The application of contaminated paper sludge on arable land in southwest Germany caused the occurrence of a broad range of poly- and perfluoroalkyl substances (PFASs) on soil. Recently, the dead-end ...transformation products (TPs) perfluorooctanoic acid and perfluorooctanesulfonic acid were detected in groundwater and drinking water. The precursors and other transformation products mostly remained unknown. Therefore, HRMS screening by Kendrick mass analysis and assignment of homologous series in combination with suspect screening were applied to identify original PFASs and their TPs in four different soil samples from sites where contaminated paper sludge was applied. In total, twelve compound classes comprising more than 61 PFASs could be fully or tentatively identified. The data reveal that contamination mainly originates from polyfluorinated dialkylated phosphate esters (from 4:2/6:2 to 12:2/14:2),
N
-ethyl perfluorooctane sulfonamide ethanol–based phosphate diesters (only C
8
/C
8
) and transformation products of these precursors. Contamination patterns can be attributed to PFASs used for paper impregnation and can vary slightly from site to site.
Graphical abstract
The aim of the study was to investigate the biodegradability of guanyl urea (GU) and the behavior of other transformation products (TPs) of Metformin (MF). Most biodegradation studies of MF with ...activated sludge of waste water treatment plants (WWTPs) showed GU as the only bacterial dead-end metabolite without further degradation. In this study, batch experiments with activated sludge revealed biodegradability of GU. GU degradation was much faster under anaerobic than under aerobic conditions. Degradation kinetics for MF was much slower under anaerobic conditions. Adsorptive removal of up to 20% was an additional elimination process of MF and GU. The batch experiments were conducted with sludge of 2 WWTPs, WWTP 1 showed decreasing concentrations of GU from influent to effluent and the other increasing concentrations. This indicates a different adaption of the sludge to GU and may explain the better GU degradation capability of the sludge from WWTP 1. Furthermore, the biodegradation potential of MF was confirmed and in addition, occurrence of the TPs methylbiguanide (MBG), 2-amino-4-methylamino-1,3,5-triazine (2,4-AMT) and the secondary TP 2,4-diamino-1,3,5-triazine (2,4-DAT) was observed in batch experiments with activated sludge of WWTP 1. After fast formation, degradation in turn was slower, especially for 2,4-AMT. In general, TPs played a minor role in MF and GU degradation.
Display omitted
•Guanyl urea revealed as biodegradable under anaerobic and aerobic conditions.•Degradation capability of guanyl urea in lab experiments is also reflected in full-scale plants.•Other transformation products of metformin were formed below 2%.
For a better process understanding of in-stream attenuation of trace organic contaminants (TrOCs), quantitative comparisons between field studies under different environmental conditions and ...controlled laboratory experiments are important to separate different processes. However, this is hampered by the challenge to transfer kinetics from the laboratory to different field conditions due to the lack of good quantitative measures to account for different boundary conditions. For phototransformation, in situ light conditions in a river are difficult to determine because light is reduced, for instance, by absorption, scattering on suspended particles, and shading effects. In this study, we present an approach to separate photochemical from non-photochemical diurnal in-stream attenuation based on rate constants relative to diclofenac, as a reference compound, to account for the difference in the in situ light conditions combined with laboratory experiments. 12 out of 45 detected target TrOCs showed a diurnal attenuation at a selected river stretch. A non-photochemical process, potentially biotransformation, was responsible for the diurnal attenuation of bisoprolol, metoprolol, O-desmethylvenlafaxine, tramadol, and venlafaxine. Attenuation of amisulpride, flufenamic acid, hydrochlorothiazide, naproxen, and xipamide can be quantitatively explained by phototransformation, partially for sotalol. Attenuation rate constants of hydrochlorothiazide at different field sites from this study and from published data range over 2 orders of magnitude. Differences can be quantitatively explained by different light exposures but not by water chemical parameters.
Organic micropollutants enter rivers mainly with discharges of wastewater treatment plants (WWTP) and pose a risk to aquatic ecosystems and water quality. A considerable knowledge gap exists for ...disentangling overlapping processes and driving conditions that control the fate of these pollutants. Thus, the aim of this study was to identify the driving parameters for attenuation of selected pharmaceuticals (carbamazepine, diclofenac, tramadol and venlafaxine) under field conditions. The presented study was performed at a small river (Ammer River, mean discharge 0.87 m3 s−1) which is hydrologically complex due to karstification, numerous artificial discharges, and engineered modifications of the channel. We applied a Lagrangian sampling scheme at two sequential river reaches. In general, for the investigated compounds and over the length of the tested reaches, the absolute net attenuation representative for 24 h was low (≤ 23% net attenuation), yet calculated half-lives were comparable to literature. Photodegradation is specifically relevant for the first river reach characterized by a higher net attenuation of the photosensitive compound diclofenac (14.5% ±11.3%) compared to the second section (9.8% ±13.7%). This is likely due to a spatial difference in canopy shading, which is supported by significant correlations (R2 ≥ 0.8) of the temporally changing ‘temperature’ and ‘solar radiation’ with time-specific degradation rate constants of photosensitive compounds for consecutive hourly water parcels. In general, the presented spatially and temporally resolved approach is a suitable tool to determine the attenuation of organic micropollutants and to narrow down the interpretation of net attenuation to a few reasonable processes.
Display omitted
•Integrated investigation combining field approaches and chemical analysis in a small river•River water influenced by (diffuse) groundwater inflow and wastewater•Application of a mass balance approach based on Lagrangian sampling•Determination of temporal and spatial variability in attenuation of organic micropollutants•Photodegradation identified as major attenuation mechanism in the studied river
Trichloramine is a volatile, irritant compound of penetrating odor, which is found as a disinfection by-product in the air of chlorinated indoor swimming pools from reactions of nitrogenous compounds ...with chlorine. Acid amides, especially urea, ammonium ions and α-amino acids have been found as most efficient trichloramine precursors at acidic and neutral pH. For urea a relative NCl
3 formation of 96% at pH 2.5 and 76% at pH 7.1 was determined. Even under sub-stoichiometric molar ratios of Cl/N the formation of NCl
3 is favored over mono and dichlorinated products. However, the reaction kinetics of urea with chlorine is slow under conditions relevant for swimming pools. Also the mass transfer of NCl
3 from water to the gas phase which was calculated by the Deacon’s boundary layer model could be shown as a relatively slow process. Mass transfer would take 20 h or 5.8 d for a rough or a quiescent surface of the water, respectively. This is much more than a typical turnover rate of 6–8 h of a treatment cycle of a 25 m swimming pool. Therefore processes to remove NCl
3 and its precursors can help to minimize the exposure of bathers.
► Trichloramine precursors. ► Reaction parameters of trichloramine formation. ► Mass transfer of trichloramine from the water to the gas phase. ► Indoor swimming pools.
Interpreting the fate of wastewater contaminants in streams is difficult because their inputs vary in time and several processes synchronously affect reactive transport. We present a method to ...disentangle the various influences by performing a conservative-tracer test while sampling a stream section at various locations for chemical analysis of micropollutants. By comparing the outflow concentrations of contaminants with the tracer signal convoluted by the inflow time series, we estimated reaction rate coefficients and calculated the contaminant removal along a river section. The method was tested at River Steinlach, Germany, where 38 contaminants were monitored. Comparing day-time and night-time experiments allowed distinguishing photo-dependent degradation from other elimination processes. While photo-dependent degradation showed to be highly efficient for the removal of metroprolol, bisoprolol, and venlafaxine, its impact on contaminant removal was on a similar scale to the photo-independent processes when averaged over 24 h. For a selection of compounds analyzed in the present study, bio- and photodegradation were higher than in previous field studies. In the Steinlach study, we observed extraordinarily effective removal processes that may be due to the higher proportion of treated wastewater, temperature, DOC and nitrate concentrations, but also a higher surface to volume ratio from low flow conditions that favorizes photodegradation through the shallow water column and a larger transient storage than observed in comparable studies.
Display omitted
•Studying reactive processes in river channels is inherently difficult.•Tracer tests allowed separating conservative transport from the measured signal.•Comparison of day and night experiments highlighted photodegradation.•Photodegradation is weaker than photo-independent elimination on the long term.
Exposure to disinfection by-products (DBPs) in drinking water and chlorinated swimming pools are associated with adverse health outcomes, but biological mechanisms remain poorly understood.
Evaluate ...short-term changes in metabolic profiles in response to DBP exposure while swimming in a chlorinated pool.
The PISCINA-II study (EXPOsOMICS project) includes 60 volunteers swimming 40min in an indoor pool. Levels of most common DBPs were measured in water and in exhaled breath before and after swimming. Blood samples, collected before and 2h after swimming, were used for metabolic profiling by liquid-chromatography coupled to high-resolution mass-spectrometry. Metabolome-wide association between DBP exposures and each metabolic feature was evaluated using multivariate normal (MVN) models. Sensitivity analyses and compound annotation were conducted.
Exposure levels of all DBPs in exhaled breath were higher after the experiment. A total of 6,471 metabolic features were detected and 293 features were associated with at least one DBP in exhaled breath following Bonferroni correction. A total of 333 metabolic features were associated to at least one DBP measured in water or urine. Uptake of DBPs and physical activity were strongly correlated and mutual adjustment reduced the number of statistically significant associations. From the 293 features, 20 could be identified corresponding to 13 metabolites including compounds in the tryptophan metabolism pathway.
Our study identified numerous molecular changes following a swim in a chlorinated pool. While we could not explicitly evaluate which experiment-related factors induced these associations, molecular characterization highlighted metabolic features associated with exposure changes during swimming.
•MWAS of exposure to Disinfection By-Products from swimming in a chlorinated pool•6471 metabolic features were detected by UHPLC-QTOF- Mass Spectrometry.•DBP exposures were measured in exhaled breath, urine and in swimming water.•293 metabolic features associated to at least one DPB, and 137 to all exposures•Annotation revealed 13 compounds involved in the tryptophan metabolism pathway.
The objective of our study was to test whether limited microbial degradation at low pesticide concentrations could explain the discrepancy between overall degradability demonstrated in laboratory ...tests and their actual persistence in the environment. Studies on pesticide degradation are often performed using unrealistically high application rates seldom found in natural environments. Nevertheless, biodegradation rates determined for higher pesticide doses cannot necessarily be extrapolated to lower concentrations. In this context, we wanted to (i) compare the kinetics of pesticide degradation at different concentrations in arable land and (ii) clarify whether there is a concentration threshold below which the expression of the functional genes involved in the degradation pathway is inhibited without further pesticide degradation taking place. We set up an incubation experiment for four weeks using 14C-ring labeled 2-methyl-4-chlorophenoxyacetic acid (MCPA) as a model compound in concentrations from 30 to 20,000 μg kg
–1
soil. To quantify the abundance of putative microorganisms involved in MCPA degradation and their degradation activity, tfdA gene copy numbers (DNA) and transcripts (mRNA) were determined by quantitative real-time PCR. Mineralization dynamics of MCPA derived-C were analyzed by monitoring 14CO
2
production and 14C assimilation by soil microorganisms. We identified two different concentration thresholds for growth and activity with respect to MCPA degradation using tfdA gene and mRNA transcript abundance as growth and activity indices, respectively. The tfdA gene expression started to increase between 1,000 and 5,000 μg MCPA kg
–1
dry soil, but an actual increase in tfdA sequences could only be determined at a concentration of 20,000 μg. Accordingly, we observed a clear shift from catabolic to anabolic utilization of MCPA-derived C in the concentration range of 1,000 to 5,000 μg kg
–1
. Concentrations ≥1,000 μg kg
–1
were mainly associated with delayed mineralization, while concentrations ≤1,000 μg kg
–1
showed rapid absolute dissipation. The persistence of pesticides at low concentrations cannot, therefore, be explained by the absence of functional gene expression. Nevertheless, significant differences in the degradation kinetics of MCPA between low and high pesticide concentrations illustrate the need for studies investigating pesticide degradation at environmentally relevant concentrations.
The aim of this work was to investigate the occurrence and fate of the antidiabetic metformin (MF) and its transformation products (TPs) in wastewater and surface water samples. New TPs of MF were ...approached by electrochemical degradation with a boron-doped-diamond electrode (at 1.5V for 10min). 2,4-Diamino-1,3,5-triazine (2,4-DAT), methylbiguanide (MBG), 2-amino-4-methylamino-1,3,5-triazine (2,4-AMT) and 4-amino-2-imino-1-methyl-1,2-dihydro-1,3,5-triazine (4,2,1-AIMT) were identified by hydrophilic interaction chromatography (HILIC) with quadrupole time-of-flight mass spectrometry (QTOF-MS) and accurate mass fragmentation. However, the well-known transformation product guanyl urea (GU) could not be formed electrochemically. In samples from wastewater treatment plants (WWTP), 2,4-AMT and 2,4-DAT showed an increasing trend from influents to effluents, which implies formation of the TPs during WWT. MBG is also formed by hydrolysis of MF and therefore didn't show this trend in WWTPs. Compared to GU, the concentrations of other TPs are generally three orders of magnitude lower. MBG and 2,4-DAT were also detected in surface water which was impacted by waste water, while 4,2,1-AIMT could not be detected in any sample. The concentrations of MF were in an expected range for influent (14 to 95μg/l), effluent (0.7 to 6.5μg/l), surface water (up to 234ng/l) and tap water (34ng/l). GU concentrations, however, were in one of the two investigated WWTP much higher in the influent (between 158μg/l and 2100μg/l) than in the effluent (between 26 and 810μg/l). This is a rather unexpected result which has not been reported yet. Obviously, GU has been already formed in parts of the sewer system from MF or from other biguanide compounds like antidiabetics or disinfection chemicals. Furthermore, lower concentrations of GU in the effluents than in the influents indicate degradation processes of guanyl urea in the waste water treatment.
Display omitted
•Electrochemical generation of metformin (MF) TPs•Identification of MF TPs by LC-high-resolution MS•Detection of MF TPs in wastewater and surface water
PDF
