was observed in the downstream reach of the Danube (upstream length >1,300 km) where P availability might frequently limit algal growth. The results suggest that eutrophication management in rivers should be based on Chl response functions, rather than universal nutrient criteria. Four Chl response classes were identified based on the observed longitudinal P and Chl gradients.

An enhanced transport-based management approach is presented, which is able to support cost-effective water quality management with respect to diffuse phosphorus pollution. Suspended solids and particulate phosphorus emissions and their transport were modeled in two hilly agricultural watersheds (Wulka River in Austria and Zala River in Hungary) with an improved version of the catchment-scale PhosFate model. Source and transmission areas were ranked by an optimization method in order to provide a priority list of the areas of economically efficient (optimal) management alternatives. The model was calibrated and validated at different gauges and for various years. The spatial distribution of the emissions shows that approximately one third of the catchment area is responsible for the majority of the emissions. However, only a few percent of the source areas can transport fluxes to the catchment outlet. These effective source areas, together with the main transmission areas are potential candidates for improved management practices. In accordance with the critical area concept, it was shown that intervention with better management practices on a properly selected small proportion of the total area (1–3%) is sufficient to reach a remarkable improvement in water quality. If soil nutrient management is also considered in addition to water quality, intervention on 4–12% of the catchment areas can fulfill both aspects.

A pilot-scale membrane bioreactor (MBR) was installed and operated for one year at a Swiss hospital. It was fed an influent directly from the hospital’s sanitary collection system. To study the efficiency of micropollutant elimination in raw hospital wastewater that comprises a complex matrix with micropollutant concentrations ranging from low ng/L to low mg/L, an automated online SPE-HPLC-MS/MS analytical method was developed. Among the 68 target analytes were the following: 56 pharmaceuticals (antibiotics, antimycotics, antivirals, iodinated X-ray contrast media, antiinflamatory, cytostatics, diuretics, beta blockers, anesthetics, analgesics, antiepileptics, antidepressants, and others), 10 metabolites, and 2 corrosion inhibitors. The MBR influent contained the majority of those target analytes. The micropollutant elimination efficiency was assessed through continuous flow-proportional sampling of the MBR influent and continuous time-proportional sampling of the MBR effluent. An overall load elimination of all pharmaceuticals and metabolites in the MBR was 22%, as over 80% of the load was due to persistent iodinated contrast media. No inhibition by antibacterial agents or disinfectants from the hospital was observed in the MBR. The hospital wastewater was found to be a dynamic system in which conjugates of pharmaceuticals deconjugate and biological transformation products are formed, which in some cases are pharmaceuticals themselves.

A mechanistic toxicokinetic and toxicodynamic model for acute toxic effects (immobilization, mortality) of the organothiophosphate insecticide diazinon in Daphnia magna is presented. The model was parameterized using measured external and internal (whole-body) concentrations of diazinon, its toxic metabolite diazoxon, and the inactive metabolite 2-isopropyl-6-methyl-4-pyrimidinol, plus acetylcholinesterase (AChE) activity measured during exposure to diazinon in vivo. The toxicokinetic and toxicodynamic model provides a coherent picture from exposure to the resulting toxic effect on an organism level through internally formed metabolites and the effect on a molecular scale. A very fast reaction of diazoxon with AChE (pseudo first-order inhibition rate constant k_i = 3.3 h⁻¹) compared with a slow formation of diazoxon (activation rate constant k_act = 0.014 h⁻¹) was responsible for the high sensitivity of D. magna toward diazinon. Recovery of AChE activity from inhibition was slow and rate-determining (99% recovery within 16 d), compared with a fast elimination of diazinon (99% elimination within 17 h). The obtained model parameters were compared with toxicokinetic and toxicodynamic parameters of Gammarus pulex exposed to diazinon from previous work. This comparison revealed that G. pulex is less sensitive because of a six times faster detoxification of diazinon and diazoxon and an approximately 400 times lower rate for damage accrual. These differences overcompensate the two times faster activation of diazinon to diazoxon in G. pulex compared to D. magna. The present study substantiates theoretical considerations that mechanistically based effect models are helpful to explain sensitivity differences among different aquatic invertebrates.

Hexavalent uranium (U^VI) can be reduced enzymatically by various microbes and abiotically by Fe²⁺-bearing minerals, including magnetite, of interest because of its formation from Fe³⁺ (oxy)hydroxides via dissimilatory iron reduction. Magnetite is also a corrosion product of iron metal in suboxic and anoxic conditions and is likely to form during corrosion of steel waste containers holding uranium-containing spent nuclear fuel. Previous work indicated discrepancies in the extent of U^VI reduction by magnetite. Here, we demonstrate that the stoichiometry (the bulk Fe²⁺/Fe³⁺ ratio, x) of magnetite can, in part, explain the observed discrepancies. In our studies, magnetite stoichiometry significantly influenced the extent of U^VI reduction by magnetite. Stoichiometric and partially oxidized magnetites with x ≥ 0.38 reduced U^VI to U^IV in UO₂ (uraninite) nanoparticles, whereas with more oxidized magnetites (x < 0.38) and maghemite (x = 0), sorbed U^VI was the dominant phase observed. Furthermore, as with our chemically synthesized magnetites (x ≥ 0.38), nanoparticulate UO₂ was formed from reduction of U^VI in a heat-killed suspension of biogenic magnetite (x = 0.43). X-ray absorption and Mössbauer spectroscopy results indicate that reduction of U^VI to U^IV is coupled to oxidation of Fe²⁺ in magnetite. The addition of aqueous Fe²⁺ to suspensions of oxidized magnetite resulted in reduction of U^VI to UO₂, consistent with our previous finding that Fe²⁺ taken up from solution increased the magnetite stoichiometry. Our results suggest that magnetite stoichiometry and the ability of aqueous Fe²⁺ to recharge magnetite are important factors in reduction of U^VI in the subsurface.

Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe²⁺-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe²⁺-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe²⁺-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe²⁺-catalysed iron oxide recrystallization.

The thermodynamics of mixing and its dependence on cation distribution in the Fe₃O₄–Fe₂TiO₄ (magnetite-ulvöspinel) spinel solid solution were studied using high-temperature oxide melt solution calorimetry and a range of structural and spectroscopic probes. The enthalpies of formation of ilmenite and ulvöspinel from the oxides and from the elements were obtained using oxidative drop solution calorimetry at 973 K in molten sodium molybdate. The enthalpy of mixing, determined from the fit to the measured enthalpies of drop solution calorimetry, is endothermic and represented by a quadratic formalism, ΔH_mix = (22.60 ± 8.46)x(1 − x) kJ/mol, where x is the mole fraction of ulvöspinel. The entropies of mixing are more complex than those for a regular solution and have been calculated based on average measured and theoretical cation distributions. Calculated free energies of mixing show evidence for a solvus at low temperature in good agreement with that observed experimentally.

Formation of soil nonextractable residues (NER) is central to the fate and persistence of pesticides. To investigate pools and extent of NER formation, an established inverse modeling approach for pesticide soil degradation time series was evaluated with a Monte Carlo Markov Chain (MCMC) sampling procedure. It was found that only half of 73 pesticide degradation time series from a homogeneous soil source allowed for well-behaved identification of kinetic parameters with a four-pool model containing a parent compound, a metabolite, a volatile, and a NER pool. A subsequent simulation indeed confirmed distinct parameter combinations of low identifiability. Taking the resulting uncertainties into account, several conclusions regarding NER formation and its impact on persistence assessment could nonetheless be drawn. First, rate constants for transformation of parent compounds to metabolites were correlated to those for transformation of parent compounds to NER, leading to degradation half-lives (DegT50) typically not being larger than disappearance half-lives (DT50) by more than a factor of 2. Second, estimated rate constants were used to evaluate NER formation over time. This showed that NER formation, particularly through the metabolite pool, may be grossly underestimated when using standard incubation periods. It further showed that amounts and uncertainties in (i) total NER, (ii) NER formed from the parent pool, and (iii) NER formed from the metabolite pool vary considerably among data sets at t→∞, with no clear dominance between (ii) and (iii). However, compounds containing aromatic amine moieties were found to form significantly more total NER when extrapolating to t→∞ than the other compounds studied. Overall, our study stresses the general need for assessing uncertainties, identifiability issues, and resulting biases when using inverse modeling of degradation time series for evaluating persistence and NER formation.

Polyhalogenated 1′-methyl-1,2′-bipyrroles are natural products that biomagnify into upper trophic levels of marine food webs. Here we demonstrate that they are unusually enriched in ¹⁵N (δ¹⁵N from +19.3‰ to +28.1‰) relative to other biosynthetic organic compounds measured to date and the mammals from which the compounds were isolated. We argue the ¹⁵N enrichment likely stems from enriched precursors and/or fractionation during biosynthesis and is not from MBP degradation. We also consider possible sources of MBPs in light of these results.

Dioxygenation of aromatic rings is frequently the initial step of biodegradation of organic subsurface pollutants. This process can be tracked by compound-specific isotope analysis to assess the extent of contaminant transformation, but the corresponding isotope effects, especially for dioxygenation of N-substituted, aromatic contaminants, are not well understood. We investigated the C and N isotope fractionation associated with the biodegradation of aniline and diphenylamine using pure cultures of Burkholderia sp. strain JS667, which can biodegrade both compounds, each by a distinct dioxygenase enzyme. For diphenylamine, the C and N isotope enrichment was normal with ε_C- and ε_N-values of −0.6 ± 0.1‰ and −1.0 ± 0.1‰, respectively. In contrast, N isotopes of aniline were subject to substantial inverse fractionation (ε_N of +13 ± 0.5‰), whereas the ε_C-value was identical to that of diphenylamine. A comparison of the apparent kinetic isotope effects for aniline and diphenylamine dioxygenation with those from abiotic oxidation by manganese oxide (MnO₂) suggest that the oxidation of a diarylamine system leads to distinct C–N bonding changes compared to aniline regardless of reaction mechanism and oxidant involved. Combined evaluation of the C and N isotope signatures of the contaminants reveals characteristic Δδ¹⁵N/Δδ¹³C-trends for the identification of diphenylamine and aniline oxidation in contaminated subsurfaces and for the distinction of aniline oxidation from its formation by microbial and/or abiotic reduction of nitrobenzene.

Titanomagnetite (Fe_3−xTi_xO₄) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge compensated by conversion of Fe(III) to Fe(II) in the unit cell. A comprehensive suite of tools was used to probe composition, structure, and magnetic properties down to site-occupancy level, emphasizing distribution and accessibility of Fe(II) as a function of x. Synthesis of nanoparticles in the range 0 ⩽ x ⩽ 0.6 was attempted; Ti, total Fe and Fe(II) content were verified by chemical analysis. TEM indicated homogeneous spherical 9–12 nm particles. μ-XRD and Mössbauer spectroscopy on anoxic aqueous suspensions verified the inverse spinel structure and Ti(IV) incorporation in the unit cell up to x ⩽ 0.38, based on Fe(II)/Fe(III) ratio deduced from the unit cell edge and Mössbauer spectra. Nanoparticles with a higher value of x possessed a minor amorphous secondary Fe(II)/Ti(IV) phase. XANES/EXAFS indicated Ti(IV) incorporation in the octahedral sublattice (B-site) and proportional increases in Fe(II)/Fe(III) ratio. XA/XMCD indicated that increases arise from increasing B-site Fe(II), and that these charge-balancing equivalents segregate to those B-sites near particle surfaces. Dissolution studies showed that this segregation persists after release of Fe(II) into solution, in amounts systematically proportional to x and thus the Fe(II)/Fe(III) ratio. A mechanistic reaction model was developed entailing mobile B-site Fe(II) supplying a highly interactive surface phase that undergoes interfacial electron transfer with oxidants in solution, sustained by outward Fe(II) migration from particle interiors and concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1.

Der Rhein ist einer der bedeutendsten Flüsse Europas. Sein Verlauf ist geprägt durch einen dicht besiedelten Kulturraum, intensiv geführte Landwirtschaft und hochtechnisierte Industrieanlagen. Sein Wasser bietet zahlreichen spezialisierten Tierund Pflanzenarten ein Zuhause und rund 20 Millionen Menschen täglich Trinkwasser zumeist aus Uferfiltrat. Daneben transportiert sein Wasser beträchtliche Mengen an häuslichen und industriellen Abwässern und entwässert intensiv genutzte Landwirtschaftsflächen. Um eine hohe Qualität des Trinkwassers gewährleisten und den Lebensraum für aquatische Organismen erhalten zu können, ist eine umfassende Kenntnis der aktuellen Wasserqualität des Rheinwassers unerlässlich. Nachdem sich 1986 ein Unfall im Industriegebiet Schweizerhalle bei Basel ereignet hatte, wobei große Mengen Chemikalien in den Rhein gelangten und dessen Ökosystem empfindlich aus dem Gleichgewicht brachten, wurde 1992 die internationale Rheinüberwachungsstation Weil am Rhein (RÜS) in Betrieb genommen. Die Hauptaufgaben der vom Land Baden-Württemberg und der Schweizerischen Eidgenossenschaft zu gleichen Anteilen betriebenen RÜS bestehen in einer langfristigen Trendüberwachung einer Vielzahl von Parametern und in der zeitnahen Detektion von Fehleinleitungen und Havarien. Ein internationaler Warn- und Alarmplan wurde eingerichtet, um flussabwärts liegende Behörden und Trinkwasserwerke im Fall bedenklicher Verunreinigungen informieren zu können.

Phosphorus concentration in rivers results from both external inputs and internal loading from the bottom sediments. Seasonal, spatial, and multi-annual dynamics of phosphorus forms in bottom sediments and their interstitial water for the river Prut (Moldova) were evaluated. In order to determine content of total phosphorus in the bottom sediments, fresh (wet) samples were subjected to persulfate oxidation. The content of inorganic phosphorus was determined after acidic oxidation of samples. The amount of organic phosphorus was obtained by subtracting inorganic phosphorus from the amount of total phosphorus. Content f phosphorus forms in interstitial water was determined after centrifugation of fresh (wet) sediments. In general, the shape of dynamics of the amounts of inorganic phosphorus in sediments was close during years 2009, 2010, and 2011, with registered higher contents of this form on the middle course of the river. The spatial dynamics of organic phosphorus is less homogeneous along the Prut River. During 2009, higher amounts of organic phosphorus were recorded on the middle sector. During the spring of year 2010, the content of organic phosphorus in sediments was practically not changed along the river. The ratio of inorganic/organic phosphorus in bottom sediments was similar during the researched years, with the predominance of the inorganic phosphorus being recorded. Also, the increasing tendency of the percentage of organic phosphorus from spring to summer was identified. Generally, appropriate spatial and seasonal dynamics of phosphorus forms in bottom sediments and their interstitial water were recorded, although sometimes with some differences.

This article explores consensus structure elucidation on the basis of GC/EI-MS, structure generation, and calculated properties for unknown compounds. Candidate structures were generated using the molecular formula and substructure information obtained from GC/EI-MS spectra. Calculated properties were then used to score candidates according to a consensus approach, rather than filtering or exclusion. Two mass spectral match calculations (MOLGEN-MS and MetFrag), retention behavior (Lee retention index/boiling point correlation, NIST Kovat’s retention index), octanol–water partitioning behavior (log K_ow), and finally steric energy calculations were used to select candidates. A simple consensus scoring function was developed and tested on two unknown spectra detected in a mutagenic subfraction of a water sample from the Elbe River using GC/EI-MS. The top candidates proposed using the consensus scoring technique were purchased and confirmed analytically using GC/EI-MS and LC/MS/MS. Although the compounds identified were not responsible for the sample mutagenicity, the structure-generation-based identification for GC/EI-MS using calculated properties and consensus scoring was demonstrated to be applicable to real-world unknowns and suggests that the development of a similar strategy for multidimensional high-resolution MS could improve the outcomes of environmental and metabolomics studies.

Organische Mikroverunreinigungen sind in Gewässern generell unerwünscht. Sie können Gewässerorganismen bereits in sehr niedrigen Konzentrationen schädigen. Bisherige Analysetechniken mussten sich technikbedingt auf den Nachweis weniger, bekannter Substanzen beschränken. Mit neuen Methoden lassen sich auch unentdeckte Stoffe erfassen.

Even at very low concentrations, organic micropollutants in natural waters can be harmful to aquatic organisms. Owing to technical constraints, analytical methods have so far been confined to the detection of a relatively small number of known compounds. With new methods, previously undetected substances can also be identified.

We investigated the mechanisms and isotope effects associated with the N-dealkylation and N-atom oxidation of substituted N-methyl- and N,N-dimethylanilines to identify isotope fractionation trends for the assessment of oxidations of aromatic N-alkyl moieties by compound-specific isotope analysis (CSIA). In laboratory batch model systems, we determined the C, H, and N isotope enrichment factors for the oxidation by MnO₂ and horseradish peroxidase (HRP), derived apparent ¹³C-, ²H-, and ¹⁵N-kinetic isotope effects (AKIEs), and characterized reaction products. The N-atom oxidation pathway leading to radical coupling products typically exhibited inverse ¹⁵N-AKIEs (up to 0.991) and only minor ¹³C- and ²H-AKIEs. Oxidative N-dealkylation, in contrast, was subject to large normal ¹³C- and ²H-AKIEs (up to 1.019 and 3.1, respectively) and small ¹⁵N-AKIEs. Subtle changes of the compound’s electronic properties due to different types of aromatic and/or N-alkyl substituents resulted in changes of reaction mechanisms, rate-limiting step(s), and thus isotope fractionation trends. The complex sequence of electron and proton transfers during the oxidative transformation of substituted aromatic N-alkyl amines suggests highly compound- and mechanism-dependent isotope effects precluding extrapolations to other organic micropollutants reacting along the same degradation pathways.

Der Kanton Bern startete 2008 das Projekt «Gewässerzustand im Aaretal» (GZA), um Fragen zum Fischrückgang zu klären und Beeinträchtigungen der Wasserqualität durch Schadstoffe wie Pestizide zu untersuchen. Die Ergebnisse des Pestizidmonitorings entsprechen für die meisten landwirtschaftlichen Pestizide den Erwartungen: Die Konzentrationen steigen während Abflusereignissen an. Allerdings zeigte sich auch, dass Biozide und Pestizide aus urbanen Quellen höhere Konzentrationsspitzen verursachen.

Backgrounds. Perfluorinated compounds (PFCs) have drawn much attention due to their environmental persistence, ubiquitous existence, and bioaccumulation potential. Wastewater treatment plants (WWTPs) are fundamental utilities in cities, playing an important role in preventing water pollution by lowering pollution load in waste waters. However, some of the emerging organic pollutants, like PFCs cannot be efficiently removed by traditional biological technologies in WWTPs, and some even increase in effluents compared to influents due to the incomplete degradation of precursors. Hence, WWTPs are considered to be a main point source in cities for PFCs that enter the aquatic environment. However, the mass flow of PFCs from WWTPs has seldom been analyzed for a whole city. Hence, in the present study, 11 PFCs including series of perfluoroalkyl carboxylic acids (PFCAs, C4–C12) and two perfluoroalkyl sulfonates (PFASs, C6 and C8) were measured in WWTP influents and effluents and sludge samples from six municipal WWTPs in Tianjin, China. Generation and dissipation of the target PFCs during wastewater treatment process and their mass flow in effluents were discussed.
Results. All the target PFCs were detected in the six WWTPs, and the total PFC concentration in different WWTPs was highly influenced by the population density and commercial activities of the corresponding catchments. Perfluorooctanoic acid (PFOA) was the predominant PFC in water phase, with concentrations ranging from 20 to 170 ng/L in influents and from 30 to 145 ng/L in effluents. Concentrations of perfluoroalkyl sulfonates decreased substantially in the effluent compared to the influent, which could be attributed to the sorption onto sludge, whereas concentrations of PFOA and some other PFCAs increased in the effluent in some WWTPs due to their weaker sorption onto solids and the incomplete degradation of precursors. Perfluorooctane sulfonic acid (PFOS) was the predominant PFC in sludge samples followed by PFOA, and their concentrations ranged from 42 to 169 g/kg and from 12 to 68 g/kg, respectively. Sludge-wastewater distribution coefficients (log K_d) ranged from 0.62 to 3.87 L/kg, increasing with carbon chain length of the homologues. The mass flow of some PFCs in the effluent was calculated, and the total mass flow from all the six municipal WWTPs in Tianjin was 26, 47, and 3.5 kg/year for perfluorohexanoic acid, PFOA, and PFOS, respectively.

We generated a new set of reference geometries of small radicals using experimental equilibrium structures, as well as a benchmark-quality coupled cluster additivity scheme including up to quadruples excitations (CCSDTQ). Using these geometries and a set of experimental vibrational frequencies of open shell diatomics, we evaluated the performance of various coupled cluster methods based mainly on unrestricted references, using Dunning basis sets both with and without core correlation. Contrary to previous results, we found that UCCSD(T) and ROCCSD(T) perform equally well for geometries, better than CCSD, and close to their performances for closed shell systems. No improvement over CCSD(T) was achieved by using a Brueckner reference (BD(T)) or full triples (CCSDT). For frequencies, ROCCSD(T), BD(T), and CCSDT improve upon UCCSD(T), especially for the troublesome NO and CO+ cases. EOMIP-CCSD yields geometries and harmonic frequencies similar to CCSD, and qualitatively correct anharmonic (VPT2) contributions in all cases, like the RO–CC methods. The double hybrid DFT functional B2PLYP-D yields geometries and frequencies of similar quality to that of CCSD but at a much reduced cost. The meta hybrid functionals M06-2X, M06-HF, and BMK perform worse than CCSD, and worse than B3LYP, on average.

Electrolysis of iohexol, an iodinated X-ray contrast medium, on synthetic boron-doped diamond (BDD) thin film electrodes was investigated for the first time. Kinetic experiments of electrochemical oxidation resulted in complete elimination of iohexol. Data from the kinetic experiments were compared against estimates by the kinetic model proposed previously by Comninellis et al. Excellent agreement between the experimental results and the kinetic model was observed. The results suggest that electrolysis on BDD electrodes is a promising method for the elimination of iohexol from wastewater.

Passive samplers for polar organic compounds often use a polyethersulfone (PES) membrane to retain the particulate sorbent material (e.g., in a POCIS; polar organic chemical integrative sampler) or to reduce the sampling rate and thus extend the kinetic regime (e.g., in a Chemcatcher). The transport kinetics over the PES membrane are evaluated here in a short-term (6 days) and a long-term (32 days) experiment with POCIS and Chemcatchers. Passive samplers were placed in a channel with flowing river water that was spiked with 22 organic chemicals including pharmaceuticals, pesticides and biocides; with logK_ow (logarithmic octanol–water partitioning coefficient) values between −2.6 and 3.8. Samplers were removed at intervals and membranes and sorbent material were extracted and analyzed with LC-MS/MS. Uptake kinetics of the compounds fell between two extremes: (1) charged chemicals and chemicals of low hydrophobicity did not accumulate in PES and rapidly transferred to the sorbent (e.g., diclofenac) and (2) more hydrophobic chemicals accumulated strongly in the PES and appeared in the sorbent after a lag-phase (e.g., diazinon and diuron). Sorption kinetics were modeled with a three-compartment first-order kinetic model to determine uptake and elimination rate constants and partitioning coefficients. Water PES partitioning coefficients fitted with the model correlated well with experimentally determined values and logK_ow. Sampling rates of Chemcatcher (0.02–0.10 L/d) and POCIS (0.02–0.30 L/d) showed similar patterns and correlated well. Thus the samplers are interchangeable in practical applications. Longer lag-phases may pose problems when calculating time-weighted average aqueous concentrations for short passive sampling windows and for a correct integrative sampling of fluctuating concentrations.

Temporally resolved environmental risk assessment of fluctuating concentrations of micropollutants is presented. We separated the prediction of toxicity over time from the extrapolation from one to many species and from acute to sublethal effects. A toxicokinetic–toxicodynamic (TKTD) model predicted toxicity caused by fluctuating concentrations of diazinon, measured by time-resolved sampling over 108 days from three locations in a stream network, representing urban, agricultural and mixed land use. We calculated extrapolation factors to quantify variation in toxicity among species and effect types based on available toxicity data, while correcting for different test durations with the TKTD model. Sampling from the distribution of extrapolation factors and prediction of time-resolved toxicity with the TKTD model facilitated subsequent calculation of the risk of undesired toxic events. Approximately one-fifth of aquatic organisms were at risk and fluctuating concentrations were more toxic than their averages. Contribution of urban and agricultural sources of diazinon to the overall risk varied. Thus using fixed concentrations as water quality criteria appears overly simplistic because it ignores the temporal dimension of toxicity. However, the improved prediction of toxicity for fluctuating concentrations may be small compared to uncertainty due to limited diversity of toxicity data to base the extrapolation factors on.

Within the framework of a model comparison, twelve different models were used to forecast water flows in the artificial catchment area of the Chicken Creek, which was created in 2005 in an open-cast mining area in the Lusatia region. To check whether it is possible to predict water flows without actually knowing measured flows, the model comparison was designed in several steps. First, modelers were only given basic data on soil texture, topography, plant coverage, climate and initial groundwater levels. Data on soil humidity and flow were not disclosed, so that it would be possible to compare models and modelers and their ability to forecast in cases where only limited data are available. In further steps, a site inspection took place, followed by a workshop, and information on further characteristics of the area was given. While model results were very different, above all in the first stage of the model application, they converged after the site inspection. Whereas in the beginning, simulation results of almost all models were dominated by subterranean flow components, the understanding of the processes changed after the site inspection, e.g. after inspecting erosion gullies and incrusted soil surfaces. This led to greater changes in model results than the provision of additional data at a later stage, which were mainly used to double-check parameterization and starting conditions. The results of the model comparison suggest that the decisions of the modelers were the main reason for the initial differences in model results. Modelers decided for themselves how to use available data, how to determine model parameters and starting conditions in the light of their respective modeling experience, while there was hardly any difference between most of the model concepts.

Ten conceptually different models were applied to predict the discharge from the 6 ha artificial Chicken Creek catchment in Lausatia, North-East Germany, which has been created in an open cast mining area. The study consisted of three steps to make a model intercomparison with the objective of a priori prediction of the water balance and the discharge dynamics. In order to test the ability of each model and modeller to predict water flows in an ungauged catchment, only soil texture, topography, vegetation coverage and climate data were provided to the modellers in the first step. Hydrological data on discharge, soil moisture and groundwater levels were withheld. This enabled us to assess the predictive capabilities of the models under sparse data conditions. The predicted components of the water balance varied in a wide range. None of the model simulations came close to the observed water balance for the entire 3-year study period. Discharge was mainly predicted as subsurface flow with little surface runoff. In reality, surface runoff was a major flow component despite the fairly coarse soil texture. In the second step, additional process knowledge was gained during a joint field visit. The occurence of gully erosion and surface crusting was detected and implemented into the models. Consequently, model predictions changed considerably. The previous simulations dominated by subsurface flow changed to surface flow-dominated simulations. Additional data, provided in the third step, mainly confirmed the parameterisations and assisted in a better definition of initial conditions and subsurface storage. The comparison indicates that, in addition to model philosophy, the personal judgement of the modellers was a major source of the differences in the model results. The model parameterisation and choice of initial conditions depended on the modeller's judgement and were therefore a result of the modellers' experience in terms of model types and case studies.

Introduction. Illicit drug use is a largely hidden phenomenon, and population measures are notoriously problematic. Reliable and valid data for local, regional, and national public health and other interventions are needed.
Methods. To address this information, we examined temporal trends within and across weeks in methamphetamine (MA) in a single location in order to inform a sampling plan for understanding long-term trends in MA use based on sampling raw influent to wastewater treatment plants. The measured concentrations in the wastewater are used to estimate the total mass of MA consumed rather than the number of doses due to the uncertainty surrounding methamphetamine purity, mass of MA per dose, and the number of doses used per day.
Results. Results from a region with high levels of MA use indicate that MA levels do not differ significantly between weekdays and weekends (p=0.1), consistent with a predominately regular, daily use pattern use. The potential contribution of legal sales of D- and L-MA to the mass of MA consumed within the community was estimated to range from 3–8%. Limitations and uncertainties associated with estimating the mass of MA consumption include small contributions of prescription and over-the-counter drugs that are metabolized to MA as well as measurement and sampling variability.

Degradation of chlorinated organic contaminants by natural and engineered reductive dechlorination reactions can occur via numerous biotic and abiotic transformation pathways giving rise to either benign or more toxic products. To assess whether dechlorination processes may lead to significant detoxification (a) the thermodynamic feasibility of a reaction, (b) rates of transformation, and (c) product formation routes need to be understood. To this end, fundamental knowledge of chlorohydrocarbon (CHC) reaction mechanisms is essential. We review insight from reaction thermodynamics, structure-reactivity relationships, and applications of radical and carbene traps, as well as of synthetic probe molecules. We summarize the state-of-knowledge about intermediates and reductive dechlorination pathways of vicinal and geminal haloalkanes, as well as of chlorinated ethenes. Transformation conditions are identified under which problematic products may be avoided. In an outlook, we discuss the potential of stable carbon and chlorine isotope fractionation to identify initial transformation mechanisms, competing transformation pathways, and common branching points.

In this paper, we evaluated the ecotoxicological potential of the 100 pharmaceuticals expected to occur in highest quantities in the wastewater of a general hospital and a psychiatric center in Switzerland. We related the toxicity data to predicted concentrations in different wastewater streams to assess the overall risk potential for different scenarios, including conventional biological pretreatment in the hospital and urine source separation. The concentrations in wastewater were estimated with pharmaceutical usage information provided by the hospitals and literature data on human excretion into feces and urine. Environmental concentrations in the effluents of the exposure scenarios were predicted by estimating dilution in sewers and with literature data on elimination during wastewater treatment. Effect assessment was performed using quantitative structure-activity relationships because experimental ecotoxicity data were only available for less than 20% of the 100 pharmaceuticals with expected highest loads. As many pharmaceuticals are acids or bases, a correction for the speciation was implemented in the toxicity prediction model.
The lists of Top-100 pharmaceuticals were distinctly different between the two hospital types with only 37 pharmaceuticals overlapping in both datasets. 31 Pharmaceuticals in the general hospital and 42 pharmaceuticals in the psychiatric center had a risk quotient above 0.01 and thus contributed to the mixture risk quotient. However, together they constituted only 14% (hospital) and 30% (psychiatry) of the load of pharmaceuticals. Hence, medical consumption data alone are insufficient predictors of environmental risk. The risk quotients were dominated by amiodarone, ritonavir, clotrimazole, and diclofenac. Only diclofenac is well researched in ecotoxicology, while amiodarone, ritonavir, and clotrimazole have no or very limited experimental fate or toxicity data available. The presented computational analysis thus helps setting priorities for further testing.
Separate treatment of hospital wastewater would reduce the pharmaceutical load of wastewater treatment plants, and the risk from the newly identified priority pharmaceuticals. However, because high-risk pharmaceuticals are excreted mainly with feces, urine source separation is not a viable option for reducing the risk potential from hospital wastewater, while a sorption step could be beneficial.

When micropollutants degrade in the environment, they may form persistent and toxic transformation products, which should be accounted for in the environmental risk assessment of the parent compounds. Transformation products have become a topic of interest not only with regard to their formation in the environment, but also during advanced water treatment processes, where disinfection byproducts can form from benign precursors. In addition, environmental risk assessment of human and veterinary pharmaceuticals requires inclusion of human metabolites as most pharmaceuticals are not excreted into wastewater in their original form, but are extensively metabolized. All three areas have developed their independent approaches to assess the risk associated with transformation product formation including hazard identification, exposure assessment, hazard assessment including dose−response characterization, and risk characterization. This review provides an overview and defines a link among those areas, emphasizing commonalities and encouraging a common approach. We distinguish among approaches to assess transformation products of individual pollutants that are undergoing a particular transformation process, e.g., biotransformation or (photo)oxidation, and approaches with the goal of prioritizing transformation products in terms of their contribution to environmental risk. We classify existing approaches for transformation product assessment in degradation studies as exposure- or effect-driven. In the exposure-driven approach, transformation products are identified and quantified by chemical analysis followed by effect assessment. In the effect-driven approach, a reaction mixture undergoes toxicity testing. If the decrease in toxicity parallels the decrease of parent compound concentration, the transformation products are considered to be irrelevant, and only when toxicity increases or the decrease is not proportional to the parent compound concentration are the TPs identified. For prioritization of transformation products in terms of their contribution to overall environmental risk, we integrate existing research into a coherent model-based, risk-driven framework. In the proposed framework, read-across from data of the parent compound to the transformation products is emphasized, but limitations to this approach are also discussed. Most prominently, we demonstrate how effect data for parent compounds can be used in combination with analysis of toxicophore structures and bioconcentration potential to facilitate transformation product effect assessment.

A Study of their Occurrence in and Impact on Bodies of Water. A measurement and model-based procedure has been developed in the "KoMet" project to evaluate systematically the significance of transformation products from micropollutants for the water quality of water bodies in Switzerland. For the 62 pesticides, biocides and pharmaceutical substances examined, 51 trans-formation products were classified as exposure-relevant on the basis of their occurrence in a range of water samples. While biological transformation typically reduces the ecotoxicological effects overall, six transformation products from wastewater compounds were identified whose effect on aquatic organisms should be further elucidated.

Input into streams due to erosion and runoff ofpesticides and nutrients from agricultural fieldspose a threat to our water bodies. Field studiesindicate that these losses originate from limitedparts of a given catchment. This holds especiallyfor fine sediments, pesticides and phosphorus,which are mainly transported by fast flowprocesses that are generated only on certainlocations. These critical source areas (CSAs) seemto cover in many cases about 20 % of the totalarea. The best empirical evidence for CSAs existsfor erosion, where losses can be observed afteran erosive event. For P losses, the concept is alsoused fairly wide-spread in many countriesoutside Switzerland. However, the empirical database supporting the concept is rather limited.Even less data exist for pesticides. For nitrogen,the CSA concept is not appropriate. For identifyingCSA in space, several tools are available. Wehave tested some of them on four different testfarms. The risk areas for erosion agreed wellwith the field experience of the local farmers.The risk areas for runoff and erosion did notoverlap in many situations. Identifying risk areasin Switzerland is in many situations severelyhampered by the coarse soil maps that areavailable.

Input into streams due to erosion and runoff ofpesticides and nutrients from agricultural fieldspose a threat to our water bodies. Field studiesindicate that these losses originate from limitedparts of a given catchment. This holds especiallyfor fine sediments, pesticides and phosphorus,which are mainly transported by fast flowprocesses that are generated only on certainlocations. These critical source areas (CSAs) seemto cover in many cases about 20 % of the totalarea. The best empirical evidence for CSAs existsfor erosion, where losses can be observed afteran erosive event. For P losses, the concept is alsoused fairly wide-spread in many countriesoutside Switzerland. However, the empirical database supporting the concept is rather limited.Even less data exist for pesticides. For nitrogen,the CSA concept is not appropriate. For identifyingCSA in space, several tools are available. Wehave tested some of them on four different testfarms. The risk areas for erosion agreed wellwith the field experience of the local farmers.The risk areas for runoff and erosion did notoverlap in many situations. Identifying risk areasin Switzerland is in many situations severelyhampered by the coarse soil maps that areavailable.

A distributed hydrological model was used to simulate the distribution of fast runoff formation as a proxy for critical source areas for herbicide pollution in a small agricultural catchment in Switzerland. We tested to what degree predictions based on prior knowledge without local measurements could be improved upon relying on observed discharge. This learning process consisted of five steps: For the prior prediction (step 1), knowledge of the model parameters was coarse and predictions were fairly uncertain. In the second step, discharge data were used to update the prior parameter distribution. Effects of uncertainty in input data and model structure were accounted for by an autoregressive error model. This step decreased the width of the marginal distributions of parameters describing the lower boundary (percolation rates) but hardly affected soil hydraulic parameters. Residual analysis (step 3) revealed model structure deficits. We modified the model, and in the subsequent Bayesian updating (step 4) the widths of the posterior marginal distributions were reduced for most parameters compared to those of the prior. This incremental procedure led to a strong reduction in the uncertainty of the spatial prediction. Thus, despite only using spatially integrated data (discharge), the spatially distributed effect of the improved model structure can be expected to improve the spatially distributed predictions also. The fifth step consisted of a test with independent spatial data on herbicide losses and revealed ambiguous results. The comparison depended critically on the ratio of event to preevent water that was discharged. This ratio cannot be estimated from hydrological data only. The results demonstrate that the value of local data is strongly dependent on a correct model structure. An iterative procedure of Bayesian updating, model testing, and model modification is suggested.

Iron-bearing clay minerals are ubiquitous in the environment and have been shown to play important roles in several biogeochemical processes. Previous efforts to characterize the Fe²⁺–Fe³⁺ redox couple in clay minerals using electrochemical techniques have been limited by experimental difficulties due to inadequate reactivity between clay minerals and electrodes. The current work overcomes this limitation by utilizing organic electron transfer mediators that rapidly transfer electrons with both the Fe-bearing clay minerals and electrodes. Here, an Fe-rich source clay mineral (ferruginous smectite, SWa-1) is examined with respect to what fraction of structural Fe participates in oxidation/reduction reactions and the relationship between bulk Fe²⁺/Fe³⁺ ratios to the reduction potential (E_h).

Sorption of aqueous Fe²⁺ at the Fe oxide-water interface has traditionally been viewed in the classic framework of sorption at static oxide surface sites as formulated in surface complexation models (SCMs). Significant experimental and theoretical evidence has accumulated, however, to indicate that the reaction of aqueous Fe²⁺ with Fe³⁺ oxides is much more complex and is comprised of sorption, electron transfer, conduction, dissolution, and, in some cases, atom exchange and/or transformation to secondary minerals. Here, we provide a brief historical review of Fe²⁺ sorption on Fe oxides and present a revised conceptual model based on the semiconducting properties of Fe oxides that incorporates recent experimental evidence for Fe²⁺ - Fe³⁺ _oxide electron transfer, bulk electron conduction, and Fe atom exchange. We also discuss the implications of this revised conceptual model for important environmental processes, such as trace metal cycling and contaminant fate.

Micropollutants from municipal wastewater generally influence the water quality of rivers with a high amount of municipal wastewater. They might also affect water bodies that have an important function as drinking water resources. For micropollutants from municipal wastewater, we distinguish four different input pathways into surface waters: (1) Input with treated wastewater through wastewater treatment plants; (2) input with untreated wastewater through sewer overflows if the capacity of the sewer system or the wastewater treatment plant is exceeded; (3) input through leaks in the sewer network or wrongly connected sewers; and (4) input of polluted rainwater from roofs and sealed areas through rainwater channels. Because many micropollutants are not considerably degraded in conventional wastewater treatment plants, the major part of them enters the surface waters with the treated wastewater effluents of wastewater treatment plants. Using a prioritization procedure, 47 Swiss-specific micropollutants were identified out of 250 candidate substances. The selected Swiss-specific micropollutants are representative for the contamination caused through micropollutants from municipal wastewater. Beside the Swiss-specific micropollutants, locally appearing chemicals from commerce and industry might be of importance. This has to be considered depending on the particular situation. For the ascertainment of micropollutants in surface waters, we suggest a procedure in two steps: (1.) Identification of potentially contaminated waterbodies; and 2.) detailed assessment of the potentially contaminated waterbodies. In the first step, mainly estimations are used, such as the estimation of the wastewater fraction in the waterbodies. In the second step, for a more detailed assessment, different sampling strategies and a selection of the Swissspecific micropollutants for chemical analysis is suggested. The proposed sampling strategies focus mainly on the determination of the basic contamnation through continuously through municipal wastewater entering substances. For the evaluation of the water quality, the measured data are compared to ecotoxicologically based quality criteria. Therefore, based on the technical guidance document for environmental quality standards of the EU, quality criteria were derived. For the assessment of the water quality, predicted environmental concentrations (PEC) are compared to annual average environmental quality standards (AA-EQS). Based on the Modular Stepwise Procedure (MSP, MSK) of the Federal Office for Environment (FOEN), the water quality is divided into five classes: excellent / good / moderate / unsatisfying / poor. Based on the presented assessment concept, further investigations can be prioritized, and reduction strategies and measures for the reduction of micropollutants from municipal wastewater can be evaluated.

Micropollutants from municipal wastewater generally influence the water quality of rivers with a high amount of municipal wastewater. They might also affect water bodies that have an important function as drinking water resources. For micropollutants from municipal wastewater, we distinguish four different input pathways into surface waters: (1) Input with treated wastewater through wastewater treatment plants; (2) input with untreated wastewater through sewer overflows if the capacity of the sewer system or the wastewater treatment plant is exceeded; (3) input through leaks in the sewer network or wrongly connected sewers; and (4) input of polluted rainwater from roofs and sealed areas through rainwater channels. Because many micropollutants are not considerably degraded in conventional wastewater treatment plants, the major part of them enters the surface waters with the treated wastewater effluents of wastewater treatment plants.Using a prioritization procedure, 47 Swiss-specific micropollutants were identified out of 250 candidate substances. The selected Swiss-specific micropollutants are representative for the contamination caused through micropollutants from municipal wastewater. Beside the Swiss-specific micropollutants, locally appearing chemicals from commerce and industry might be of importance. This has to be considered depending on the particular situation. For the ascertainment of micropollutants in surface waters, we suggest a procedure in two steps: (1.) Identification of potentially contaminated waterbodies; and (2.) detailed assessment of the potentially contaminated waterbodies. In the first step, mainly estimations are used, such as the estimation of the wastewater fraction in the waterbodies. In the second step, for a more detailed assessment, different sampling strategies and a selection of the Swiss-specific micropollutants for chemical analysis is suggested. The proposed sampling strategies focus mainly on the determination of the basic contamnation through continuously through municipal wastewater entering substances. For the evaluation of the water quality, the measured data are compared to ecotoxicologically based quality criteria. Therefore, based on the technical guidance document for environmental quality standards of the EU, quality criteria were derived. For the assessment of the water quality, predicted environmental concentrations (PEC) are compared to annual average environmental quality standards (AA-EQS). Based on the Modular Stepwise Procedure (MSK) of the federal office for environment (FOEN), the water quality is divided into five classes: excellent / good / moderate / unsatisfying / poor. Based on the presented assessment concept, further investigations can be prioritized, and reduction strategies and measures for the reduction of micropollutants from municipal wastewater can be evaluated.

The analysis of variations in stable isotope composition is becoming an essential approach for evaluating enzymatic and abiotic reactions of organic contaminants in soils and aquatic systems. Different, sometimes complementary analytical techniques are currently used and developed to determine stable isotope ratios in individual organic compounds. Anticipating an increasing demand for compound-specific isotope analysis, this survey compiles information for choosing the most promising analytical approach to an isotope-related problem. To this end, we review the principles of instrumentation for compound-specific isotope analysis and show how they can be exploited to assess contaminant transformation processes. Using chlorinated solvents and triazine herbicides as illustrative examples, we discuss how the isotope-sensitive techniques impact the investigation of stable isotope fractionation in environmental chemistry and microbiology.

The quantitative description of enzymatic or abiotic transformations of man-made organic micropollutants in rivers, lakes, and groundwaters is one of the major challenges associated with the risk assessment of water resource contamination. Compound-specific isotope analysis enables one to identify (bio)degradation pathways based on changes in the contaminants’ stable isotope ratios even if multiple reactive and non-reactive processes cause concentrations to decrease. Here, we investigated how the magnitude and variability of isotope fractionation in some priority pollutants is determined by the kinetics and mechanisms of important enzymatic and abiotic redox reactions. For nitroaromatic compounds and substituted anilines, we illustrate that competing transformation pathways can be assessed via trends of N and C isotope signatures.

Anaerobic degradation processes play an important role in contaminated aquifers. To indicate active biodegradation processes signature metabolites can be used. In this study field samples from a high-resolution multilevel well in a tar oil-contaminated, anoxic aquifer were analyzed for metabolites by liquid chromatography-tandem mass spectrometry and time-of-flight mass spectrometry. In addition to already known specific degradation products of toluene, xylenes, and naphthalenes, the seldom reported degradation products benzothiophenemethylsuccinic acid (BTMS), benzofuranmethylsuccinic acid (BFMS), methylnaphthyl-2-methylsuccinic acid (MNMS), and acenaphthene-5-carboxylic acid (AC) could be identified (BFMS, AC) and tentatively identified (BTMS, MNMS). The occurrence of BTMS and BFMS clearly show that the fumarate addition pathway, known for toluene and methylnaphthalene, is also important for the anaerobic degradation of heterocyclic contaminants in aquifers. The molar concentration ratios of metabolites and their related parent compounds differ over a wide range which shows that there is no simple and consistent quantitative relation. However, generally higher ratios were found for the more recalcitrant compounds, which are putatively cometabolically degraded (e.g., 2-carboxybenzothiophene and acenaphthene-5-carboxylic acid), indicating an accumulation of these metabolites. Vertical concentration profiles of benzylsuccinic acid (BS) and methyl-benzylsuccinic acid (MBS) showed distinct peaks at the fringes of the toluene and xylene plume indicating hot spots of biodegradation activity and supporting the plume fringe concept. However, there are some compounds which show a different vertical distribution with the most prominent concentrations where also the precursor compounds peaked.

Over 1.5 years continuous piloting of a municipal wastewater plant upgraded with a double membrane system (ca. 0.6 m³ d⁻¹ of product water produced) have demonstrated the feasibility of achieving high water quality with a water yield of 90% by combining a membrane bioreactor (MBR) with a submerged ultrafiltration membrane followed by a reverse osmosis membrane (RO). The novelty of the proposed treatment scheme consists of the appropriate conditioning of MBR effluent prior to the RO and in recycling the RO concentrates back to the biological unit.
All the 15 pharmaceuticals measured in the influent municipal sewage were retained below 100 ng L⁻¹, a proposed quality parameter, and mostly below detection limits of 10 ng L⁻¹. The mass balance of the micropollutants shows that these are either degraded or discharged with the excess concentrate, while only minor quantities were found in the excess sludge. The micropollutant load in the concentrate can be significantly reduced by ozonation. A low treated water salinity (<10 mM inorganic salts; 280 ± 70 μS cm⁻¹) also confirms that the resulting product has a high water quality.
Solids precipitation and inorganic scaling are effectively mitigated by lowering the pH in the RO feed water with CO₂ conditioning, while the concentrate from the RO is recycled to the biological unit where CO₂ is stripped by aeration. This causes precipitation to occur in the bioreactor bulk, where it is much less of a process issue. SiO₂ is the sole exception. Equilibrium modeling of precipitation reactions confirms the effectiveness of this scaling-mitigation approach for CaCO₃ precipitation, calcium phosphate and sulfate minerals.

Micropollutants (MPs) from municipal wastewater are frequently detected in surface waters and occur in ecotoxicologically relevant concentrations. Therefore a broadly accepted method for the assessment of MPs is needed. Here we propose a procedure for the assessment of MPs from municipal wastewater. The method suggested comprises (1) an approach for the identification of potentially polluted sites, (2) a compilation of a substance list with relevant MPs, (3) (eco)toxicologically based quality criteria, (4) a sampling strategy that considers the input-dynamics of chemicals and (5) a scheme to rate water quality with respect to MP contamination. In the proposed concept the assessment focuses upon those substances found repeatedly in municipal wastewaters (continuous inputs). Additionally, we explain how the Environmental Quality Standard (EQS) proposals were derived in accordance with the Water Framework Directive (WFD), and the currently developed Technical Guidance Document for EQS (TGD for EQS). Based on the proposed EQS, we provide a Swiss-wide risk assessment for 6 selected MPs.

Transformation products (TPs) of chemicals released to soil, for example, pesticides, are regularly detected in surface and groundwater with some TPs even dominating observed pesticide levels. Given the large number of TPs potentially formed in the environment, straightforward prioritization methods based on available data and simple, evaluative models are required to identify TPs with a high aquatic exposure potential. While different such methods exist, none of them has so far been systematically evaluated against field data. Using a dynamic multimedia, multispecies model for TP prioritization, we compared the predicted relative surface water exposure potential of pesticides and their TPs with experimental data for 16 pesticides and 46 TPs measured in a small river draining a Swiss agricultural catchment. Twenty TPs were determined quantitatively using solid-phase extraction liquid chromatography mass spectrometry (SPE-LC-MS/MS), whereas the remaining 26 TPs could only be detected qualitatively because of the lack of analytical reference standards. Accordingly, the two sets of TPs were used for quantitative and qualitative model evaluation, respectively. Quantitative comparison of predicted with measured surface water exposure ratios for 20 pairs of TPs and parent pesticides indicated agreement within a factor of 10, except for chloridazon-desphenyl and chloridazon-methyl-desphenyl. The latter two TPs were found to be present in elevated concentrations during baseflow conditions and in groundwater samples across Switzerland, pointing toward high concentrations in exfiltrating groundwater. A simple leaching relationship was shown to qualitatively agree with the observed baseflow concentrations and to thus be useful in identifying TPs for which the simple prioritization model might underestimate actual surface water concentrations. Application of the model to the 26 qualitatively analyzed TPs showed that most of those TPs categorized as exhibiting a high aquatic exposure potential could be confirmed to be present in the majority of water samples investigated. On the basis of these results, we propose a generally applicable, model-based approach to identify those TPs of soil-applied organic contaminants that exhibit a high aquatic exposure potential to prioritize them for higher-tier, experimental investigations.

The organothiophosphate diazinon inhibits the target site acetylcholinesterase only after activation to its metabolite diazoxon. Commonly, the toxicity of xenobiotics toward aquatic organisms is expressed as a function of the external concentration and the resulting effect on the individual level after fixed exposure times. This approach does not account for the time dependency of internal processes such as uptake, metabolism, and interaction of the toxicant with the target site. Here, we develop a mechanistic toxicodynamic model for Daphnia magna and diazoxon, which accounts for the inhibition of the internal target site acetylcholinesterase and its link to the observable effect, immobilization, and mortality. The model was parametrized by experiments performed in vitro with the active metabolite diazoxon on enzyme extracts and in vivo with the parent compound diazinon. The mechanism of acetylcholinesterase inhibition was shown to occur irreversibly in two steps via formation of a reversible enzyme–inhibitor complex. The corresponding kinetic parameters revealed a very high sensitivity of acetylcholinesterase from D. magna toward diazoxon, which corresponds well with the high toxicity of diazinon toward this species. Recovery of enzyme activity but no recovery from immobilization was observed after in vivo exposure to diazinon. The toxicodynamic model combining all in vitro and in vivo parameters was successfully applied to describe the time course of immobilization in dependence of acetylcholinesterase activity during exposure to diazinon. The threshold value for enzyme activity below which immobilization set in amounted to 40% of the control activity. Furthermore, the model enabled the prediction of the time-dependent diazoxon concentration directly present at the target site.

A toxicokinetic model for Daphnia magna, which simulates the internal concentration of the insecticide diazinon, its detoxification product 2-isopropyl-6-methyl-4-pyrimidinol, and its active metabolite diazoxon, is presented. During in vivo exposure to diazinon with and without inhibition of cytochrome P450 by piperonyl butoxide, the parent compound as well as its metabolites were quantified with high-performance liquid chromatography–tandem mass spectrometry (LC-MS/MS) in extracts of D. magna. Rate constants of all relevant toxicokinetic steps were obtained by modeling the time course of the internal concentrations with a multicomponent first-order kinetics model. When cytochrome P450 was inhibited, the kinetic bioconcentration factor (BCF) of diazinon increased from 17.8 to 51.0 mL·g_ww^–1. This clearly indicates that diazinon is biotransformed to a high degree by cytochrome P450 in D. magna. The dominant elimination step of diazinon was shown to be its oxidative dearylation to pyrimidinol (62% of total elimination) with a corresponding rate constant of 0.16 h^–1. In contrast, oxidative activation to diazoxon with a rate constant of 0.02 h^–1 amounted to only 8% of the total elimination. During exposure to diazinon, the active metabolite diazoxon could be detected only in very low concentrations (approximately 0.5% of the parent compound), presumably due to a very fast reaction with the target site acetylcholinesterase. During the exposure experiments (no feeding of daphnids), an exponential decline of the lipid content in D. magna with a first-order rate constant of 0.013 h^–1 was observed. For short exposure times (≤24 h), this had only a minor influence on the determined TK parameters. Such a TK model containing detailed biotransformation processes is an important tool for estimation of the toxic potential of chemicals, particularly, when active metabolites are formed inside an organism.

Point-source measures have been suggested to decrease pharmaceuticals in water bodies. We analyzed 68 and 50 alternatives, respectively, for a typical Swiss general and psychiatric hospital to decrease pharmaceutical discharge. Technical alternatives included reverse osmosis, ozonation, and activated carbon; organizational alternatives included urine separation. To handle this complex decision, we used Multiple-Criteria Decision Analysis (MCDA) and combined expert predictions (e.g., costs, pharmaceutical mass flows, ecotoxicological risk, pathogen removal) with subjective preference-valuations from 26 stakeholders (authorities, hospital-internal actors, experts). The general hospital contributed ca. 38% to the total pharmaceutical load at the wastewater treatment plant, the psychiatry contributed 5%. For the general hospital, alternatives removing all pharmaceuticals (especially reverse osmosis, or vacuum-toilets and incineration), performed systematically better than the status quo or urine separation, despite higher costs. They now require closer scrutiny. To remove X-ray contrast agents, introducing roadbags is promising. For the psychiatry with a lower pharmaceutical load, costs were more critical. Stakeholder feedback concerning MCDA was very positive, especially because the results were robust across different stakeholder-types. Our MCDA results provide insight into an important water protection issue: implementing measures to decrease pharmaceuticals will likely meet acceptance. Hospital point-sources merit consideration if the trade-off between costs and pharmaceutical removal is reasonable.

As one of the largest European drinking water reservoirs, Lake Constance supplies about 4.5 million people with superior quality drinking water. The monitoring of the water quality is of major interest. In this study, a new dataset of organic micropollutants was determined and evaluated for Lake Constance and its tributaries. A three step procedure was established, to investigate this issue: (1) screening micropollutants in selected samples using the latest analytical technique, (2) modelling the occurrence of contamination of leading compounds in the lake and in its catchment, (3) evaluating the results based on national and international quality standards.

Anthropogenic perfluorinated compounds (PFCs), especially the perfluoroalkyl acids (PFAAs) are ubiquitously found in surface waters around the globe. Emissions from households, industries and also atmospheric transport/deposition are discussed as the possible sources. In this study, these sources are evaluated using Switzerland as the study area. Forty-four surface water locations in different rivers and an Alpine lake were investigated for 14 PFAAs, four precursors and acesulfame, an artificial sweetener used as a population marker. Concentrations of individual PFAAs were generally low, between 0.02 and 10 ng/L. Correlation analysis showed that some PFAAs concentrations correlated well with population and less with catchment area, indicating that emissions from population, i.e., from consumer products, is the most important source to surface waters in Switzerland. The correlation with the population marker acesulfame confirmed this observation but highlighted also a few elevated PFAA levels, some of which could be attributed to industrial emissions.

Redox processes of structural Fe in clay minerals play an important role in biogeochemical cycles and for the dynamics of contaminant transformation in soils and aquifers. Reactions of Fe(II)/Fe(III) in clay minerals depend on a variety of mineralogical and environmental factors, which make the assessment of Fe redox reactivity challenging. Here, we use middle and near infrared (IR) spectroscopy to identify reactive structural Fe(II) arrangements in four smectites that differ in total Fe content, octahedral cationic composition, location of the negative excess charge, and configuration of octahedral hydroxyl groups. Additionally, we investigated the mineral properties responsible for the reversibility of structural alterations during Fe reduction and re-oxidation. For Wyoming montmorillonite (SWy-2), a smectite of low structural Fe content (2.8 wt%), we identified octahedral AlFe(II)–OH as the only reactive Fe(II) species, while high structural Fe content (>12 wt%) was prerequisite for the formation of multiple Fe(II)-entities (dioctahedral AlFe(II)–OH, MgFe(II)–OH, Fe(II)Fe(II)–OH, and trioctahedral Fe(II)Fe(II)Fe(II)–OH) in iron-rich smectites Ölberg montmorillonite, and ferruginous smectite (SWa-1), as well as in synthetic nontronite. Depending on the overall cationic composition and the location of excess charge, different reactive Fe(II) species formed during Fe reduction in iron-rich smectites, including tetrahedral Fe(II) groups in synthetic nontronite. Trioctahedral Fe(II) domains were found in tetrahedrally charged ferruginous smectite and synthetic nontronite in their reduced state while these Fe(II) entities were absent in Ölberg montmorillonite, which exhibits an octahedral layer charge. Fe(III) reduction in iron-rich smectites was accompanied by intense dehydroxylation and structural rearrangements, which were only partially reversible through re-oxidation. Re-oxidation of Wyoming montmorillonite, in contrast, restored the original mineral structure. Fe(II) oxidation experiments with nitroaromatic compounds as reactive probes were used to link our spectroscopic evidence to the apparent reactivity of structural Fe(II) in a generalized kinetic model, which takes into account the presence of Fe(II) entities of distinctly different reactivity as well as the dynamics of Fe(II) rearrangements.