Should Transformation Products Change the Way We Manage Chemicals?

When chemical pollutants enter the environment, they can undergo diverse transformation processes, forming a wide range of transformation products (TPs), some of them benign and others more harmful than their precursors. To date, the majority of TPs remain largely unrecognized and unregulated, particularly as TPs are generally not part of routine chemical risk or hazard assessment. Since many TPs formed from oxidative processes are more polar than their precursors, they may be especially relevant in the context of persistent, mobile, and toxic (PMT) and very persistent and very mobile (vPvM) substances, which are two new hazard classes that have recently been established on a European level. We highlight herein that as a result, TPs deserve more attention in research, chemicals regulation, and chemicals management. This perspective summarizes the main challenges preventing a better integration of TPs in these areas: (1) the lack of reliable high-throughput TP identification methods, (2) uncertainties in TP prediction, (3) inadequately considered TP formation during (advanced) water treatment, and (4) insufficient integration and harmonization of TPs in most regulatory frameworks. A way forward to tackle these challenges and integrate TPs into chemical management is proposed.

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.

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.

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.

Are (fluorinated) ionic liquids relevant environmental contaminants? High-resolution mass spectrometric screening for per- and polyfluoroalkyl substances in environmental water samples led to the detection of a fluorinated ionic liquid.

Fragmentation flagging (FF), a high-resolution mass spectrometric screening variant that utilizes intentionally produced indicative in-source fragments, was used to screen for per- and polyfluoroalkyl substances (PFASs) in surface waters. Besides expected legacy PFAS, FF enabled the detection of some rarely investigated representatives, such as trifluoromethanesulfonic acid (TFMSA). Additionally, a novel PFAS was detected and identified as tris(pentafluoroethyl)trifluorophosphate (FAP) via MS/MS experiments and confirmed with a reference standard. The first monitoring of FAP in 20 different surface waters revealed a localized contamination affecting three connected rivers with peak concentrations of up to 3.4 µg/L. To the best of our knowledge, this is the first time FAP has been detected in environmental water samples. The detection of FAP, which is exclusively used as a constituent of ionic liquids (ILs), raises questions about the environmental relevance of ILs in general and particularly fluorinated ILs. A following comprehensive literature search revealed that ILs have already been intensely discussed as potential environmental contaminants, but findings reporting ILs in environmental (water) samples are almost non-existent. Furthermore, we address the relevance of ILs in the context of persistent, mobile, and toxic chemicals, which are at present gaining increasing scientific and regulatory interest, and as part of the PFAS "dark matter" that represents the gap between the amount of fluorine originating from known PFAS and the total adsorbable organically bound fluorine. Graphical abstract.

Analysis of mobile chemicals in the aquatic environment-current capabilities, limitations and future perspectives.

Persistent and mobile water contaminants are rapidly developing into a focal point of environmental chemistry and chemical regulation. Their defining parameter that sets them apart from the majority of regularly monitored and regulated contaminants is their mobility in the aquatic environment, which is intrinsically tied to a high polarity. This high polarity, however, may have severe implications in the analytical process and thus the most polar of these mobile contaminants may not be covered by widely utilized trace-analytical methods, and thus, alternatives are required. In this review, we infer the physical and chemical properties of mobile water contaminants from a set of almost 1800 prioritized REACH chemicals and discuss the implications these substance properties may have on four integral steps of the analytical process: sampling and sample storage, sample pre-treatment, separation and detection. We discuss alternatives to widely utilized trace-analytical methods, examine their application range and limitations, highlight potential analytical techniques on the horizon and emphasize research areas we believe still offer the most room for further improvement. While we have a comprehensive set of analytical methods to cover a large portion of the known mobile chemicals, these methods are still only infrequently utilized. 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.

Sources of persistent and mobile chemicals in municipal wastewater: a sewer perspective in Leipzig, Germany.

Persistent and mobile (PM) chemicals spread in the water cycle and have been widely detected, yet information about their sources is still scarce. In this study, 67 PM chemicals were analyzed in 19 wastewater samples taken in the sewer system of the city of Leipzig, Germany, covering different industrial, clinical, and domestic discharges. A total of 37 of these analytes could be detected, with highly variable median concentrations between substances (median: 0.5-800 µg L-1) and for single substances between samples (e.g., 1,4-diazabicyclo[2.2.2]octane) by up to three orders of magnitude, with the highest single concentration exceeding 10 mg L-1 (p-cumenesulfonic acid). The emission of PM chemicals into the sewer system was classified as stemming from diffuse (14 analytes) or point sources (23 analytes), while 9 analytes fulfill both criteria. Many so-called industrial chemicals were also discharged from households (e.g., tris(2-chloroethyl) phosphate or 1H-benzotriazole). Examples for analytes showing specific sources are tetrafluoroborate (traffic-related industry and metal production and finishing), ε-caprolactam (large-scale laundry), or cyanuric acid (likely swimming pool). Furthermore, a correlation between 1-cyanoguanidine and guanylurea was observed for the traffic-related industry. This study outlines that sewer sampling can provide valuable information on the sources of PM chemicals. This knowledge is a prerequisite for their future emission control at source or substitution as an alternative to end-of-pipe treatment in municipal wastewater treatment plants.

Leaching of tire particles and simultaneous biodegradation of leachables.

The fate of organic compounds released from tire wear particle (TWP) in the aquatic environment is still poorly understood. This is especially true near sources where biotic and abiotic transformation and leaching from TWP are simultaneous and competing processes. To address this knowledge-gap an experiment was performed, allowing for biodegradation (a) during the leaching from a suspension of cryo-milled tire tread (CMTT) and (b) subsequent to leaching. Besides measuring the Dissolved Organic Carbon (DOC) content, 19 tire-related chemicals were quantified, and non-target screening was performed by LC-HRMS. The non-inoculated control experiment exhibited a DOC of up to 4 mg g-1, with up to 700 µg g-1 of 1,3-diphenylguanidine (DPG) as the most prominent compound, followed by three benzothiazoles (2-mercaptobenzothiazole (2-MBT), 2-hydroxybenzothiazole (2-OHBT) and benzothiazole-2-sulfonic acid (BTSA); 50 µg g-1 each) and 4-hydroxydiphenylamine (4-HDPA) (50 µg g-1). Biodegradation reduced the DOC by 88 % and the concentration of most organic compounds by more than 85 %. At the end of the experiment hexamethoxymethylmelamine (HMMM) was the most prominent single compounds (18 µg g-1). Non-target screening showed a more complex picture. Another 25 transformation products (TPs) of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6-PPD) and 44 TPs and derivatives related to DPG were detected in solution, of which 11 and 28 were still present after or formed by biodegradation, respectively. Of these 39 TPs and derivatives, 31 could be detected in road runoff samples. This study provides a more comprehensive picture of the leachables of tire particles that are of environmental relevance. It also outlines that derivatives of tire additives formed during tire production and use may deserve more attention as leachables. The large extent of biodegradation of tire leachables suggests that settling ponds may be a useful treatment option for road runoff.

Narrowing the analytical gap for water-soluble polymers: A novel trace-analytical method and first quantitative occurrence data for polyethylene oxide in surface and wastewater.

Water-soluble polymers (WSPs) like polyethylene oxide (PEO) have annual production volumes ranging from thousands to millions of tonnes and are used in a wide variety of applications that enable a release into the aquatic environment. Despite these facts, a lack of quantitative trace-analytical methods for WSPs prevents the comprehensive study of their environmental occurrence. Here, size exclusion chromatography was hyphenated with electrospray ionization high-resolution mass spectrometry. An all-ion fragmentation approach for the formation of diagnostic fragments independent of molecular weight, charge state, and ion species was used to quantify PEO and its derivatives in wastewater treatment plants (WWTPs) and surface water samples. Despite its inherent biodegradability, PEO concentrations found in the samples analysed ranged from 1 µg/L) and reached up to 20 µg/L (effluent) and 400 µg/L (influent) for WWTPs. A substantial shift in molecular weight ranges was observed between influent and effluent, pointing towards a molecular weight fraction between 1.3 and 4 kDa being dominant in the effluent. Due to an assumed size exclusion during sample enrichment, information on the MW-distribution of PEO is limited to MW < 55 kDa. The high concentrations widely detected for a readily biodegradable WSP such as PEO, raise strong concerns about the occurrence and fate of recalcitrant WSPs in the aquatic environment. The method presented herein may provide the tools necessary to assess the burden of these high production volume chemicals and the risk they may pose.

Efficacy of activated carbon filtration and ozonation to remove persistent and mobile substances - A case study in two wastewater treatment plants.

Persistent and mobile (PM) substances are able to spread quickly in the water cycle and were thus identified as potentially problematic for the environment and water quality. If also toxic (PMT) or very persistent and very mobile (vPvM) their regulation under REACH as substances of very high concern is foreseen. Yet, knowledge on the effectiveness of advanced wastewater treatment in removing PM-substances from WWTP effluents is limited to few rather well-known chemicals. The occurrence and behavior of 111 suspected and known PM-substances was investigated in two wastewater treatment plants employing either powdered activated carbon (PAC, full-scale) or ozonation with subsequent sand/anthracite filtration (pilot-scale) and an additional granular activated carbon (GAC) filtration was investigated. 72 of the 111 PM-substances analyzed were detected at least once in the secondary effluent of either wastewater treatment plant, resulting in total concentrations of 104 µg/L and 40 µg/L, respectively. While PAC removed 32 % of PM-substances well, the total PM burden in the effluent was only reduced from 103 µg/L to 87 µg/L. Ozonation and the subsequent sand/anthracite filtration was able to reduce the PM burden in wastewater from 40 µg/L to 19 µg/L, showing a higher removal efficacy than PAC in this study. The additional GAC filtration further reduced the total PM-concentration to 13 µg/L. Among the investigated PM-chemicals detected were constituents of ionic liquids: The anion hexafluorophosphate was one of few chemicals that was detected in effluent concentrations >1 µg/L and could not be removed by the processes studied, showing that for some chemicals preventive actions may be required.

Probing the chemical complexity of tires: Identification of potential tire-borne water contaminants with high-resolution mass spectrometry.

Tire wear particles are not only the type of polymer particles most prevalent in the environment but also act as source of various organic micropollutants, many of which are likely still unknown. We extracted particles prepared from nine tires in artificial freshwater (28 d) with the goal to characterize leachables (max intensity >105 in artificial freshwater), which are tire-borne water contaminants. A subsequent extraction of these particles with acetone (3 h) was used to assess the long-term leaching potential. A suspect and nontarget screening in aliquots of each extract led to the detection of 214 organic substances of which 145 were classified as leachables. The intrinsic polarity of some leachables (mean log D (pH 7.4) 3.9), which facilitates an increased aquatic mobility, highlights their potential as environmental water contaminants. With N,N'-diphenylguanidine (DPG) and benzothiazole, two of the ten unequivocally identified leachables, are classified as potential persistent, mobile and toxic substance by the German Environment Agency. Of the identified chemicals DPG showed the highest intensities in aqueous extracts and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6-PPD), the precursor of 6-PPD-quinone, in acetone extracts. A comparison between the 69 detected suspects and 174 high-intensity signals (>106) detected in the nontarget screening led to an overlap of only 29 features. A detailed investigation of the remaining high-intensity suspects revealed the presence of 13 proposed DPG reaction products, further highlighting the chemical complexity of tires. Consequently, we conclude that there are many, often still unrecognized chemicals entering the aquatic environment through leaching from tire wear particles.

Assessing the protection gap for mobile and persistent chemicals during advanced water treatment - A study in a drinking water production and wastewater treatment plant.

Persistent and mobile (PM) chemicals spread quickly in the water cycle and can reach drinking water. If these chemicals are also toxic (PMT) they may pose a threat to the aquatic environment and drinking water alike, and thus measures to prevent their spread are necessary. In this study, nontarget screening and cell-based toxicity tests after a polarity-based fractionation into polar and non-polar chemicals are utilized to assess and compare the effectiveness of ozonation and filtration through activated carbon in a wastewater treatment and drinking water production plant. Especially during wastewater treatment, differences in removal efficiency were evident. While median areas of non-polar features were reduced by a factor of 270, median areas for polar chemicals were only reduced by a factor of 4. Polar features showed significantly higher areas than their non-polar counterparts in wastewater treatment plant effluent and finished drinking water, implying a protection gap for these chemicals. Toxicity tests revealed higher initial toxicities (especially oxidative stress and estrogenic activity) for the non-polar fraction, but also showed a more pronounced decrease during treatment. Generally, the toxicity of the effluent was low for both fractions. Combined, these results imply a less effective removal but also a lower toxicity of polar chemicals. The behaviour of features during advanced waste and drinking water treatment was used to classify them as either PM chemicals or mobile transformation products (M-TPs). A suspect screening of the 476 highest intensity PM chemicals and M-TPs in 57 environmental and tap water samples showed high frequencies of detection (median >80%), which indicates the wide distribution of these chemicals in the aquatic environment and thus supports the chosen classification approach and the more generally applicability of obtained insights.

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.

Filling the knowledge gap: A suspect screening study for 1310 potentially persistent and mobile chemicals with SFC- and HILIC-HRMS in two German river systems.

Persistent and mobile chemicals (PM chemicals) were searched for in surface waters by hydrophilic interaction liquid chromatography (HILIC) and supercritical fluid chromatography (SFC), both coupled to high resolution mass spectrometry (HRMS). A suspect screening was performed using a newly compiled list of 1310 potential PM chemicals to the data of 11 surface water samples from two river systems. In total, 64 compounds were identified by this approach. The overlap between HILIC- and SFC-HRMS was limited (31 compounds), confirming the complementarity of the two methods used. The identified PM candidates are characterized by a high polarity (median logD -0.4 at pH 7.5), a low molecular weight (median 187 g/mol), are mostly ionic (54 compounds) and contain a large number of heteroatoms (one per four carbons on average). Among the most frequently detected novel or yet scarcely investigated water contaminants were cyanoguanidine (11/11 samples), adamantan-1-amine (10/11), trifluoromethanesulfonate (9/11), 2-acrylamido-2-methylpropanesulfonate (10/11), and the inorganic anions hexafluorophosphate (11/11) and tetrafluoroborate (10/11). 31% of the identified suspects are mainly used in ionic liquids, a chemically diverse group of industrial chemicals with numerous applications that is so far rarely studied for their occurrence in the environment. Prioritization of the findings of PM candidates is hampered by the apparent lack of toxicity data. Hence, precautionary principles and minimization approaches should be applied for the risk assessment and risk management of these substances. The large share of novel water contaminants among these findings of the suspect screening indicates that the universe of PM chemicals present in the environment has so far only scarcely been explored. Dedicated analytical methods and screening lists appear essential to close the analytical gap for PM compounds.

Making waves: Water-soluble polymers in the aquatic environment: An overlooked class of synthetic polymers?

Synthetic polymers have been one of the defining environmental topics of the last decade. Synthetic polymers in the environment are usually classified by their size. They encompass the widely discussed size fractions of macroplastic, microplastic, and nanoplastic. Water-soluble polymers (WSPs), however, are mostly absent in this discussion. In this paper, we argue that WSPs are produced in large quantities and have many applications that facilitate a discharge into the environment, where their fate and impact remain mostly unclear. We argue that there are yet no suitable analytical methods for the quantification of WSPs in environmental matrices and propose an analytical method that utilizes size exclusion chromatography - mass spectrometry to detect and potentially also quantify WSPs through specific fragments generated by in-source fragmentation. With the detection of polyethylene glycol in a wastewater treatment plant effluent and a surface water sample we provide a first prove of principle for the applicability of this novel analytical approach to WSPs. Ultimately, we conclude that WSPs are currently in a similar position as MP were in the advent of their investigation: We know of an environmental contamination but are uncertain of its extent and impact and still lack the tools to investigate them thoroughly.

Occurrence of emerging persistent and mobile organic contaminants in European water samples.

The release of persistent and mobile organic chemicals (PMOCs) into the aquatic environment puts the quality of water resources at risk. PMOCs are challenging to analyze in water samples, due to their high polarity. The aim of this study was to develop novel analytical methods for PMOCs and to investigate their occurrence in surface and groundwater samples. The target compounds were culled from a prioritized list of industrial chemicals that were modeled to be persistent, mobile, and emitted into the environment. Analytical screening methods based on mixed-mode liquid chromatography (LC), hydrophilic interaction LC, reversed phase LC, or supercritical fluid chromatography in combination with mass spectrometric detection were successfully developed for 57 target PMOCs and applied to 14 water samples from three European countries. A total of 43 PMOCs were detected in at least one sample, among them 23 PMOCs that have not been reported before to occur in environmental waters. The most prevalent of these novel PMOCs were methyl sulfate, 2-acrylamino-2-methylpropane sulfonate, benzyltrimethylammonium, benzyldimethylamine, trifluoromethanesulfonic acid, 6-methyl-1,3,5-triazine-diamine, and 1,3-di-o-tolylguanidine occurring in ≥50% of the samples at estimated concentrations in the low ng L-1 up to µg L-1 range. The approach of focused prioritization combined with sensitive target chemical analysis proved to be highly efficient in revealing a large suite of novel as well as scarcely investigated PMOCs in surface and groundwater.

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.

An integrated scale-down plant for optimal recombinant enzyme production by Pichia pastoris.

An integrated bioprocess was created in a scale-down production plant by developing a two-stage enzyme production process with Pichia pastoris, containing a cell-breeding reactor and a production reactor in combination with a three-stage downstream process. To harvest the secreted enzymes, a disc separator and a cross-flow microfiltration clear the broth from the cells. Purification with hydrophobic interaction chromatography removes other proteins, concentrates the product, and prepares the enzyme solution for lyophilization. Fully automated and broad observable multi-stage parallel process courses have been developed using industrial process control systems and at-line measurements for enzyme concentration and enzyme activity. Optimal process conditions were found by application of Design of Experiments (DoE) for the production process.