Interspecies comparison of metabolism of two novel prototype PFAS.

As a result of proposed global restrictions and regulations on current-use per-and polyfluoroalkyl substances (PFAS), research on possible alternatives is highly required. In this study, phase I in vitro metabolism of two novel prototype PFAS in human and rat was investigated. These prototype chemicals are intended to be safer-by-design and expected to mineralize completely, and thus be less persistent in the environment compared to the PFAS available on the market. Following incubation with rat liver S9 (RL-S9) fractions, two main metabolites per initial substance were produced, namely an alcohol and a short-chain carboxylic acid. While with human liver S9 (HL-S9) fractions, only the short-chain carboxylic acid was detected. Beyond these major metabolites, two and five additional metabolites were identified at very low levels by non-targeted screening for the ether- and thioether-linked prototype chemicals, respectively. Overall, complete mineralization during the in vitro hepatic metabolism of these novel PFAS by HL-S9 and RL-S9 fractions was not observed. The reaction kinetics of the surfactants was determined by using the metabolite formation, rather than the substrate depletion approach. With rat liver enzymes, the formation rates of primary metabolite alcohols were at least two orders of magnitude higher than those of secondary metabolite carboxylic acids. When incubating with human liver enzymes, the formation rates of single metabolite carboxylic acids, were similar or smaller than those experienced in rat. It also indicates that the overall metabolic rate and clearance of surfactants are significantly higher in rat liver than in human liver. The maximum formation rate of the thioether congener exceeded 10-fold that of the ether in humans but were similar in rats. Overall, the results suggest that metabolism of the prototype chemicals followed a similar trend to those reported in studies of fluorotelomer alcohols.

Finding a way out? Comprehensive biotransformation study of novel fluorinated surfactants.

In this study the environmental fate of two novel trifluoromethoxy-substituted surfactants with respectively an ether or thioether linkage were investigated, of which the design aimed for less persistency and complete mineralization. Long-term microbial transformation studies under aerobic conditions in activated sludge-wastewater medium were performed for 126 days. A semi-closed experimental system with a trapping sorbent was selected to avoid losses of possible volatile transformation products (TPs). The changes in the concentration of the surfactants and their expected TPs were monitored by target analysis using liquid chromatography-tandem mass spectrometry. Significant decrease in the concentration of the surfactants was observed over the incubation period. The main detected TPs were short-chained carboxylic acids (CAs), including a CA with two fluorinated carbon atoms representing the last product prior to mineralization. High stability of these CAs and lack in the formation of inorganic fluoride over the incubation time was however observed. Consequently, unequivocal final mineralization of the investigated surfactants could not be confirmed. Regarding the mass balance, the total amount of detected substances achieved only 30-37% of the expected concentration at the end of the incubation time. The reason of the incomplete mass balance should be further investigated.

Unraveling the dynamics of organic micropollutants in wastewater: Online LC-MS/MS analysis at high temporal resolution.

Online monitoring of organic micropollutants (OMPs) in the aquatic environment at high temporal resolution is an upcoming technique that provides insights into their dynamics and has the potential to bring water research and management to a new level. An online monitoring setup was developed to quantify OMPs in wastewater treatment plant (WWTP) influent and effluent using automated and continuous sampling, sample preparation, online solid-phase extraction-liquid chromatography-tandem mass spectrometry analysis and data evaluation. This online monitoring setup provided high selectivity and sensitivity (limit of quantification down to 1 ng/L) as well as a stable performance during one week of constant operation whilst using a high sampling frequency of 10 min (>1000 samples). Custom automated data evaluation enabled quantification within seconds after each measurement and results were comparable to those from a commercial software. Additionally, an alarm tool was included in the evaluation application, which automatically notified the user in case a substance exceeded a predefined threshold. The online monitoring setup was applied to WWTP influent and effluent, where 57 substances were monitored over a period of one week and two days, respectively. High temporal resolution enabled the observation of periodic patterns of pharmaceuticals as well as pollution by OMPs originating from point and diffuse sources, while dynamics of OMPs in WWTP effluent were less pronounced. These new insights into the dynamics of OMPs in WWTP influent, which would not be observable using 24 h composite samples, will be a starting point for new stormwater and wastewater research and management strategies.

Nontarget screening of production waste samples from Leuckart amphetamine synthesis using liquid chromatography - high-resolution mass spectrometry as a complementary method to GC-MS impurity profiling.

The established approaches of suspect and nontarget screening (NTS) using liquid chromatography-high-resolution mass spectrometry (LC-HRMS) are usually applied in the field of environmental and bioanalytical analysis. Herein, these approaches were employed on a forensic-toxicological application by analyzing different production waste samples from controlled amphetamine synthesis via Leuckart route to evaluate the suitability of this methodology for identification of route-specific organic substances in such waste samples. For analysis, two complementary LC techniques were used to cover a broad polarity spectrum. After data processing and peak picking using the enviMass software and further manual data restriction, 17 features were tentatively identified as suspects, three of which were subsequently identified with reference substances. All suspects had been previously identified in studies, in which gas chromatography-mass spectrometry (GC-MS) was successfully applied for synthesis marker assessment in waste and amphetamine samples. Remaining features with high signal intensity and assigned sum formula were selected for the attempt of structure elucidation. Seven potential synthesis markers were tentatively identified, which were not yet reported, except the sum formula of one compound, and which were partly also detected in real case waste samples afterward. The innovative application of the NTS approach using LC-HRMS for the analysis of aqueous amphetamine synthesis waste samples showed its suitability as extension to GC-MS analysis as it was possible to successfully identify seven new potential marker compounds, which are specific either for the conversion of the pre-precursors α-phenylacetoacetonitrile and α-phenylacetoacetamide to benzyl methyl ketone or for the subsequent Leuckart synthesis route after their conversion.

Synthetic cannabinoid receptor agonists and their human metabolites in sewage water: Stability assessment and identification of transformation products.

Since their first appearance in 2008, synthetic cannabinoid receptor agonists (SCRAs) remain the most popular new psychoactive substances (NPS) in the EU. Following consumption, these drugs and their metabolites are urinary excreted and enter the sewage system enabling the application of wastewater-based epidemiology (WBE). Knowing the fate of target analytes in sewage water is essential for successful application of WBE. This study investigates the stability of several chemically diverse SCRAs and selected human metabolites under sewage conditions utilizing a combination of liquid chromatography-tandem mass spectrometry and high-resolution mass spectrometry (HRMS). Target analytes included SCRAs with indole (5F-PB-22, PB-22 pentanoic acid), indazole (AMB-FUBINACA, 5F-ADB, 5F-ADB dimethylbutanoic acid), carbazole (MDMB-CHMCZCA, EG-018), and γ-carboline (Cumyl-PeGaClone) chemical core structures representing most of the basic core structures that have occurred up to now. Stability tests were performed using wastewater effluent containing 5% activated sludge as inoculum to monitor degradation processes and formation of transformation products (TPs). The majority of investigated SCRAs, excluding the selected human metabolites, was recalcitrant to microbial degradation in sewage systems over a period of 29 days. Their stability was rather controlled by physico-chemical processes like sorption and hydrolysis. Considering a typical hydraulic in-sewer retention time of 24 h, the concentration of AMB-FUBINACA decreased by 90% thus representing the most unstable SCRA investigated in this study. Among the 10 newly identified TPs, three could be considered as relevant markers and should be included into future WBE studies to gain further insight into use and prevalence of SCRAs on the drug market.

Matrix effects in the analysis of polar organic water contaminants with HILIC-ESI-MS.

Matrix effects have been shown to be very pronounced and highly variable in the analysis of mobile chemicals, which may severely exacerbate accurate quantification. These matrix effects, however, are still scarcely studied in combination with hydrophilic interaction liquid chromatography (HILIC) and for very polar chemicals. In this study, the matrix effects of 26 polar model analytes were investigated in enriched drinking water, wastewater treatment plant effluent and solutions of inorganic salts, utilizing post-column infusion of the analytes into a HILIC-electrospray ionisation (ESI)-high-resolution mass spectrometry system. These experiments revealed the occurrence of structure-specific and unspecific matrix effects. The unspecific matrix effects were mainly observed in positive ESI polarity and predominantly coincided with a high ion count, resulting in ion suppression of all analytes. Thus, the excess charge is hypothesized to be the limiting factor in ion formation. Structure-specific matrix effects were more pronounced in negative ESI polarity and even structurally similar compounds were observed to react entirely differently: perfluoroalkyl carboxylic acids were suppressed, while perfluoroalkane sulfonic acids were simultaneously enhanced. These matrix effects were traced back to inorganic anions and cations, which eluted over a significant fraction of the chromatographic run time with this setup. Hence, it was concluded that inorganic ions are a main cause for matrix effects in the analysis of mobile chemicals utilizing HILIC. Graphical abstract.

Halomethanesulfonic Acids-A New Class of Polar Disinfection Byproducts: Standard Synthesis, Occurrence, and Indirect Assessment of Mitigation Options.

Halomethanesulfonic acids (HMSAs) are recently discovered polar disinfection byproducts without commercially available reference materials. To allow for their accurate quantification, we successfully synthesized standards for the four presumably most prevalent HMSA congeners: chloromethanesulfonic acid, bromomethanesulfonic acid, dichloromethanesulfonic acid, and bromochloromethanesulfonic acid. After structure confirmation and quantification with high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy, we integrated them into a multilayer solid phase extraction and hydrophilic interaction liquid chromatography-tandem mass spectrometry method dedicated to the analysis of polar water contaminants. With this method we monitored HMSAs in drinking water production plants from four European countries and tap water samples taken in six countries. HMSAs were detected in the low µg/L range after the chlorination step during drinking water production, all tap waters samples, and two surface waters used for drinking water production. Concentrations in tap water samples ranged from 0.07 µg/L to 11.5 µg/L while the HMSA concentrations in surface waters were in the range of 100 ng/L. We utilized the HMSA formation potential to indirectly assess the behavior of hitherto unknown HMSA precursors, consequently identifying ozonation, filtration through activated carbon, and reverse osmosis as efficient removal tools for HMSA precursors, thus limiting their formation during subsequent water disinfection.

Multi-layer solid-phase extraction and evaporation-enrichment methods for polar organic chemicals from aqueous matrices.

Analysis of polar organic chemicals in the aquatic environment is exacerbated by the lack of suitable and widely applicable enrichment methods. In this work, we assessed the suitability of a novel combination of well-known solid-phase extraction (SPE) materials in one cartridge as well as an evaporation method and for the enrichment of 26 polar model substances (predominantly log D < 0) covering a broad range of physico-chemical properties in three different aqueous matrices. The multi-layer solid-phase extraction (mlSPE) and evaporation method were investigated for the recovery and matrix effects of the model substances and analyzed with hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS). In total, 65% of the model substances were amenable (> 10% recovery) to the mlSPE method with a mean recovery of 76% while 73% of the model substances were enriched with the evaporation method achieving a mean recovery of 78%. Target and non-target screening comparison of both methods with a frequently used reversed-phase SPE method utilizing "hydrophilic and lipophilic balanced" (HLB) material was performed. Target analysis showed that the mlSPE and evaporation method have pronounced advantages over the HLB method since the HLB material retained only 30% of the model substances. Non-target screening of a ground water sample with the investigated enrichment methods showed that the median retention time of all detected features on a HILIC system decreased in the order mlSPE (3641 features, median tR 9.7 min), evaporation (1391, 9.3 min), HLB (4414, 7.2 min), indicating a higher potential of the described methods to enrich polar analytes from water compared with HLB-SPE. Graphical abstract Schematic of the method evaluation (recovery and matrix effects) and method comparison (target and non-target analysis) of the two investigated enrichment methods for very polar chemicals in aqueousmatrices.

HPLC-MS/MS methods for the determination of 52 perfluoroalkyl and polyfluoroalkyl substances in aqueous samples.

Two quantitative methods using high-performance liquid chromatography (HPLC) combined with triple quadrupole tandem mass spectrometry (MS/MS) were developed to determine perfluoroalkyl and polyfluoroalkyl substances (PFASs) in aqueous samples. The first HPLC-MS/MS method was applied to 47 PFASs of 12 different substance classes with acidic characteristics such as perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs), as well as precursor substances and biotransformation intermediates (e.g., unsaturated fluorotelomer carboxylic acids). In addition, 25 13C-, 18O-, and 2H-labeled PFASs were used as internal standards in this method. The second HPLC-MS/MS method was applied to fluorotelomer alcohols (FTOHs) and perfluorooctane sulfonamidoethanols as these compounds have physicochemical properties different from those of the previous ones. Accuracy between 82% and 110% and a standard deviation in the range from 2% to 22% depending on the substances were determined during the evaluation of repeatability and precision. The method quantification limit after solid-phase extraction ranged from 0.3 to 199 ng/L depending on the analyte and matrix. The HPLC-MS/MS methods developed were suitable for the determination of PFASs in aqueous samples (e.g., wastewater treatment plant effluents or influents after solid-phase extraction). These methods will be helpful in monitoring campaigns to evaluate the relevance of precursor substances as indirect sources of perfluorinated substances in the environment. In one exemplary application in an industrial wastewater treatment plant, FTOHs were found to be the major substance class in the influent; in particular, 6:2-FTOH was the predominant compound in the industrial samples and accounted for 74% of the total PFAS concentration. The increase in the concentration of the transformation products of FTOHs in the corresponding effluent, such as fluorotelomer carboxylic acids, unsaturated fluorotelomer carboxylic acids, n:3 polyfluorinated saturated carboxylic acids (n indicates the number of nonfluorinated carbon atoms), and PFCAs, indicated biotransformation of FTOHs or their derivatives during wastewater treatment. However, only 33 mol% of the total amount of PFASs present in the influent was quantified in the corresponding effluent. Graphical abstract Method development of an HPLC-MS/MS multi-method for the determination of PFASs in aqueos samples.

Sampling and simultaneous determination of volatile per- and polyfluoroalkyl substances in wastewater treatment plant air and water.

Volatile per- and polyfluoroalkyl substances (PFASs) are often used as precursors in the synthesis of nonvolatile PFASs. The volatile PFASs, which include the perfluoroalkyl iodides (PFAIs), fluorotelomer iodides (FTIs), fluorotelomer alcohols (FTOHs), fluorotelomer olefins (FTOs), fluorotelomer acrylates (FTACs), and fluorotelomer methacrylates (FTMACs), are often produced starting from the telomerization process. These volatile compounds can be present in the air and water environment and can be transformed into highly persistent perfluoroalkyl carboxylic acids. With the exception of FTOHs, which are well studied, the determination of other volatile PFASs is also of prime importance in studying the sources and fate of PFASs. In this study, a method was developed to determine representative precursor compounds that included PFAIs, FTIs, FTOs, FTACs, and FTMACs in wastewater treatment plant (WWTP) air and water samples. The sampling and sample preparation step involved the use of solid-phase extraction (SPE) cartridges with HLB™ material to enrich the analyte. Gas chromatography with mass spectrometry was employed for the detection and quantification of the analytes. Method validation results showed high linearity and sensitivity in the positive electron ionization-selected ion monitoring mode (+EI-SIM). The absolute instrumental limits of detection were in the range of 0.5 to 2 pg. The method detection limit (MDL) in air was 1 ng/m3 with the exception of the FTACs which could be only be detected at concentrations higher than 40 ng/m3. The MDL in water was 10 ng/L. Direct spiking of the cartridges and analyte introduction by volatilization from the glass surface onto the SPE material had recoveries between 86 and 100%. The volatile PFASs were shown to readily partition into the air rather than into water. Consequently, large losses in the amount of PFASs were observed when these were spiked into the water. Graphical abstract Wastewater treatment plant air and water samples were passed through HLB™ solid-phase materials. The eluates were injected onto a GC-MS system to simultaneously determine the volatile PFASs.

Systematic determination of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in outdoor jackets.

Sixteen outdoor jackets were purchased in 2011/12 and analyzed for 23 different perfluoroalkyl and polyfluoroalkyl substances (PFASs). The jackets were selected based on their origin of production, price, market, and textile, such as polyester, nylon, polyamide, and content of poly(tetrafluoroethylene) membranes. Two robust analytical methods based on high pressure liquid chromatography combined with tandem mass spectrometry, as well as two liquid extractions, were developed enabling the analysis of PFASs with widely different physico-chemical properties. The jackets were found to contain PFASs in a range between 0.03 and 719 µg/m(2). Perfluorooctanoic acid (PFOA) was omnipresent (0.02-171 µg/m(2)), although at lower concentrations compared to the precursors of perfluoroalkyl carboxylic acids (PFCAs), namely fluorotelomer alcohols (FTOHs) (<0.001-698 µg/m(2)). Perfluoroalkane sulfonic acids and their putative precursors, in particular perfluoroalkane sulfonamides, were detected much less frequently at concentrations up to 5 µg/m(2). To determine the effect of the volatility of FTOHs, four selected jackets were stored in a sealed bag in the dark at room temperature and re-analyzed after 3.5 years. Only 10%-20% of the initial concentration of 8:2-FTOH and 20%-50% of 10:2-FTOH were found, whereas the concentrations of PFOA and perfluorodecanoic acid increased significantly. This supports the hypothesis that PFAS concentrations in textiles are also strongly dependent on age, and conditions of transport and storage.

Halogenated methanesulfonic acids: A new class of organic micropollutants in the water cycle.

Mobile and persistent organic micropollutants may impact raw and drinking waters and are thus of concern for human health. To identify such possible substances of concern nineteen water samples from five European countries (France, Switzerland, The Netherlands, Spain and Germany) and different compartments of the water cycle (urban effluent, surface water, ground water and drinking water) were enriched with mixed-mode solid phase extraction. Hydrophilic interaction liquid chromatography - high resolution mass spectrometry non-target screening of these samples led to the detection and structural elucidation of seven novel organic micropollutants. One structure could already be confirmed by a reference standard (trifluoromethanesulfonic acid) and six were tentatively identified based on experimental evidence (chloromethanesulfonic acid, dichloromethanesulfonic acid, trichloromethanesulfonic acid, bromomethanesulfonic acid, dibromomethanesulfonic acid and bromochloromethanesulfonic acid). Approximated concentrations for these substances show that trifluoromethanesulfonic acid, a chemical registered under the European Union regulation REACH with a production volume of more than 100 t/a, is able to spread along the water cycle and may be present in concentrations up to the µg/L range. Chlorinated and brominated methanesulfonic acids were predominantly detected together which indicates a common source and first experimental evidence points towards water disinfection as a potential origin. Halogenated methanesulfonic acids were detected in drinking waters and thus may be new substances of concern.

Characterization of 3-Aminopropyl Oligosilsesquioxane.

The synthesis routes in the production of polysilsesquioxanes have largely relied upon in situ formations. This perspective often leads to polymers in which their basic structures including molecular weight and functionality are unknown [ Lichtenhan , J. D. ; et al. Silsesquioxane-siloxane copolymers from polyhedral silsesquioxanes Macromolecules , 1993 , 26 , 2141 - 2142 , http://dx.doi.org/10.1021/ma0060a053 ]. For a better understanding of the polysilsesquioxane properties and applications, there is a need to develop more techniques to enable their chemical characterization. An innovative method was developed to determine the molecular weight distribution (MWD) of an oligosilsesquioxane synthesized in-house from (3-aminopropyl)triethoxysilane. This method, which can be applied to other silsesquioxanes, siloxanes, and similar oligomers and polymers, involved separation using high performance liquid chromatography (HPLC) and detection using mass spectrometry (MS) with electrospray ionization (ESI). The novelty of the method lies on the unique determination of the absolute concentrations of the individual homologues present in the sample formulation. The use of absolute concentrations is necessary in estimating the MWD of the formulation when relative percentage, which is based solely on mass spectral ion intensities, becomes irrelevant due to the disproportionate response factors of the homologues. Determination of absolute concentration requires the use of single-homologue calibration standards. Because of commercial unavailability, these standards were prepared by efficient fractionation of the original formulation.

High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation.

High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid of an instrument data processor. Highly accurate mass spectral data enabled the calculation of higher-order mass defects. The different plots of MW and the nth-order mass defects (up to n = 3) could aid in assessing the structure of the different repeating units and estimating their absolute and relative number per molecule. The three major repeating units were -C2H4O-, -C2F4O-, and -CF2O-. Tandem MS was used to identify the end groups that appeared to be phosphates, as well as the possible distribution of the repeating units. Reversed-phase HPLC separated of the polymer molecules on the basis of number of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health. Graphical Abstract ᅟ.

Photodegradation of sulfonamides and their N (4)-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts.

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N (4)-acetylated metabolites (N (4)-acetylsulfadiazine, N (4)-acetylsulfamethazine, and N (4)-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N (4)-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO2 extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N (4)-acetylsulfadiazine and N (4)-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.

Biodegradation studies of N4-acetylsulfapyridine and N4-acetylsulfamethazine in environmental water by applying mass spectrometry techniques.

This work evaluates the biodegradation of N(4)-acetylsulfapyridine (AcSPY) and N(4)-acetylsulfamethazine (AcSMZ), metabolites of two of the most commonly used sulfonamides (SAs) in human and veterinary medicine, respectively. Aerobic transformation in effluent wastewater was simulated using aerated fixed-bed bioreactors. No visible changes in concentration were observed in the AcSMZ reactor after 90 days, whereas AcSPY was fully degraded after 32 days of experiment. It was also demonstrated that AcSPY transformed back to its parent compound sulfapyridine (SPY). The environmental presence of these two metabolites in wastewater effluent had been previously investigated and confirmed, together with three more SA acetylated metabolites and their corresponding parent compounds, in 18 different wastewater treatment plants in Hesse (Germany). Sulfamethoxazole (SMX) and SPY were the two SAs detected most frequently (90% and 89% of the samples, respectively) and in the highest concentrations (682 ng L(-1) for SMX and 532 ng L(-1) for SPY). To conclude, hazard quotients were calculated whenever toxicity data were available. None of the SAs studied posed an environmental risk.

Acute toxicity of poly- and perfluorinated compounds to two cladocerans, Daphnia magna and Chydorus sphaericus.

With their global distribution, environmental persistence, and potential risk to human beings and ecosystems, poly- and perfluorinated compounds (PFCs) are of particular concern for research and regulatory communities. However, insufficient toxicity data are available for most poly- and perfluorinated compounds to assess their possible environmental hazards accurately. Therefore, the acute toxicity of seven poly- and perfluorinated carboxylic acids and alcohols on two cladocerans, Daphnia magna and Chydorus sphaericus, was evaluated in the present study. The adverse effects of these PFCs on these two cladocerans decreased with increasing fluorinated carbon chain length (nC) and quantitative structure-activity relationships were developed to quantify this observation. Because the 50% inhibition effects (EC50) values obtained are far above concentrations typically found in surface water, acute harmful effects of these chemicals to D. magna and C. sphaericus are not expected in the real environment.

Biodegradation of fluorinated alkyl substances.

The incorporation of fluorine into organic molecules entails both positive and adverse effects. Although fluorine imparts positive and unique properties such as water-and oil-repellency and chemical stability, adverse effects often pervade members of this compound class. A striking property of long perfluoroalkyl chains is their very pronounced environmental persistence. The present review is the first one designed to summarize recent accomplishments in the field of biodegradation of fluorine-containing surfactants, their metabolites, and structural analogs. The pronounced scientific and public interest in these chemicals has given impetus to undertake numerous degradation studies to assess the sources and origins of different fluorinated analog chemical known to exist in the environment. It was shown that biodegradation plays an important role in understanding how fluorinated substances reach the environment and, once they do, what their fate is. Today, PFOS and PFOA are ubiquitously detected as environmental contaminants. Their prominence as contaminants is mainly due to their extreme persistence, which is linked to their perfluoroalkyl chain length. It appears that desulfonation of a highly fluorinated surfactants can be achieved if an α-situated H atom, in relation to the sulfonate group, is present, at least under sulfur-limiting conditions. Molecules that are less heavily fluorinated can show very complex metabolic behavior, as is the case for fluorotelomer alcohols. These compounds are degraded via different but simultaneous pathways, which produce different stable metabolites, one of which is the respective perfluoroalkanoate (8:2-FTOH is transformed to PFOA). Preliminary screening tests indicate that fluorinated functional groups, such as the trifluoromethoxy group and the p-(trifluoromethyl)phenoxy group, may be useful implementations in novel, environmentally benign fluorosurfactants. More specifically, trifluoromethoxy groups constitute a substitute for those that have been used in the past; this functionality is degradable when it appears in structures that are normally subject to biodegradation. Other compounds tested did not meet this criterion. Interdisciplinary investigations on fluorinated surfactants are still very much needed and will certainly continue during the next many years. For instance, the role of fluorinated polymers in contributing small fluorinated molecules to the environmental burden still has not been fully understood.

Fluorotelomer ethoxylates: sources of highly fluorinated environmental contaminants part I: biotransformation.

Polyethoxylated 2-perfluoroalkylethanols ('fluorotelomer ethoxylates', F-(CF(2)-CF(2)-)(x)-(CH(2)-CH(2)-O)(y)-H, FTEO) are an important class of non-ionic fluorinated surfactants, which have been disregarded as potential source of per- and polyfluorinated organic pollutants despite their high production and application amounts. A commercial mixture of FTEO with a perfluoroalkyl chain length between 6 and 10 carbon atoms and an ethoxymer distribution between 0 and 13 was subjected to a biodegradation test. Monitoring of the aerobic biotransformation process by HPLC-ESI-MS/MS showed that FTEO are rapidly transformed with a half-life of approximately 1d. Structural elucidation of the biotransformation products with the help of hybrid quadrupole--linear ion trap tandem mass spectrometry revealed oxidation to the respective carboxylic acid followed by sequential shortening of ethoxylate units which led to FTEO carboxylates (FTEOC). The conversion rate of FTEOC was found to diminish with decreasing number of ethoxylate units and virtually ceased for compounds with seven intact ethoxy units. These short-chain FTEOC were not further degraded within 48d. Nonetheless, perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA) were detected, whose formation is ascribed to degradation of residual fluorotelomer alcohols present in the commercial product. This article represents the first of two parts of a series concerning FTEO. Whilst this part is clearly focused on results of a biodegradation study of FTEO, part two will pinpoint analytical aspects, synthesis of biotransformation products and first evidence of environmental presence of the biotransformation products.

Environmental occurrence and degradation of the herbicide n-chloridazon.

A sampling campaign was carried out for n-chloridazon (n-CLZ) and its degradation product desphenyl-chloridazon (DPC) in the Hesse region (Germany) during the year 2007: a total of 548 environmental samples including groundwater, surface water and wastewater treatment plant (WWTP) effluent were analysed. Furthermore, aerobic degradation of n-CLZ has been studied utilising a fixed bed bioreactor (FBBR). In surface water, n-CLZ was detected at low concentrations (average 0.01+/-0.06mugL(-1); maximum 0.89mugL(-1)) with a seasonal peak, whereas DPC was present throughout the year at much higher concentrations (average 0.72+/-0.81mugL(-1); maximum 7.4mugL(-1)). Higher n-CLZ concentrations were observed in the North compared with South Hesse, which is ascribed to a higher density of agricultural areas. Furthermore, methylated DPC (Me-DPC), another degradation product, was detected in surface water. In the degradation test, n-CLZ was completely converted to DPC at all concentrations tested (Me-DPC was not formed under the test conditions). DPC was resistant to further degradation during the whole experimental period of 98 days. The results obtained suggest persistence and high dispersion of DPC in the aquatic environment.