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Once inhaled, organic compounds in ambient PM 2.5 permeate the bloodstream, resulting in internal exposure. The intricate composition of these internalized organic molecules complicates the processes of source attribution and toxicity assessment. A systematic framework to assess the health impacts of water-soluble organic molecules (WSOMs) originating from diverse sources is still undeveloped. This study aims to comprehensively analyze the source-specific health effects of internalized organics in urban PM 2.5 through human serum albumin (HSA) non-covalent adductomes with WSOMs. Using high-resolution mass spectrometry, surface plasmon resonance, and machine learning, we mapped HSA-WSOM interactions, uncovering WSOM's potential internal exposure through its HSA adductome. The study identified eight distinct sources of internalized WSOMs, primarily from biogenic emissions, gasoline exhaust, and biomass combustion. Notably, WSOMs from these sources exhibited a predominant interaction with HSA residues ARG257, LEU238, and TRP150, substantially altering the functional dynamics of fatty acid binding site two and the hydrophobic cavity via hydrogen bonding and hydrophobic interactions. The primary health impacts of internalized WSOMs were identified as neurotoxicity and respiratory toxicity. WSOMs originating from biogenic sources and ocean emissions were mainly responsible for neurotoxic effects, whereas those from biomass burning and gasoline exhaust predominantly caused respiratory toxicity. Using the HSA adductome framework, our study identifies source-specific profiles and health effects of internally exposed WSOMs in urban PM 2.5 , emphasizing the importance of targeted mitigation strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Publicly available chemical assessments of hydraulic fracturing related waters are generally based on shale gas practices in the U.S. There is a lack of information on hydraulic fracturing related gas development from EU countries and more generally on other types of extractions. This research fills this knowledge gap by presenting chemical and bioassay assessments of hydraulic fracturing related waters from a tight gas development in the Netherlands. Fracturing fluid, flowback water and groundwater from surrounding aquifers before and after the actual fracturing were analysed by means of high resolution liquid chromatography tandem mass spectrometry, the Ames test and three chemical activated luciferase gene expression bioassays aimed at determining genotoxicity, oxidative stress response and polyaromatic hydrocarbon contamination. After sample enrichment a higher number of peaks can be found in both fracturing fluid and flowback samples. No clear differences in chemical composition were shown in the groundwater samples before and after hydraulic fracturing. Preliminary environmental fate data of the tentatively identified chemicals points towards persistence in water. Clear genotoxic and oxidative stress responses were found in the fracturing fluid and flowback samples. A preliminary suspect screening resulted in 25 and 36 matches in positive and negative ionisation respectively with the 338 possible suspect candidates on the list. Extensive measures relating to the handling, transport and treatment of hydraulic fracturing related waters are currently in place within the Dutch context. The results of the present study provide a scientific justification for such measures taken to avoid adverse environmental and human health impacts. Unlabelled Image • Lack of European hydraulic fracturing related water assessments • Chemical and bioassay assessment of Dutch hydraulic fracturing related water samples • Fracturing/flowback fluids potentially pose human and environmental health concerns. • Clear genotoxic and oxidative stress responses found for fracturing/flowback fluids • Measures justified to handle, transport and treat fracturing/flowback fluids. [ABSTRACT FROM AUTHOR]

Abstract N -nitrosodimethylamine (NDMA) is a disinfection byproduct that has been classified as probable human carcinogen by the US Environmental Protection Agency. According to the published literature, natural dissolved organic matter (DOM) can be a source of NDMA precursors in drinking water. New advances in chemical characterization of DOM with high resolution mass spectrometry (HRMS) are allowing researchers to understand these ultra-complex mixtures. The objective of this study is to investigate analytical methodologies based on HRMS to explore NDMA formation from natural waters. To this aim, different waters from drinking water reservoirs in Spain containing NDMA precursors (quantified by means of NDMA formation potential) in concentrations between 17 and 60 ng/L have been studied. The workflow includes DOM solid-phase extraction and Orbitrap analysis with and without chromatographic separation. Here, we show that the molecular composition of DOM across the studied drinking water reservoirs is correlated with the NDMA formation potential. In particular, we found that NDMA formation potential is associated with compounds with high hydrogen saturation (H/C ≥ 1.5), corresponding also to reservoirs with higher background nutrient concentrations and wastewater indicators. Further chromatographic fractionation did not allow better definition of these possible precursors as they were present in different fractions of the chromatogram, suggesting that they were isomerically complex. Graphical abstract Unlabelled Image Highlights • Orbitrap is used for DOM fingerprinting and data is visualized with Van Krevelen plots. • PCoA is used to investigate relationship between NDMA formation potential and DOM. • Compounds correlated with NDMA formation potential appear in the H/C ≥ 1.5 region. • Chromatographic separation does not provide better results than direct infusion. [ABSTRACT FROM AUTHOR]

On-site sewage treatment facilities (OSSFs), which are used to reduce nutrient emissions in rural areas, were screened for anthropogenic compounds with two-dimensional gas chromatography–mass spectrometry (GC × GC–MS). The detected compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, removal efficiency, and concentrations. This comprehensive prioritization strategy, which was used for the first time on OSSF samples, ranked galaxolide, α -tocopheryl acetate, octocrylene, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, several chlorinated organophosphorus flame retardants and linear alkyl benzenes as the most relevant compounds being emitted from OSSFs. Twenty-six target analytes were then selected for further removal efficiency analysis, including compounds from the priority list along with substances from the same chemical classes, and a few reference compounds. We found significantly better removal of two polar contaminants 2,4,7,9-tetramethyl-5-decyn-4,7-diol ( p = 0.0003) and tris(2-butoxyethyl) phosphate ( p = 0.005) in soil beds, a common type of OSSF in Sweden, compared with conventional sewage treatment plants. We also report median removal efficiencies in OSSFs for compounds not studied in this context before, viz. α -tocopheryl acetate (96%), benzophenone (83%), 2-(methylthio)benzothiazole (64%), 2,4,7,9-tetramethyl-5-decyn-4,7-diol (33%), and a range of organophosphorus flame retardants (19% to 98%). The environmental load of the top prioritized compounds in soil bed effluents were in the thousands of nanogram per liter range, viz. 2,4,7,9-tetramethyl-5-decyn-4,7-diol (3000 ng L − 1 ), galaxolide (1400 ng L − 1 ), octocrylene (1200 ng L − 1 ), and α -tocopheryl acetate (660 ng L − 1 ). [ABSTRACT FROM AUTHOR]

Aquatic environments are often contaminated with complex mixtures of chemicals that may pose a risk to ecosystems and human health. This contamination cannot be addressed with target analysis alone but tools are required to reduce this complexity and identify those chemicals that might cause adverse effects. Effect-directed analysis (EDA) is designed to meet this challenge and faces increasing interest in water and sediment quality monitoring. Thus, the present paper summarizes current experience with the EDA approach and the tools required, and provides practical advice on their application. The paper highlights the need for proper problem formulation and gives general advice for study design. As the EDA approach is directed by toxicity, basic principles for the selection of bioassays are given as well as a comprehensive compilation of appropriate assays, including their strengths and weaknesses. A specific focus is given to strategies for sampling, extraction and bioassay dosing since they strongly impact prioritization of toxicants in EDA. Reduction of sample complexity mainly relies on fractionation procedures, which are discussed in this paper, including quality assurance and quality control. Automated combinations of fractionation, biotesting and chemical analysis using so-called hyphenated tools can enhance the throughput and might reduce the risk of artifacts in laboratory work. The key to determining the chemical structures causing effects is analytical toxicant identification. The latest approaches, tools, software and databases for target-, suspect and non-target screening as well as unknown identification are discussed together with analytical and toxicological confirmation approaches. A better understanding of optimal use and combination of EDA tools will help to design efficient and successful toxicant identification studies in the context of quality monitoring in multiply stressed environments. [ABSTRACT FROM AUTHOR]

Abstract: Qualitative non-target and post-target analysis methods using gas chromatography–time-of-flight mass spectrometry were applied for analysing neutral and acidic organic xenobiotics in urban and suburban water samples. Ten water samples representing wastewater, stormwater and surface water matrices were collected and concentrated using solid phase extraction. Compound identification was performed using a spectral deconvolution program, accurate mass measurements and comparisons with library spectra. The non-target and post-target analyses identified 36 and 18 compounds, respectively. The identification of 10 compounds was afterwards confirmed with standard compounds. Organophosphate esters were the most abundant compound group detected. The combination of non-target and post-target analyses proved a useful tool in the tentative identification of xenobiotics in water samples. Post-target analysis can complement non-target analysis results at low analyte concentrations. Results showed that several organic xenobiotics originate in urban areas and accumulate in the environment. The wastewater sample produced the highest number of identified compounds, but most of these compounds were also found in stormwater samples from the city centre. Nearly all the compounds present in wastewater were additionally detected in the surface water sample taken 3km downstream from the wastewater effluent discharge point. Only a few xenobiotics were otherwise detected in the surface water samples. [Copyright &y& Elsevier]

The benchmarks to assess reproducibility are not well defined for non-target analysis. Parameters to evaluate analytical performance, such as accuracy, precision and selectivity, are well defined for target analysis, but remain elusive for non-target screening analysis. In this study, quality control (QC) guidelines are proposed to assure reliable data in non-target screening methodologies using a simple set of standards. Workflow reproducibility was assessed using an in-house QC mixture containing selected compounds with a wide range of polarity that can be detected either by electrospray ionization (ESI) in positive or negative mode. The analysis was performed by online solid phase extraction (SPE) liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). Data processing was done by a commercially available software, Compound Discoverer v. 3.0 using an environmental working template, which searched a multitude of databases, including Chemspider, EPA Toxcast, MzCloud among others. We have specifically evaluated method specificity, precision, accuracy and reproducibility in terms of peak area and retention time variability, true positive identification rate, intraday (within days) and interday (consecutive days) variations and the use of QC samples to reduce false positives. The method showed a satisfactory accuracy with an identification rate of ≥70% for most of the QC compounds. Precision estimated based on peak area relative standard deviation (RSD) ranged between 30 and 50% for most of the compounds. Data normalization to a single internal standard did not improve peak area variability. Retention time precision showed great repeatability and reproducibility (RSD ≤ 5%). In addition, a simple model of RT vs log K ow was designed based on our QC mixtures to efficiently reduced false positives by an average of 49.1%. Unlabelled Image • Intraday and interday accuracy showed an identification rate of ≥70% for most compounds. • Intraday and interday peak area precision varied largely depending on the compounds. • Retention time precision showed great repeatability and reproducibility. • Data normalization to a single internal standard did not improve variability. • A simple model of RT vs log Kow efficiently reduced false positives. [ABSTRACT FROM AUTHOR]

Industrial wastewater is characterised by a complex composition of trace organic compounds (TrOC) in a difficult matrix. The identification of unknown pollutants is of high interest. On the one hand to ensure protection of the environment by elucidating contaminations and on the other hand to protect the biological treatment step in the wastewater treatment plant (WWTP). Due to the high variability of the matrix, the identification of compounds of interest is very time consuming and often unsuccessful. To overcome this limitation, a prioritisation method was developed to identify so called ' known unknowns ', i.e. compounds frequently detected but not identified, as prioritised compounds in industrial wastewater. The method based on an offline two-dimensional (offline 2D) liquid chromatography (LC) approach with ultra violet (UV) detection in the first and high-resolution mass spectrometry (HRMS) in the second dimension. As a proof of concept, an identification process of one ' known unknown ' is described. The compound was identified as a dichlorodinitrophenol isomer by retention time in two dimensions, UV spectrum, exact mass, mass fragmentation and 1H- NMR. As prioritisation method, the offline 2D LC in combination with non-target analysis provides a powerful workflow to determine tentative structures of unknown organic compounds in industrial wastewater. Unlabelled Image • Frequently observed contaminants named ' known unknowns ' serve as prioritised compounds. • 2D offline LC-UV/LC-HRMS was used for identification. • 1st dimension provides clean-up of interfering signals and UV absorption. • 2nd dimension provides HRMS for elucidation of unknown wastewater compounds. [ABSTRACT FROM AUTHOR]