Metabolites are overlooked in environmental risk assessments and monitoring of pharmaceuticals: The case study of pantoprazole.

The proton-pump inhibitor pantoprazole (PPZ) is one of the most consumed pharmaceuticals worldwide. Despite its high usage, reported PPZ concentrations in environmental water samples are comparatively low, which can be explained by the extensive metabolism of PPZ in the human body. Since most previous studies did not consider human PPZ metabolites it can be assumed that the current environmental exposure associated with the application of PPZ is substantially underestimated. In our study, 4'-O-demethyl-PPZ sulfide (M1) was identified as the predominant PPZ metabolite by analyzing urine of a PPZ consumer as well as the influent and effluent of a wastewater treatment plant (WWTP) using liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). M1 was found to be ubiquitously present in WWTP effluents (max. concentration: 3 000 ng/L) and surface waters in Germany. On average, the surface water concentrations of M1 were approximately 30 times higher than those of the parent compound PPZ. Laboratory scale experiments demonstrated that activated carbon can considerably adsorb M1 und thus improve its removal during wastewater and drinking water treatment. Laboratory ozonation experiments showed a fast oxidation of M1, accompanied by the formation of several ozonation products. Certain ozonation products (identities confirmed via synthesized reference standards) were also detected in water samples collected after ozonation in a full-scale WWTP. Overall lower signal intensities were observed in the effluents of a sand filter and biologically active granular activated carbon filter, suggesting that the compounds were significantly removed during these post-ozonation treatment stages.

The fate of nitrification and urease inhibitors in simulated bank filtration.

The application of nitrification and urease inhibitors (NUI) in conjunction with nitrogen (N) fertilizers improves the efficiency of N fertilizers. However, NUI are frequently found in surface waters through leaching or surface runoff. Bank filtration (BF) is considered as a low-cost water treatment system providing high quality water by efficiently removing large amounts of organic micropollutants from surface water. The fate of NUI in managed aquifer recharge systems such as BF is poorly known. The aim of this work was to investigate sorption and degradation of NUI in simulated BF under near-natural conditions. Besides, the effect of NUI on the microbial biomass of slowly growing microorganisms and the role of microbial biomass on NUI removal was investigated. Duplicate sand columns (length 1.7 m) fed with surface water were spiked with a pulse consisting of four nitrification (1,2,4-triazole, dicyanodiamide, 3,4-dimethylpyrazole and 3-methylpyrazole) and two urease inhibitors (n-butyl-thiophosphoric acid triamide and n-(2-nitrophenyl) phosphoric triamide). The average spiking concentration of each NUI was 5 µg/L. Experimental and modeled breakthrough curves of NUI indicated no retardation for any of the inhibitors. Therefore, biodegradation was identified as the main elimination pathway for all substances and was highest in zones of high microbial biomass. Removal of 1,2,4-triazole was 50% and n-butyl-thiophosphoric acid triamide proved to be highly degradable and was completely removed after a hydraulic retention time (HRT) of 24 h. 50% of the mass recovery for nitrification inhibitors except for 3,4-dimethylpyrazole was observed at the effluent (4 days HRT). In addition, a mild effect of NUI on microbial biomass was noted. This study highlights that the degradation of NUI in BF depends on HRT and microbial biomass.

Occurrence, Distribution, and Environmental Behavior of Persistent, Mobile, and Toxic (PMT) and Very Persistent and Very Mobile (vPvM) Substances in the Sources of German Drinking Water.

Persistent, mobile, and toxic (PMT) and very persistent and very mobile (vPvM) substances have been recognized as a threat to both the aquatic environment and to drinking water resources. These substances are currently prioritized for regulatory action by the European Commission, whereby a proposal for the inclusion of hazard classes for PMT and vPvM substances has been put forward. Comprehensive monitoring data for many PMT/vPvM substances in drinking water sources are scarce. Herein, we analyze 34 PMT/vPvM substances in 46 surface water, groundwater, bank filtrate, and raw water samples taken throughout Germany. Results of the sampling campaign demonstrated that known PMT/vPvM substances such as 1H-benzotriazole, melamine, cyanuric acid, and 1,4-dioxane are responsible for substantial contamination in the sources of German drinking water. In addition, the results revealed the widespread presence of the emerging substances 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and diphenylguanidine (DPG). A correlation analysis showed a pronounced co-occurrence of PMT/vPvM substances associated predominantly with consumer or professional uses and also demonstrated an inhomogeneous co-occurrence for substances associated mainly with industrial use. These data were used to test the hypothesis that most PMT/vPvM substances pass bank filtration without significant concentration reduction, which is one of the main reasons for introducing PMT/vPvM as a hazard class within Europe.

Combining target analysis with sum parameters-a comprehensive approach to determine sediment contamination with PFAS and further fluorinated substances.

Recent studies aiming at a fluorine mass balance analysis in sediments combined the determination of extractable organic fluorine (EOF) with target analysis. They reported high fractions of unidentified organic fluorine (UOF) compounds, as the target analysis covers only a limited number of per- and polyfluoroalkyl substances (PFAS). For this reason, in this study, a comprehensive approach was used combining target analysis with an extended PFAS spectrum, the EOF and a modified total oxidisable precursor (TOP) assay, which includes trifluoroacetic acid, to determine the PFAS contamination in sediments (n=41) and suspended solids (n=1) from water bodies in Northern Germany (Lower Saxony). PFAS are ubiquitous in the sediments (detected in 83% of the samples). Perfluorinated carboxylic acids (PFCAs) were found in 64% of the samples; perfluorinated sulfonic acids (PFSAs) were detected less frequently (21%), with the highest concentration observed for perfluorooctanesulfonic acid (PFOS). Levels of precursors and substitutes were lower. Applying the TOP assay resulted in an increase in PFCAs in 43% of the samples analysed. In most cases, target analysis and the TOP assay could not account for the EOF concentrations measured. However, as the fraction of UOF decreased significantly, the application of the TOP assay in fluorine mass balance analysis proved to be an important tool in characterising the PFAS contamination of riverine sediments.

Ultra-Short-Chain PFASs in the Sources of German Drinking Water: Prevalent, Overlooked, Difficult to Remove, and Unregulated.

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.

Biological effect and chemical monitoring of Watch List substances in European surface waters: Steroidal estrogens and diclofenac - Effect-based methods for monitoring frameworks.

Three steroidal estrogens, 17α-ethinylestradiol (EE2), 17ß-estradiol (E2), estrone (E1), and the non-steroidal anti-inflammatory drug (NSAID), diclofenac have been included in the first Watch List of the Water Framework Directive (WFD, EU Directive 2000/60/EC, EU Implementing Decision 2015/495). This triggered the need for more EU-wide surface water monitoring data on these micropollutants, before they can be considered for inclusion in the list of priority substances regularly monitored in aquatic ecosystems. The revision of the priority substance list of the WFD offers the opportunity to incorporate more holistic bioanalytical approaches, such as effect-based monitoring, alongside single substance chemical monitoring. Effect-based methods (EBMs) are able to measure total biological activities (e.g., estrogenic activity or cyxlooxygenase [COX]-inhibition) of specific group of substances (such as estrogens and NSAIDs) in the aquatic environment at low concentrations (pg/L). This makes them potential tools for a cost-effective and ecotoxicologically comprehensive water quality assessment. In parallel, the use of such methods could build a bridge from chemical status assessments towards ecological status assessments by adressing mixture effects for relevant modes of action. Our study aimed to assess the suitability of implementing EBMs in the WFD, by conducting a large-scale sampling and analysis campaign of more than 70 surface waters across Europe. This resulted in the generation of high-quality chemical and effect-based monitoring data for the selected Watch List substances. Overall, water samples contained low estrogenicity (0.01-1.3 ng E2-Equivalent/L) and a range of COX-inhibition activity similar to previously reported levels (12-1600 ng Diclofenac-Equivalent/L). Comparison between effect-based and conventional analytical chemical methods showed that the chemical analytical approach for steroidal estrogens resulted in more (76%) non-quantifiable data, i.e., concentrations were below detection limits, compared to the EBMs (28%). These results demonstrate the excellent and sensitive screening capability of EBMs.

Evidence for Specific Receptor-Mediated Toxicity of Pharmaceuticals in Aquatic Organisms Derived from Acute and Chronic Standard Endpoints.

The toxicity of 17 active pharmaceutical ingredients (APIs) was investigated using standardized acute and chronic tests with Daphnia magna and 2 algae species. Chronic toxicity was generally greater for Daphnia than for algae. Compilation of additional data resulted in 100 APIs for which the acute-to-chronic ratio (ACR) was determined for Daphnia. The frequency of high ACRs (~20% with ACRs > 100) indicates that specific receptor-mediated toxicity toward D. magna is rather common among APIs. The 11 APIs with ACRs > 1000 included lipid-modifying agents, immunosuppressants, antibiotics, antineoplastics, antiobesics, antivirals, and antihistamines. There was no consistent association between ACR and chronic toxicity, ionization status, or lipophilicity. High ACRs were not exclusively associated with the presence of orthologs of the pharmacological target in Daphnia. Statins, acetylcholinesterase inhibitors, and antihistamines are discussed in more detail regarding the link between targets and toxic mode of action. For acetylcholinesterase inhibitors, receptor-mediated toxicity was already apparent after acute exposure, whereas the high ACR and chronic toxicity of some antihistamines probably related to interaction with a secondary rather than the primary pharmacological target. Acute or modeled chronic toxicity estimates have often been used for prioritizing pharmaceuticals. This may be seriously misleading because chronic effects are currently not predictable for APIs with specific receptor-mediated toxicity. However, it is exactly these APIs that are the most relevant in terms of environmental risks. Environ Toxicol Chem 2022;41:601-613. © 2021 SETAC.

Can determination of extractable organofluorine (EOF) be standardized? First interlaboratory comparisons of EOF and fluorine mass balance in sludge and water matrices.

The high proportion of unidentified extractable organofluorine (EOF) observed globally in humans and the environment indicates widespread occurrence of unknown per- and polyfluoroalkyl substances (PFAS). However, efforts to standardize or assess the reproducibility of EOF methods are currently lacking. Here we present the first EOF interlaboratory comparison in water and sludge. Three participants (four organizations) analyzed unfortified and PFAS-fortified ultrapure water, two unfortified groundwater samples, unfortified wastewater treatment plant effluent and sludge, and an unfortified groundwater extract. Participants adopted common sample handling strategies and target lists for EOF mass balance but used in-house combustion ion-chromatography (CIC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods. EOF accuracy ranged from 85-101% and 76-109% for the 60 and 334 ng L-1 fluorine (F) - fortified water samples, respectively, with between-laboratory variation of 9-19%, and within-laboratory variation of 3-27%. In unfortified sludge and aqueous samples, between-laboratory variation ranged from 21-37%. The contribution from sum concentrations of 16 individual PFAS (∑PFAS-16) to EOF ranged from 2.2-60% but extended analysis showed that other targets were prevalent, in particular ultra-short-chain perfluoroalkyl acids (e.g. trifluoroacetic acid) in aqueous samples and perfluoroalkyl acid-precursors (e.g. polyfluoroalkyl phosphate diesters) in sludge. The EOF-CIC method demonstrated promising accuracy, robustness and reporting limits but poor extraction efficiency was observed for some targets (e.g. trifluoroacetic acid).

Ultrashort-chain perfluoroalkyl substance trifluoroacetate (TFA) in beer and tea - An unintended aqueous extraction.

Trifluoroacetate (TFA) is an ultrashort-chain perfluoroalkyl substance, which is ubiquitously present in the aqueous environment. Due to its high mobility, it accumulates in plant material. The study presented here shows for the first time that TFA is a widely spread contaminant in beer and tea / herbal infusions. In 104beer samples from 23countries, TFA was detected up to 51 µg/L with a median concentration of 6.1 µg/L. An indicative brewing test and a correlation approach with potassium (K) indicate that the main source of TFA in beer is most likely the applied malt. It could be proven that the impact of the applied water is negligible in terms of TFA, which was supported by the analysis of numerous tap water samples from different countries. The unintended extraction of TFA was also demonstrated for tea / herbal infusions with a median concentration of 2.4 µg/L.

Microplastic analysis in drinking water based on fractionated filtration sampling and Raman microspectroscopy.

Microplastics (MP) as emerging persistent pollutants were found in raw and drinking water worldwide. Since different methods were used, there is an urgent need for harmonized protocols for sampling, sample preparation, and analysis. In this study, a holistic and validated analytical workflow for MP analysis in aqueous matrices down to 5 µm is presented. For sampling of several cubic meters of water, an easily portable filter cascade unit with different pore sizes (100-20-5 µm) was developed and successfully applied for the sampling of three processed drinking waters, two tap waters and one groundwater. The size distribution and polymer types of MP were determined using a two-step semi-automated Raman microspectroscopy analysis. For quality control, comprehensive process blanks were considered at all times and a recovery test yielded an overall recovery of 81%. The average concentration of identified MP was 66 ± 76 MP/m3 ranging from 1 MP/m3 to 197 MP/m3. All found concentrations were below the limit of quantitation (LOQ) of 1880 MP/m3. The majority consisted of PE (86% ± 111%) while comparatively low numbers of PET (10% ± 25%), PP (3% ± 6%), and PA (1% ± 4%) were found. 79% of all particles were smaller than 20 µm. In summary, this study presents the application of a workflow for sampling and analysis of MP down to 5 µm with first results of no significant contamination in drinking water and groundwater.

Extending the knowledge about PFAS bioaccumulation factors for agricultural plants - A review.

A main source of perfluoroalkyl and polyfluoroalkyl substances (PFASs) residues in agricultural plants is their uptake from contaminated soil. Bioaccumulation factors (BAFs) can be an important tool to derive recommendations for cultivation or handling of crops prior consumption. This review compiles >4500 soil-to-plant BAFs for 45 PFASs from 24 studies involving 27 genera of agricultural crops. Grasses (Poaceae) provided most BAFs with the highest number of values for perfluorooctanoic acid and perfluorooctane sulfonic acid. Influencing factors on PFAS transfer like compound-specific properties (hydrophobicity, chain length, functional group, etc.), plant species, compartments, and other boundary conditions are critically discussed. Throughout the literature, BAFs were higher for vegetative plant compartments than for reproductive and storage organs. Decreasing BAFs per additional perfluorinated carbon were clearly apparent for aboveground parts (up to 1.16 in grains) but not always for roots (partly down to zero). Combining all BAFs per single perfluoroalkyl carboxylic acid (C4-C14) and sulfonic acid (C4-C10), median log BAFs decreased by -0.25(±0.029) and -0.24(±0.013) per fluorinated carbon, respectively. For the first time, the plant uptake of ultra-short-chain (≤ C3) perfluoroalkyl acids (PFAAs) was reviewed and showed a ubiquitous occurrence of trifluoroacetic acid in plants independent from the presence of other PFAAs. Based on identified knowledge gaps, it is suggested to focus on the uptake of precursors to PFAAs, PFAAs ≤C3, and additional emerging PFASs such as GenX or fluorinated ethers in future research. Studies regarding the uptake of PFASs by sugar cane, which accounts for about one fifth of the global crop production, are completely lacking and are also recommended. Furthermore, aqueous soil leachates should be tested as an alternative to the solvent extraction of soils as a base for BAF calculations.

Air-drying of soil samples - A crucial step in the determination of leachable concentrations of per- and polyfluoroalkyl substances.

Batch leaching tests at a liquid to solid ratio of 2 L/kg are a valuable tool for the assessment of low PFAS levels in soils. Data from different monitoring programs comprising samples without known local source of PFAS contamination showed that soil-sample drying at ambient temperature or at 40 °C prior to the leaching process leads to higher PFAS leachate levels compared to non-dried samples. The effect was greater for perfluoroalkyl carboxylic acids (PFCAs) than for perfluoroalkyl sulfonic acids (PFSAs). In a controlled field study comparing field-fresh (frozen to -18 °C and thawed) samples with air-dried (room temperature) samples median levels after drying increased to 140%-470% for C4 to C10 PFCAs and to 130%-200% for C4, C6, and C8 PFSAs, respectively. Thus, using field-fresh samples for batch leaching tests might underestimate the leachable fraction of PFAA in the field, where drying and leaching periods alternate.

Trifluoroacetate in Precipitation: Deriving a Benchmark Data Set.

Although precipitation is considered to be the most important diffuse source of trifluoroacetate (TFA) to the nonmarine environment, information regarding the wet deposition of TFA as well as general data on the spatial and temporal variations in TFA concentration in precipitation is scarce. This is the first study to provide a comprehensive overview of the occurrence of TFA in precipitation by a systematic and nation-wide field monitoring campaign. In total, 1187 precipitation samples, which were collected over the course of 12 consecutive months at eight locations across Germany, were analyzed. The median, the estimated average, and the precipitation-weighted average TFA concentration of all analyzed wet deposition samples were 0.210, 0.703, and 0.335 µg/L, respectively. For Germany, an annual wet deposition flux of 190 µg/m2 or approximately 68 t was calculated for the sampling period from February 2018 to January 2019. The campaign revealed a pronounced seasonality of the TFA concentration and wet deposition flux of collected samples. Correlation analysis suggested an enhanced transformation of TFA precursors in the troposphere in the summertime due to higher concentrations of photochemically generated oxidants such as hydroxyl radicals, ultimately leading to an enhanced atmospheric deposition of TFA during summer.

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

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

Uptake and Effects of the Beta-Adrenergic Agonist Salbutamol in Fish: Supporting Evidence for the Fish Plasma Model.

The fish plasma model (FPM) predicts the fish blood plasma concentration of a pharmaceutical from the water concentration to which the fish is exposed and compares it with the human therapeutic plasma concentration (Hther PC) with the postulate that no adverse toxic effects occur below the Hther PC. The present study provides several lines of evidence supporting the FPM for the beta-adrenergic agonist salbutamol, a small cationic molecule at ambient pH. Salbutamol exhibited very low acute toxicity to early and adult life stages of fish. Biomass reduction in fish early life stages was the most sensitive apical endpoint, with no-observed-effect concentrations (NOECs) in the low mg/L range after continuous exposure for up to 120 d. Given that predicted and measured environmental concentrations are at least 1000-fold lower, the risk of salbutamol in freshwater is deemed very low. Increase in heart beat rate and decrease in total triglyceride content in fish also occurred at the low mg/L range and resembled effects known from humans. This finding supports the FPM assumption of conserved targets in fish with similar functionality. Plasma concentrations measured in adult and juvenile fish exposed to water concentrations at approximately the NOECs exceeded Hther PC and even approached plasma concentrations toxic to humans. This result confirms for salbutamol the FPM hypothesis that no adverse (i.e., population-relevant) toxic effects occur in fish below the Hther PC. Environ Toxicol Chem 2019;38:2509-2519. © 2019 SETAC.

Closing the gap - inclusion of ultrashort-chain perfluoroalkyl carboxylic acids in the total oxidizable precursor (TOP) assay protocol.

An improved protocol of the total oxidizable precursor (TOP) assay was developed for precursors to C2-C14 perfluoroalkyl carboxylic acids (PFCAs) and C4-C8 and C10 perfluoroalkyl sulfonic acids (PFSAs). The proposed protocol was tested and validated for contaminated soil samples. The perfluoroalkyl acids (PFAAs) present in the soil extract solutions after oxidation with persulfate were separated from the inorganic salts by vacuum-assisted drying of the digestion solution followed by solid-liquid extraction of the PFAAs with acetonitrile from the dry residue. Ion chromatography (for C2-C4 PFCAs) and reversed phase liquid chromatography (for all other PFASs), both coupled to tandem mass spectrometry, were used for quantification. High procedural recoveries of PFAAs between 68% and 123% with RSDs between 0.2% and 25% (n = 3) were achieved. The method was validated using selected polyfluoroalkyl phosphoric acid esters (PAPs) and bis-[2-(N-ethyl perfluorooctane-1-sulfonamido)ethyl] phosphoric acid ester (diSAmPAP) as model precursors in pure solutions and in the presence of soil matrix. The oxidation led to characteristic and reproducible PFCA patterns (in the case of PAPs) or PFOA (in the case of diSAmPAP) with total reaction yields between 92 ± 4% and 123 ± 13% (n = 3). The impact of the soil matrix on transformation yields was negligible. In a soil core from a PFAS-polluted agricultural site, precursors were concentrated in the upper 40 cm with long-chain precursors being prevalent. After oxidative digestion, the total molar PFAA-concentrations increased by factors of 1.6 to 5.0. More than 40 cm below ground precursors of TFAA, PFPrA and PFBA accounted for ∼50% of the reaction products, underlining the importance of their inclusion in mass balances based on the TOP assay.

Occurrence and potential environmental risk of surfactants and their transformation products discharged by wastewater treatment plants.

Seven-day composite effluent samples from a German monitoring campaign including 33 conventional wastewater treatment plants (WWTP) were analyzed for linear alkylbenzene sulfonates (LAS) and alkyl ethoxysulfates (AES) and were screened by wide-scope suspect screening for 1564 surfactants and their transformation products (TPs) by UHPLC-ESI-QTOF-MS. Corresponding seven-day composite influent samples of selected WWTPs showed high influent concentrations as well as very high removal rates for LAS and AES. However, average total LAS and AES effluent concentrations were still 14.4 µg/L and 0.57 µg/L, respectively. The LAS-byproducts di-alkyl tetralin sulfonates (DATSs), the TPs sulfophenyl alkyl carboxylic acids (SPACs) and sulfo-tetralin alkyl carboxylic acids (STACs) reached maximum effluent concentrations of 19 µg/L, 17 µg/L and 5.3 µg/L, respectively. In many cases the sum of the concentration of all LAS-related byproducts and TPs surpassed the concentration of the precursors. High concentrations of up to 7.4 µg/L were found for 41 polyethylenoglycol homologs. Quantified surfactants and their TPs and by-products together accounted for concentrations up to 82 µg/L in WWTP effluents. To determine the risk of individual surfactants and their mixtures, single homologs were grouped by a "weighted carbon number approach" to derive normalized Predicted No-Effect Concentrations (PNEC), based on experimental ecotoxicity data from existing risk assessments, complemented by suitable Quantitative Structure-Activity Relationships (QSAR) predictions. Predicted Environmental Concentrations (PEC) were derived by dividing effluent concentrations of surfactants by local dilution factors. Risks for all analyzed surfactants were below the commonly accepted PEC/PNEC ratio of 1 for single compounds, while contributions to mixture toxicity effects from background levels of LAS and DATS cannot be excluded. Maximum LAS concentrations exceeded half of its PNEC, which may trigger country-wide screening to investigate potential environmental risks.

Approach for analytical characterization and toxicological assessment of ozonation products in drinking water on the example of acesulfame.

The monitoring and control of drinking water quality is generally important as it significantly contributes to the health of the population. In this context, particular attention has to be paid to the use of treatment techniques during drinking water treatment. It is known that the formation of reaction products (transformation products) has to be taken into account when oxidizing agents such as ozone are used. Different transformation products are classified as critical to health and require analytical examination. The risk assessment for previously unknown transformation products can be difficult as far as not all transformation products are present as single substances or the individual substances are not present in a sufficient high concentration or cannot be isolated from the original solution. The aim of this work is to show exemplarily the identification and quantification of ozonation products (OPs) after ozonation and their toxicological characterization, using the artificial sweetener acesulfame. It was shown that OPs can be fully characterized using ion chromatography in combination with different detection systems. A major OP could be recovered as a pure substance by crystallization and direct genotoxicological testing was possible without previous enrichment processes. Acesulfame samples of different concentrations in ultrapure and in drinking water after ozonation were tested in several genotoxicity tests. These tests revealed genotoxic effects of acesulfame after ozonation in ultrapure water in several genotoxicological test systems (micronucleus test, umu test, Ames-fluctuation-test and comet assay). In contrast, the crystallized ozonation product OP168 did not show any positive effects. Therefore, it seems likely that the observed effect was caused by the second major product OP170. However, a sufficiently large amount of analytically pure substance OP170 could not be obtained. It was also shown that the rate of the OP170 formation in drinking water is significantly lower than in ultrapure water and that ozonation in drinking water did not induce genotoxic effects.