NobleBlocks

DVGW - Technologiezentrum Wasser

facilityDresden, Germany

Research output, citation impact, and the most-cited recent papers from DVGW - Technologiezentrum Wasser (Germany). Aggregated across the NobleBlocks index of 300M+ scholarly works.

Total works
681
Citations
65.7K
h-index
119
i10-index
797
Also known as
DVGW - Technologiezentrum WasserDVGW - Water Technology Center

Top-cited papers from DVGW - Technologiezentrum Wasser

Removal of Pharmaceuticals during Drinking Water Treatment
Thomas A. Ternes, Martin Meisenheimer, Derek McDowell, Frank Sacher +4 more
2002· Environmental Science & Technology1.3Kdoi:10.1021/es015757k

The elimination of selected pharmaceuticals (bezafibrate, clofibric acid, carbamazepine, diclofenac) during drinking water treatment processes was investigated at lab and pilot scale and in real waterworks. No significant removal of pharmaceuticals was observed in batch experiments with sand under natural aerobic and anoxic conditions, thus indicating low sorption properties and high persistence with nonadapted microorganisms. These results were underscored by the presence of carbamazepine in bank-filtrated water with anaerobic conditions in a waterworks area. Flocculation using iron(III) chloride in lab-scale experiments (Jar test) and investigations in waterworks exhibited no significant elimination of the selected target pharmaceuticals. However, ozonation was in some cases very effective in eliminating these polar compounds. In lab-scale experiments, 0.5 mg/L ozone was shown to reduce the concentrations of diclofenac and carbamazepine by more than 90%, while bezafibrate was eliminated by 50% with a 1.5 mg/L ozone dose. Clofibric acid was stable even at 3 mg/L ozone. Under waterworks conditions, similar removal efficiencies were observed. In addition to ozonation, filtration with granular activated carbon (GAC) was very effective in removing pharmaceuticals. Except for clofibric acid, GAC in pilot-scale experiments and waterworks provided a major elimination of the pharmaceuticals under investigation.

<i>Nitrosopumilus maritimus</i> genome reveals unique mechanisms for nitrification and autotrophy in globally distributed marine crenarchaea
C. B. Walker, José R. de la Torre, Martin G. Klotz, Hidetoshi Urakawa +4 more
2010· Proceedings of the National Academy of Sciences937doi:10.1073/pnas.0913533107

Ammonia-oxidizing archaea are ubiquitous in marine and terrestrial environments and now thought to be significant contributors to carbon and nitrogen cycling. The isolation of Candidatus "Nitrosopumilus maritimus" strain SCM1 provided the opportunity for linking its chemolithotrophic physiology with a genomic inventory of the globally distributed archaea. Here we report the 1,645,259-bp closed genome of strain SCM1, revealing highly copper-dependent systems for ammonia oxidation and electron transport that are distinctly different from known ammonia-oxidizing bacteria. Consistent with in situ isotopic studies of marine archaea, the genome sequence indicates N. maritimus grows autotrophically using a variant of the 3-hydroxypropionate/4-hydroxybutryrate pathway for carbon assimilation, while maintaining limited capacity for assimilation of organic carbon. This unique instance of archaeal biosynthesis of the osmoprotectant ectoine and an unprecedented enrichment of multicopper oxidases, thioredoxin-like proteins, and transcriptional regulators points to an organism responsive to environmental cues and adapted to handling reactive copper and nitrogen species that likely derive from its distinctive biochemistry. The conservation of N. maritimus gene content and organization within marine metagenomes indicates that the unique physiology of these specialized oligophiles may play a significant role in the biogeochemical cycles of carbon and nitrogen.

Beyond the Calvin Cycle: Autotrophic Carbon Fixation in the Ocean
Michael Hügler, Stefan M. Sievert
2010· Annual Review of Marine Science683doi:10.1146/annurev-marine-120709-142712

Organisms capable of autotrophic metabolism assimilate inorganic carbon into organic carbon. They form an integral part of ecosystems by making an otherwise unavailable form of carbon available to other organisms, a central component of the global carbon cycle. For many years, the doctrine prevailed that the Calvin-Benson-Bassham (CBB) cycle is the only biochemical autotrophic CO2 fixation pathway of significance in the ocean. However, ecological, biochemical, and genomic studies carried out over the last decade have not only elucidated new pathways but also shown that autotrophic carbon fixation via pathways other than the CBB cycle can be significant. This has ramifications for our understanding of the carbon cycle and energy flow in the ocean. Here, we review the recent discoveries in the field of autotrophic carbon fixation, including the biochemistry and evolution of the different pathways, as well as their ecological relevance in various oceanic ecosystems.

Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO <sub>2</sub> fixation
Martin Könneke, Daniel M. Schubert, Philip C. Brown, Michael Hügler +4 more
2014· Proceedings of the National Academy of Sciences506doi:10.1073/pnas.1402028111

Archaea of the phylum Thaumarchaeota are among the most abundant prokaryotes on Earth and are widely distributed in marine, terrestrial, and geothermal environments. All studied Thaumarchaeota couple the oxidation of ammonia at extremely low concentrations with carbon fixation. As the predominant nitrifiers in the ocean and in various soils, ammonia-oxidizing archaea contribute significantly to the global nitrogen and carbon cycles. Here we provide biochemical evidence that thaumarchaeal ammonia oxidizers assimilate inorganic carbon via a modified version of the autotrophic hydroxypropionate/hydroxybutyrate cycle of Crenarchaeota that is far more energy efficient than any other aerobic autotrophic pathway. The identified genes of this cycle were found in the genomes of all sequenced representatives of the phylum Thaumarchaeota, indicating the environmental significance of this efficient CO2-fixation pathway. Comparative phylogenetic analysis of proteins of this pathway suggests that the hydroxypropionate/hydroxybutyrate cycle emerged independently in Crenarchaeota and Thaumarchaeota, thus supporting the hypothesis of an early evolutionary separation of both archaeal phyla. We conclude that high efficiency of anabolism exemplified by this autotrophic cycle perfectly suits the lifestyle of ammonia-oxidizing archaea, which thrive at a constantly low energy supply, thus offering a biochemical explanation for their ecological success in nutrient-limited environments.

Critical Assessment of Analytical Methods for the Harmonized and Cost-Efficient Analysis of Microplastics
Sebastian Primpke, Silke Christiansen, Win Cowger, Hannah De Frond +4 more
2020· Applied Spectroscopy452doi:10.1177/0003702820921465

Microplastics are of major concerns for society and is currently in the focus of legislators and administrations. A small number of measures to reduce or remove primary sources of microplastics to the environment are currently coming into effect. At the moment, they have not yet tackled important topics such as food safety. However, recent developments such as the 2018 bill in California are requesting the analysis of microplastics in drinking water by standardized operational protocols. Administrations and analytical labs are facing an emerging field of methods for sampling, extraction, and analysis of microplastics, which complicate the establishment of standardized operational protocols. In this review, the state of the currently applied identification and quantification tools for microplastics are evaluated providing a harmonized guideline for future standardized operational protocols to cover these types of bills. The main focus is on the naked eye detection, general optical microscopy, the application of dye staining, flow cytometry, Fourier transform infrared spectroscopy (FT-Ir) and microscopy, Raman spectroscopy and microscopy, thermal degradation by pyrolysis-gas chromatography-mass spectrometry (py-GC-MS) as well as thermo-extraction and desorption gas chromatography-mass spectrometry (TED-GC-MS). Additional techniques are highlighted as well as the combined application of the analytical techniques suggested. An outlook is given on the emerging aspect of nanoplastic analysis. In all cases, the methods were screened for limitations, field work abilities and, if possible, estimated costs and summarized into a recommendation for a workflow covering the demands of society, legislation, and administration in cost efficient but still detailed manner.

<i>N,N</i>-Dimethylsulfamide as Precursor for <i>N</i>-Nitrosodimethylamine (NDMA) Formation upon Ozonation and its Fate During Drinking Water Treatment
Carsten K. Schmidt, Heinz‐Jürgen Brauch
2008· Environmental Science & Technology311doi:10.1021/es7030467

Application and microbial degradation of the fungicide tolylfluanide gives rise to a new decomposition product named N,N-dimethylsulfamide (DMS). In Germany, DMS was found in groundwaters and surface waters with typical concentrations in the range of 100-1000 ng/L and 50-90 ng/L, respectively. Laboratory-scale and field investigations concerning its fate during drinking water treatment showed that DMS cannot be removed via riverbank filtration, activated carbon filtration, flocculation, and oxidation or disinfection procedures based on hydrogen peroxide, potassium permanganate, chlorine dioxide, or UV irradiation. Even nanofiltration does not provide a sufficient removal efficiency. During ozonation about 30-50% of DMS are converted to the carcinogenic N-nitrosodimethylamine (NDMA). The NDMA being formed is biodegradable and can at least partially be removed by subsequent biologically active drinking water treatment steps including sand or activated carbon filtration. Disinfection with hypochlorous acid converts DMS to so far unknown degradation products but not to NDMA or 1,1-dimethylhydrazine (UDMH).

Critical Review of Processing and Classification Techniques for Images and Spectra in Microplastic Research
Win Cowger, Andrew B. Gray, Silke Christiansen, Hannah DeFrond +4 more
2020· Applied Spectroscopy271doi:10.1177/0003702820929064

Microplastic research is a rapidly developing field, with urgent needs for high throughput and automated analysis techniques. We conducted a review covering image analysis from optical microscopy, scanning electron microscopy, fluorescence microscopy, and spectral analysis from Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, pyrolysis gas-chromatography mass-spectrometry, and energy dispersive X-ray spectroscopy. These techniques were commonly used to collect, process, and interpret data from microplastic samples. This review outlined and critiques current approaches for analysis steps in image processing (color, thresholding, particle quantification), spectral processing (background and baseline subtraction, smoothing and noise reduction, data transformation), image classification (reference libraries, morphology, color, and fluorescence intensity), and spectral classification (reference libraries, matching procedures, and best practices for developing in-house reference tools). We highlighted opportunities to advance microplastic data analysis and interpretation by (i) quantifying colors, shapes, sizes, and surface topologies with image analysis software, (ii) identifying threshold values of particle characteristics in images that distinguish plastic particles from other particles, (iii) advancing spectral processing and classification routines, (iv) creating and sharing robust spectral libraries, (v) conducting double blind and negative controls, (vi) sharing raw data and analysis code, and (vii) leveraging readily available data to develop machine learning classification models. We identified analytical needs that we could fill and developed supplementary information for a reference library of plastic images and spectra, a tutorial for basic image analysis, and a code to download images from peer reviewed literature. Our major findings were that research on microplastics was progressing toward the use of multiple analytical methods and increasingly incorporating chemical classification. We suggest that new and repurposed methods need to be developed for high throughput screening using a diversity of approaches and highlight machine learning as one potential avenue toward this capability.

Analysis of microplastics in drinking water and other clean water samples with micro-Raman and micro-infrared spectroscopy: minimum requirements and best practice guidelines
Darena Schymanski, Barbara E. Oßmann, Nizar Benismail, Kada Boukerma +4 more
2021· Analytical and Bioanalytical Chemistry248doi:10.1007/s00216-021-03498-y

Microplastics are a widespread contaminant found not only in various natural habitats but also in drinking waters. With spectroscopic methods, the polymer type, number, size, and size distribution as well as the shape of microplastic particles in waters can be determined, which is of great relevance to toxicological studies. Methods used in studies so far show a huge diversity regarding experimental setups and often a lack of certain quality assurance aspects. To overcome these problems, this critical review and consensus paper of 12 European analytical laboratories and institutions, dealing with microplastic particle identification and quantification with spectroscopic methods, gives guidance toward harmonized microplastic particle analysis in clean waters. The aims of this paper are to (i) improve the reliability of microplastic analysis, (ii) facilitate and improve the planning of sample preparation and microplastic detection, and (iii) provide a better understanding regarding the evaluation of already existing studies. With these aims, we hope to make an important step toward harmonization of microplastic particle analysis in clean water samples and, thus, allow the comparability of results obtained in different studies by using similar or harmonized methods. Clean water samples, for the purpose of this paper, are considered to comprise all water samples with low matrix content, in particular drinking, tap, and bottled water, but also other water types such as clean freshwater.

Oxidation of <i>N</i>-Nitrosodimethylamine (NDMA) Precursors with Ozone and Chlorine Dioxide:  Kinetics and Effect on NDMA Formation Potential
Changha Lee, Carsten K. Schmidt, Jeyong Yoon, Urs von Gunten
2007· Environmental Science & Technology241doi:10.1021/es062484q

The oxidation of N-nitrosodimethylamine (NDMA) precursors chlorine dioxide (ClO2). Second-order rate constants for the reactions of model NDMA precursors (dimethylamine (DMA) and 7 tertiary amines) with ozone (kapp at pH 7 = 2.4 x 10(-1) to 2.3 x 10(9) M(-1) s(-1)), ClO2 (kapp at pH 7 = 6.7 x 10(-3) to 3.0 x 10(7) M(-1) s(-1)), and hydroxyl radical (*OH) (kapp at pH 7 = 6.2 x 10(7) to 1.4 x 10(10) M(-1) s(-1)) were determined, which showed that the selected NDMA precursors, with the exception of dimethylformamide (DMFA) can be completely transformed via their direct reaction with ozone. During ozonation, DMFA may be partially transformed through oxidation by the secondary oxidant *OH. ClO2 was also shown to effectively transform most of the precursors, with the exceptions of DMA and DMFA. In the second part of the study, the NDMA formation potentials (NDMA-FP) in synthetic and natural waters were measured with and without pre-oxidation with ozone and ClO2. A significant reduction in the NDMA-FPs was observed after complete transformation of the model NDMA precursors. Ozonation generally led to more effective reduction of the NDMA-FP than ClO2. For most of the precursors, the formation of DMA could account for the NDMA-FPs remaining after complete transformation of the model NDMA precursors. In contrast, dimethylethanolamine and dimethyldithiocarbamate yielded other NDMA precursors (not DMA) as their oxidation products. Pre-oxidation by ozone and ClO2 of several natural waters showed behavior similar to that of the oxidation of model NDMA precursors with a reduction of the NDMA-FP by 32-94% for various natural water sources.

Prevalence of Clinically Relevant Antibiotic Resistance Genes in Surface Water Samples Collected from Germany and Australia
Claudia Stoll, Jatinder Sidhu, Andreas Tiehm, S. Toze
2012· Environmental Science & Technology233doi:10.1021/es302020s

The prevalence and proliferation of antibiotic resistant bacteria is profoundly important to human health, but the extent to which aquatic environments contribute toward the dissemination of antibiotic resistant genes (ARGs) is poorly understood. The prevalence of 24 ARGs active against eight antibiotic classes (β-lactams, aminoglycosides, glycopeptides, chloramphenicols, tetracycline, macrolides, trimethoprim, and sulfonamides) was evaluated in surface water samples collected from Germany and Australia with culture independent methods. The ARGs most frequently detected both in Germany and Australia were sulI, sulII (77-100%), and dfrA1 (43-55%) which code for resistance to sulfonamide and trimethoprim. Macrolides resistance gene ermB was relatively more prevalent in the surface water from Germany (68%) than Australia (18%). In contrast, the chloramphenicol resistance gene catII was more frequently detected in Australia (64%) than Germany (9%). Similarly, β-lactams resistance gene ampC was more prevalent in the samples from Australia (36%) than Germany (19%). This study highlights wide distribution of ARGs for sulfonamide, trimethoprim, macroline, β-lactams and chloramphenicol in the aquatic ecosystems. Aquatic ecosystems can therefore be reservoirs of ARGs genes which could potentially be transferred from commensal microorganisms to human pathogens.

Development of a common priority list of pharmaceuticals relevant for the water cycle
Pim de Voogt, M.-L. Janex-Habibi, Frank Sacher, Leo Puijker +1 more
2009· Water Science & Technology220doi:10.2166/wst.2009.764

Pharmaceutically active compounds (PhACs), including prescription drugs, over-the-counter medications, drugs used in hospitals and veterinary drugs, have been found throughout the water cycle. A desk study was initiated by the Global Water Research Coalition to consolidate a uniform selection of such compounds in order to judge risks of PhACs for the water cycle. By identifying major existing prioritization efforts and evaluating the criteria they use, this study yields a representative and qualitative profile ('umbrella view') of priority pharmaceuticals based on an extensive set of criteria. This can then be used for further studies on analytical methods, occurrence, treatability and potential risks associated with exposure to PhACs in water supply, identifying compounds most likely to be encountered and that may have significant impact on human health. For practical reasons, the present study excludes veterinary drugs. The pragmatic approach adopted provides an efficient tool to manage risks related to pharmaceuticals and provides assistance for selecting compounds for future studies.

Reversibility of citrate synthase allows autotrophic growth of a thermophilic bacterium
Achim Mall, Jessica Sobotta, Claudia Huber, Carolin Tschirner +4 more
2018· Science201doi:10.1126/science.aao2410

About-face for citrate synthase Classically, it is thought that citrate synthase only works in one direction: to catalyze the production of citrate from acetyl coenzyme A and oxaloacetate in the tricarboxylic acid (TCA) cycle. The TCA cycle can run in reverse to cleave citrate and fix carbon dioxide autotrophically, but this was thought to occur only with alternative enzymes, such as citrate lyase. Now Nunoura et al. and Mall et al. have discovered thermophilic bacteria with highly efficient and reversible citrate synthase that requires reduced ferredoxin (see the Perspective by Ragsdale). This function is undetectable by metagenomics, but classical biochemistry filled in the gaps seen between the genome sequences and the phenotypes of the organisms. The direction of catalysis depends on the availability of organic versus inorganic carbon and reflects a flexible bet-hedging strategy for survival in fluctuating environments. In evolutionary terms, this capacity might predate the classical TCA cycle and is likely to occur in a wide range of anaerobic microorganisms. Science , this issue p. 559 , p. 563 ; see also p. 517

Thioarsenates in Sulfidic Waters
Stefan Stauder, Brigitte Raue, Frank Sacher
2005· Environmental Science & Technology196doi:10.1021/es048034k

It has long been recognized that the formation of soluble arsenic sulfur complexes plays a key role for the mobility and toxicity of arsenic in sulfate-reducing environments. Knowledge of the exact arsenic species is essential to understand the behavior of arsenic in sulfidic aquifers and to develop remediation strategies. In the past, monomeric and trimeric thioarsenites were assumed to be the existing species in sulfidic systems. In this study, thioarsenates were identified by IC-ICP/MS in arsenite- and sulfide-containing solutions as well as in a reduced groundwater from a contaminated site. The unexpected finding of an oxidation of As(lll) to As(V) in thioarsenates in strongly reducing systems can be explained by the high affinity between As(Ill) and sulfur. In sulfide-containing solutions without oxidant, As(lll) therefore undergoes disproportionation to thioarsenates (As(V)) and elemental arsenic. It has previously been supposed that mobility as well as toxicity of arsenic increases if the redox state decreases. For sulfidic waters, the opposite is probably the case. Thus, the formation of thioarsenates could be used in connection with remediation strategies. Thioarsenates are highly sensitive to oxygen and pH. This is important for analytical procedures. A loss of soluble arsenic as well as a conversion to arsenite and arsenate may occur if water samples containing thioarsenates are analyzed with conventional methods.

Ultra-Short-Chain PFASs in the Sources of German Drinking Water: Prevalent, Overlooked, Difficult to Remove, and Unregulated
Isabelle Neuwald, Daniel Hübner, Hanna Laura Wiegand, Vassil Valkov +4 more
2022· Environmental Science & Technology186doi:10.1021/acs.est.1c07949

Per- and polyfluoroalkyl substances (PFASs) have been a focal point of environmental chemistry and chemical regulation in recent years, culminating in a shift from individual PFAS regulation toward a PFAS group regulatory approach in Europe. PFASs are a highly diverse group of substances, and knowledge about this group is still scarce beyond the well-studied, legacy long-chain, and short-chain perfluorocarboxylates (PFCAs) and perfluorosulfonates (PFSAs). Herein, quantitative and semiquantitative data for 43 legacy short-chain and ultra-short-chain PFASs (≤2 perfluorocarbon atoms for PFCAs, ≤3 for PFSAs and other PFASs) in 46 water samples collected from 13 different sources of German drinking water are presented. The PFASs considered include novel compounds like hexafluoroisopropanol, bis(trifluoromethylsulfonyl)imide, and tris(pentafluoroethyl)trifluorophosphate. The ultra-short-chain PFASs trifluoroacetate, perfluoropropanoate, and trifluoromethanesulfonate were ubiquitous and present at the highest concentrations (98% of sum target PFAS concentrations). “PFAS total” parameters like the adsorbable organic fluorine (AOF) and total oxidizable precursor (TOP) assay were found to provide only an incomplete picture of PFAS contamination in these water samples by not capturing these highly prevalent ultra-short-chain PFASs. These ultra-short-chain PFASs represent a major challenge for drinking water production and show that regulation in the form of preventive measures is required to manage them.

Selectivity of solid phase extraction of freshwater dissolved organic matter and its effect on ultrahigh resolution mass spectra
Julia Raeke, Oliver J. Lechtenfeld, Martin Wagner, Peter Herzsprung +1 more
2016· Environmental Science Processes & Impacts184doi:10.1039/c6em00200e

Solid phase extraction (SPE) is often used for enrichment and clean-up prior to analysis of dissolved organic matter (DOM) by electrospray ionization (ESI) coupled to ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). It is generally accepted that extraction by SPE is not quantitative with respect to carbon concentration. However, little information is available on the selectivity of different SPE sorbents and the resulting effect for the acquired DOM mass spectra. Freshwater samples were extracted by the widely used PPL, HLB and C18 sorbents and the molecular composition and size distribution of the DOM in the extracts and in the permeates was compared to the original sample. Dissolved organic carbon (DOC) recoveries ranged between 20% and 65% for the three tested SPE sorbents. Size-exclusion chromatography coupled to organic carbon detection (SEC-OCD) revealed that limited recovery by PPL and HLB was primarily due to incomplete elution of a fraction of apparent high molecular weight from the solid phase. In contrast, incomplete retention on the solid phase, mainly observed for the C18 cartridge, was attributed to a fraction of low molecular weight. The FT-ICR mass spectra of the original sample and the SPE extracts did not differ significantly in their molecular weight distribution, but they showed sorbent specific differences in the degree of oxygenation and saturation. We concluded that the selective enrichment of freshwater DOM by SPE is less critical for subsequent FT-ICR MS analysis, because those fractions that are not sufficiently recovered have comparatively small effects on the mass spectra. This was confirmed by the extraction of model compounds, showing that very polar and small molecules are poorly extracted, but also have a low response in ESI-MS. Of the three tested SPE cartridges the PPL material offered the best properties for DOM enrichment for subsequent FT-ICR MS analysis as it minimizes too strong and too weak DOM-sorbent interactions.

Sludge As a Potential Important Source of Antibiotic Resistance Genes in Both the Bacterial and Bacteriophage Fractions
William Calero‐Cáceres, Ana Melgarejo, Marta Colomer-Lluch, Claudia Stoll +3 more
2014· Environmental Science & Technology184doi:10.1021/es501851s

The emergence and prevalence of antibiotic resistance genes (ARGs) in the environment is a serious global health concern. ARGs found in bacteria can become mobilized in bacteriophage particles in the environment. Sludge derived from secondary treatment in wastewater treatment plants (WWTPs) constitutes a concentrated pool of bacteria and phages that are removed during the treatment process. This study evaluates the prevalence of ARGs in the bacterial and phage fractions of anaerobic digested sludge; five ARGs (blaTEM, blaCTX-M, qnrA, qnrS, and sul1) are quantified by qPCR. Comparison between the wastewater and sludge revealed a shift in the prevalence of ARGs (blaTEM and sul1 became more prevalent in sludge), suggesting there is a change in the bacterial and phage populations from wastewater to those selected during the secondary treatment and the later anaerobic mesophilic digestion of the sludge. ARGs densities were higher in the bacterial than in the phage fraction, with high densities in both fractions; particularly for blaTEM and sul1 (5 and 8 log10 gene copies (GC)/g, respectively, in bacterial DNA; 5.5 and 4.4 log10 GC/g, respectively, in phage DNA). These results question the potential agricultural uses of treated sludge, as it could contribute to the spread of ARGs in the environment and have an impact on the bacterial communities of the receiving ecosystem.

Correlation of Aqueous-Phase Adsorption Isotherms
John C. Crittenden, Sompop Sanongraj, John L. Bulloch, David W. Hand +3 more
1999· Environmental Science & Technology176doi:10.1021/es981082i

A correlation was developed to estimate the adsorption equilibrium capacity of various adsorbents and organic compounds using a combination of Polanyi potential theory and linear solvation energy relationships (LSERs). Polanyi theory provided the basic mathematical form for the correlation. LSERs were used to normalize the Polanyi theory based on the fundamental interaction forces between the solvent, adsorbate, and adsorbent expected in aqueous-phase adsorption. The correlation was developed using 56 organic compounds and eight adsorbents. The following classes of organic compounds were used: (i) halogenated aliphatics, (ii) aromatics and halogenated aromatics, (iii) polyfunctional organic compounds and (iv) sulfonated aromatics. The adsorbents were (i) three coal-based activated carbons (F-300, F-400, and APA), (ii) one coconut shell based activated carbon (580-26), (iii) one unspecified activated carbon, and (iv) three synthetic polymeric adsorbents (XAD-4, XAD-7, and XEN-563). The proposed correlation, which considers the fundamental solvent−adsorbate−adsorbent interaction forces, showed a significant improvement in predicting the adsorption capacity over a correlation that considered only van der Waals forces. However, the correlations did not predict the adsorption capacities of highly soluble organic compounds such as polysulfonated aromatics and polyfunctional organic compounds.

Occurrence of the antidiabetic drug metformin in sewage and surface waters in Germany
Marco Scheurer, Frank Sacher, Heinz‐Jürgen Brauch
2009· Journal of Environmental Monitoring173doi:10.1039/b909311g

The antidiabetic drug metformin is among the pharmaceuticals with the highest production numbers world-wide. This paper presents first data on the occurrence of metformin in sewage and surface waters in Germany. Analysis of metformin is based on pre-concentration of the analyte onto a polymeric solid-phase material and subsequent determination by liquid chromatography and tandem mass spectrometry. Applying the method to sewage and surface waters, recoveries >90% and limits of detection of 10 ng L(-1) could be achieved by pre-concentration of a sample volume of only 10 mL. Measurements in sewage and surface waters showed an almost ubiquitous presence of metformin in the aquatic environment. The measured concentration levels in sewage treatment plant influents correlate nicely to the prescription numbers for metformin in Germany. During sewage treatment a significant reduction of metformin concentrations was observed which seems to be mainly due to microbial degradation. Despite this significant elimination during sewage treatment, metformin was found in all river waters under investigation. Concentration levels depend on the sewage fraction of the receiving waters and for most rivers are in the range of several 100 ng L(-1), i.e. in the same order of magnitude or even higher than for other relevant pharmaceutical residues.

Kinetics and Mechanisms of <i>N</i>-Nitrosodimethylamine Formation upon Ozonation of <i>N</i>,<i>N</i>-Dimethylsulfamide-Containing Waters: Bromide Catalysis
Urs von Gunten, Elisabeth Salhi, Carsten K. Schmidt, William A. Arnold
2010· Environmental Science & Technology167doi:10.1021/es1011862

N,N-Dimethylsulfamide (DMS), a newly identified, ubiquitous degradation product of the fungicide tolylfluanide, has been shown to be a N-nitrosodimethylamine (NDMA) precursor during ozonation. In this study, batch ozonation experiments in ultrapure buffered water, surface water, and tap water were performed to determine the kinetics and elucidate the mechanism of NDMA formation from DMS. It was found that at circumneutral pH, DMS reacts slowly with ozone (k approximately 20 M(-1) s(-1)) and moderately with hydroxyl radicals (k=1.5x10(9) M(-1)s(-1)). The reaction of DMS with these oxidants does not lead to NDMA. NDMA was only formed if bromide was present during ozonation of DMS-containing waters. Bromide is oxidized to hypobromous acid (HOBr) by ozone which then reacts with the primary amine of DMS to form a Br-DMS species. The rate limiting step of the formation of Br-DMS is the formation of HOBr. The reaction to form Br-DMS has an apparent second order rate constant at pH 8 of >3x10(4) M(-1)s(-1). The Br-DMS is transformed by ozone to NDMA and nitrate (k>or=5000 M(-1) s(-1)), with yields of 54% and 39%, respectively, based on the primary amine nitrogen of DMS. These reactions release bromide, making bromide a catalyst. NDMA is also formed during ozonation of DMS in the presence of hypochlorous acid (20-30% yield). The last step of NDMA formation is an intramolecular rearrangement with sulfur dioxide extrusion. On the basis of the mechanistic and kinetic information, it was possible to model NDMA formation in DMS-containing Lake Zurich water.

Biodegradation of the artificial sweetener acesulfame in biological wastewater treatment and sandfilters
Sandro Castronovo, Arne Wick, Marco Scheurer, Karsten Nödler +2 more
2016· Water Research161doi:10.1016/j.watres.2016.11.041

A considerable removal of the artificial sweetener acesulfame (ACE) was observed during activated sludge processes at 13 wastewater treatment plants (WWTPs) as well as in a full-scale sand filter of a water works. A long-term sampling campaign over a period of almost two years revealed that ACE removal in WWTPs can be highly variable over time. Nitrifying/denitrifying sequencing batch reactors (SBR) as well as aerobic batch experiments with activated sludge and filter sand from a water works confirmed that both activated sludge as well as filter sand can efficiently remove ACE and that the removal can be attributed to biologically mediated degradation processes. The lab results strongly indicated that varying ACE removal in WWTPs is not associated with nitrification processes. Neither an enhancement of the nitrification rate nor the availability of ammonium or the inhibition of ammonium monooxygenase by N-allylthiourea (ATU) affected the degradation. Moreover, ACE was found to be also degradable by activated sludge under denitrifying conditions, while being persistent in the absence of both dissolved oxygen and nitrate. Using ion chromatography coupled with high resolution mass spectrometry, sulfamic acid (SA) was identified as the predominant transformation product (TP). Quantitative analysis of ACE and SA revealed a closed mass balance during the entire test period and confirmed that ACE was quantitatively transformed to SA. Measurements of dissolved organic carbon (DOC) revealed an almost complete removal of the carbon originating from ACE, thereby further confirming that SA is the only relevant final TP in the assumed degradation pathway of ACE. A first analysis of SA in three municipal WWTP revealed similar concentrations in influents and effluents with maximum concentrations of up to 2.3 mg/L. The high concentrations of SA in wastewater are in accordance with the extensive use of SA in acid cleaners, while the degradation of ACE in WWTPs adds only a very small portion of the total load of SA discharged into surface waters. No removal of SA was observed by the biological treatment applied at these WWTPs. Moreover, SA was also stable in the aerobic batch experiments conducted with the filter sand from a water works. Hence, SA might be a more appropriate wastewater tracer than ACE due to its chemical and microbiological persistence, the negligible sorbing affinity (high negative charge density) and its elevated concentrations in WWTP effluents.