Ultraviolet photodissociation for non-target screening-based identification of organic micro-pollutants in water samples

Non-target screening (NTS) based on the combination of liquid chromatography coupled to high-resolution mass spectrometry has become the key method to identify organic micro-pollutants (OMPs) in water samples. However, a large number of compounds remains unidentified with current NTS approaches due to poor quality fragmentation spectra generated by suboptimal fragmentation methods. Here, the potential of the alternative fragmentation technique ultraviolet photodissociation (UVPD) to improve identification of OMPs in water samples was investigated. A diverse set of water-relevant OMPs was selected based on k-means clustering and unsupervised artificial neural networks. The selected OMPs were analyzed using an Orbitrap Fusion Lumos equipped with UVPD. Therewith, information-rich MS2 fragmentation spectra of compounds that fragment poorly with higher-energy collisional dissociation (HCD) could be attained. Development of an R-based data analysis workflow and user interface facilitated the characterization and comparison of HCD and UVPD fragmentation patterns. UVPD and HCD generated both unique and common fragments, demonstrating that some fragmentation pathways are specific to the respective fragmentation method, while others seem more generic. Application of UVPD fragmentation to the analysis of surface water enabled OMP identification using existing HCD spectral libraries. However, high-throughput applications still require optimization of informatics workflows and spectral libraries tailored to UVPD.ISSN:1420-304

Liquid chromatography-high-resolution mass spectrometry-based target and nontarget screening methods to characterize film-forming amine-treated steam-water systems

Film-forming amine products (FFAP) are frequently used as corrosion inhibitors in steam-water systems. To have a better understanding of their behavior in the treated system, a liquid chromatography coupled to the high-resolution mass spectrometry (LC–HRMS) method was developed. This method enabled the concurrent targeted quantitative analysis of the film-forming amine oleyl propylenediamine (OLDA) and the nontarget screening (NTS)-based analysis of potential degradation products of FFAP or other organic matter in the system. The method was applied to samples collected from an FFAP-treated industrial steam-water system. OLDA was detected at a concentration of 0.027 mg/L after the FFAP dosing in the low-pressure steam drum. A feature (a combination of mass-to-charge ratio and retention time associated with a signal intensity) prioritization workflow was designed and applied to the NTS results to focus on the potential thermal degradation products of FFAP that could affect the studied steam-water system. Six features were prioritized from a total of 4596 detected features. Structural elucidation of these features was attempted based on mass spectrometry fragmentation data. One of the prioritized features was successfully identified as 2,2′-(tridecylimino)diethanol, presumably a degradation product of the FFAP emulsifier. Because of the chemical structure of the molecule, 2,2′-(tridecylimino)diethanol was considered as noncorrosive to the system. Overall, the developed LC–HRMS method facilitated the efficient analysis of OLDA with a limit of quantification of 0.002 mg/L and a comprehensive monitoring of organic matter across the steam-water system, including potential degradation products of the dosed FFAP

Data-driven prioritization of chemicals for various water types using suspect screening LC-HRMS

For the prioritization of more than 5200 anthropogenic chemicals authorized on the European market, we use a large scale liquid chromatography-high resolution mass spectrometry (LC-HRMS) suspect screening study. The prioritization is based on occurrence in 151 water samples including effluent, surface water, ground water and drinking water.The suspect screening linked over 700 detected compounds with known accurate masses to one or multiple suspects. Using a prioritization threshold and removing false positives reduced this to 113 detected compounds linked to 174 suspects, 24 compounds reflect a confirmed structure by comparison with the pure reference standard. The prioritized compounds and suspects are relevant for detailed risk assessments after confirmation of their identity. Only one of the 174 prioritized compounds and suspects is mentioned in water quality regulations, and only 20% is mentioned on existing lists of potentially relevant chemicals. This shows the complementarity to commonly used target-based methods.The semi-quantitative total concentration, expressed as internal standard equivalents of detected compounds linked to suspects, in effluents is approximately 10 times higher than in surface waters, while ground waters and drinking waters show the lowest response. The average retention time, a measure for hydrophobicity, of the detected compounds per sample decreased from effluent to surface- and groundwater to drinking water, confirming the occurrence of more polar compounds in drinking water. The semi-quantitative total concentrations exceed the conservative and precautionary threshold of toxicological concern. Therefore, adverse effects of mixtures cannot be neglected without a more thorough risk assessment

Tracing Nitrogenous Disinfection Byproducts after Medium Pressure UV Water Treatment by Stable Isotope Labeling and High Resolution Mass Spectrometry

Advanced oxidation processes are important barriers for organic micropollutants (e.g., pharmaceuticals, pesticides) in (drinking) water treatment. Studies indicate that medium pressure (MP) UV/H₂O₂ treatment leads to a positive response in Ames mutagenicity tests, which is then removed after granulated activated carbon (GAC) filtration. The formed potentially mutagenic substances were hitherto not identified and may result from the reaction of photolysis products of nitrate with (photolysis products of) natural organic material (NOM). In this study we present an innovative approach to trace the formation of disinfection byproducts (DBPs) of MP UV water treatment, based on stable isotope labeled nitrate combined with high resolution mass spectrometry. It was shown that after MP UV treatment of artificial water containing NOM and nitrate, multiple nitrogen containing substances were formed. In total 84 N-DBPs were detected at individual concentrations between 1 to 135 ng/L bentazon-d₆ equivalents, with a summed concentration of 1.2 μg/L bentazon-d₆ equivalents. The chemical structures of three byproducts were confirmed. Screening for the 84 N-DBPs in water samples from a full-scale drinking water treatment plant based on MP UV/H₂O₂ treatment showed that 22 of the N-DBPs found in artificial water were also detected in real water samples

Fate and removal of trace pollutants from an anion exchange spent brine during the recovery process of natural organic matter and salts

The results of this sampling campaign on pilot scale processes aim to evaluate the occurrence and behavior of trace organic micro-pollutants and metal elements during anion exchange treatment of surface water and the subsequent treatment of generated spent brine with two types of electrodialysis membrane pairs. This knowledge is relevant to assess the quality and reusability of secondary products created during brine treatment; specifically the excess of sodium chloride to be recycled onsite and the natural organic matter, mostly consisting of humic substances, which find multiple applications in the agricultural industry. This study highlights that (1) the attachment mechanism of organic micro-pollutants to anion exchange resin occurs through electrostatic interaction and the subsequent transfer through ion exchange membranes is restricted by size exclusion; and (2) the complexation of trace metals compounds with the natural organic matter partly explains their removal by anion exchange. Complexes remain stable during treatment of the brine with electrodialysis.BT/Environmental BiotechnologyOLD BT/Cell Systems Engineerin

Spatial and temporal assessment of crack cocaine use in 13 European cities through wastewater-based epidemiology

Already in early 2000s, concerns have been growing in the EU about increasing use of cocaine and it is estimated that below 1% of the population administer the drug by smoking crack cocaine. New available data suggests an increase in the use of crack cocaine and an increase in the number of crack cocaine users entering treatment has been reported in several European countries. Robust estimations of crack cocaine use are however not available yet. The use of crack cocaine has long been associated with severe adverse socio-economic conditions as well as mental health problems, such as suicide ideation and depression. The aim of this study was to assess spatial trends in population-normalized mass loads of crack cocaine biomarkers (i.e., anhydroecgonine and anhydroecgonine methyl ester) in 13 European cities in six countries (the Netherlands, Belgium, Ireland, Portugal, Spain and Italy). Furthermore, temporal trends over a five-year period were evaluated through the analysis of historic samples collected in the Netherlands. Finally, the stability of the crack cocaine biomarkers in wastewater was investigated through batch experiments. The samples were analyzed with a new developed and validated hydrophilic interaction liquid chromatography coupled to mass spectrometry method. Targeted crack cocaine biomarkers were found in all cities. Also, crack cocaine biomarker was detected in wastewater from 2017 to 2021 in the Netherlands, but no significance between the years were found. With respect to biomarker in-sample stability, AEME was found to be stable in wastewater. This study assessed crack cocaine use for the first time on a broad scale, both temporal and in cities across Europe, with wastewater-based epidemiology and it shows the importance of wastewater analysis to monitor community loads of crack cocaine use

Spatial and temporal assessment of crack cocaine use in 13 European cities through wastewater-based epidemiology.

Already in early 2000s, concerns have been growing in the EU about increasing use of cocaine and it is estimated that below 1 % of the population administer the drug by smoking crack cocaine. New available data suggests an increase in the use of crack cocaine and an increase in the number of crack cocaine users entering treatment has been reported in several European countries. Robust estimations of crack cocaine use are however not available yet. The use of crack cocaine has long been associated with severe adverse socio-economic conditions as well as mental health problems, such as suicide ideation and depression. The aim of this study was to assess spatial trends in population-normalized mass loads of crack cocaine biomarkers (i.e., anhydroecgonine and anhydroecgonine methyl ester) in 13 European cities in six countries (the Netherlands, Belgium, Ireland, Portugal, Spain and Italy). Furthermore, temporal trends over a five-year period were evaluated through the analysis of historic samples collected in the Netherlands. Finally, the stability of the crack cocaine biomarkers in wastewater was investigated through batch experiments. The samples were analyzed with a new developed and validated hydrophilic interaction liquid chromatography coupled to mass spectrometry method. Targeted crack cocaine biomarkers were found in all cities. Also, crack cocaine biomarker was detected in wastewater from 2017 to 2021 in the Netherlands, but no significance between the years were found. With respect to biomarker in-sample stability, AEME was found to be stable in wastewater. This study assessed crack cocaine use for the first time on a broad scale, both temporal and in cities across Europe, with wastewater-based epidemiology and it shows the importance of wastewater analysis to monitor community loads of crack cocaine use