Publications by authors named "Thomas P Knepper"

Persistent and mobile (PM) chemicals are considered detrimental for drinking water resources as they may pass through all barriers protecting these resources against pollution. However, knowledge on the occurrence of PM chemicals in the water cycle, that make their way into drinking water resources, is still limited. The effluents of six municipal wastewater treatment plants (WWTPs, n = 38), surface water of two rivers (n = 32) and bank filtrate of one site (n = 15) were analyzed for 127 suspected PM chemicals.

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Article Synopsis
  • Proposed global regulations on PFAS have spurred research into safer alternative chemicals, leading to the investigation of two novel prototype PFAS designed for better environmental outcomes.
  • The study examined the in vitro metabolism of these prototypes in both human and rat liver fractions, revealing the production of primary metabolites like alcohols and carboxylic acids, but not complete mineralization.
  • Results indicated that rat liver enzymes metabolized the prototypes more efficiently than human liver enzymes, supporting the need for further research on the metabolic pathways and environmental impact of these alternative PFAS.
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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).

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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.

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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.

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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).

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Continuously increasing plastic production causes a constant accumulation of microplastic particles (MPs) in the aquatic environment, especially in industrialized and urbanized areas with elevated wastewater discharges. This coincides with the release of persistent organic pollutants (polycyclic aromatic hydrocarbons (PAHs), pesticides) entering limnic ecosystems. Although the assessment of potential effects of environmental pollutants sorbed to MPs under chronic exposure scenarios seems vital, data on potential hazards and risk by combined exposure to pollutants and microplastics for aquatic vertebrates is still limited.

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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.

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Given the increasing amounts of plastic debris entering marine and freshwater ecosystems, there is a growing demand for environmentally relevant exposure scenarios to improve the risk assessment of microplastic particles (MPs) in aquatic environments. So far, data on adverse effects in aquatic organisms induced by naturally exposed MPs are scarce and controversially discussed. As a consequence, we investigated the potential role of MPs regarding the sorption and transfer of environmental contaminants under natural conditions.

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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.

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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 >10 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.

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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.

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The continuously growing plastic production and incomplete recycling processes open manifold entry routes for microplastic particles (MPs) into the environment. Since knowledge on trophic transfer of contaminants sorbed to MPs is still insufficient for freshwater systems, the transfer of the model pollutant benzo(k)fluoranthene (BkF) sorbed to polymethyl methacrylate (PMMA) particles in a limnic food web was investigated: Two freshwater invertebrates (Daphnia magna and Chironomus riparius larvae) were selected and either left untreated, exposed to pristine PMMA, PMMA-associated BkF, or exposed to dissolved BkF (BkF). As second-level consumers, zebrafish (Danio rerio) were fed twice daily with pre-treated invertebrates over two days.

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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.

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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.

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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.

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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.

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Alkylphenols (APs) are chemicals of largely anthropogenic origin. Longer chain derivatives like 4-nonylphenol (4NP) or 4-tert.-octylphenol (4tOP) are mainly used for the production of alkylphenol ethoxylates, while short chain alkylphenols (SCAPs) can be applied during the production of phenolic or epoxide resins that are used in paint, glue or adhesive formulations.

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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.

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Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are applied during the production of various consumer and industrial goods. As a consequence of their use in building materials and fabrics, unreacted nonpolymeric PFASs might enter the environment by evaporation or urban run-off. Since the PFAS content of building materials and industrial fabrics is hardly investigated, studies have to be performed in order to assess their total PFAS load.

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On December 28, 2018, Carl Remigius Fresenius would have celebrated his 200th birthday. Called a father, nestor, or pioneer and forerunner of analytical chemistry, he left behind a remarkable heritage which lives on today. This journal and several others have published various articles commemorating him and more comprehensive monographies are available.

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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.

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There is a high demand for easy, cheap, comparable, and robust methods for microplastic (MP) analysis, due to the ever-increasing public and scientific interest in (micro-) plastic pollution in the environment. Today, a multitude of methodologies for sampling, sample preparation, and analysis of MPs are in use. This feature article deals with the most prominent detection methods as well as with sampling strategies and sample preparation techniques.

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More than half of the freshwater lakes in the Philippines are small with surface areas of <2 km. The dynamics in these lakes are different from those in the bigger lakes. This study was conducted to determine the organic pollutants and their sources in three of the seven lakes of San Pablo City in Laguna, Philippines: lakes Palakpakin, Sampaloc, and Pandin.

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