Groundwater is a major drinking water resource, but its quality is threatened by a broad variety of anthropogenic micropollutants (MPs), originating from agriculture, industry, or households, and ...undergoing various transformation processes during subsurface passage. To determine a worst-case impact of pesticide application in agriculture on groundwater quality, a target and suspect screening for more than 300 pesticides and more than 1100 pesticide transformation products (TPs) was performed in 31 Swiss groundwater samples which predominantly originated from areas with intensive agriculture. To assess additional urban contamination sources, more than 250 common urban MPs were quantified. Most of the screened pesticide TPs were experimentally observed by the pesticide producers within the European pesticide registration. To cover very polar pesticide TPs, vacuum-assisted evaporative concentration was used for enrichment, followed by liquid chromatography high-resolution tandem mass spectrometry (LC-HRMS/MS). Based on intensity, isotope pattern, retention time, and in silico fragmentation, the suspect hits were prioritised and verified. We identified 22 suspects unequivocally and five tentatively; 13 TPs are reported here for the first time to be detected in groundwater. In 13 out of 31 groundwater samples, the total concentration of the 20 identified and quantified suspects (1 pesticide and 19 pesticide TPs) exceeded the total concentration of the 519 targets (236 pesticides and TPs; 283 urban MPs) for which we screened. Pesticide TPs had higher concentrations than the parent pesticides, illustrating their importance for groundwater quality. The newly identified very polar chlorothalonil TP R471811 was the only compound detected in all samples with concentrations ranging from 3 to 2700 ng/L. Agricultural MP concentration and detection frequency correlated with agricultural land use in the catchment, except for aquifers, where protective top layers reduced MP transport from the surface. In contrast to agricultural MPs, urban MPs displayed almost no correlation with land use. The dominating entry pathway of urban MPs was river bank filtration.
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•Suspect screening in groundwater revealed 13 new pesticide transformation products.•Drinking water quality endangered by chlorothalonil transformation products.•23 of 130 detected compounds (556 quantified) above 0.1 μg/L.•Land use and hydrogeological setting strongly drove micropollutant pattern.
Surfactants are surface‐active agents widely used in numerous applications in our daily lives as personal care products, domestic, and industrial detergents. To determine complex mixtures of ...surfactants and their degradation products, unselective and rather insensitive methods, based on colorimetric and complexometric analyses are no longer employable. Analytical methodologies able to determine low concentration levels of surfactants and closely related compounds in complex matrices are required. The recent introduction of robust, sensitive, and selective mass spectrometry (MS) techniques has led to the rapid expansion of the surfactant research field including complex mixtures of isomers, oligomers, and homologues of surfactants as well as their chemically and biodegradation products at trace levels. In this review, emphasis is given to the state‐of‐the‐art MS‐based analysis of surfactants and their degradation products with an overview of the current research landscape from traditional methods involving hyphenate techniques (gas chromatography‐MS and liquid chromatography‐MS) to the most innovative approaches, based on high‐resolution MS. Finally, we outline a detailed explanation on the utilization of MS for mechanistic purposes, such as the study of micelle formation in different solvents.
The formation of chlorinated organic compounds in concrete debris exposed to reactive chlorine was studied to search for markers specific to chlorine gas exposure. Concrete materials of different ...origins were exposed to a range of species of reactive chlorine including bleach, humid and dry chlorine gas at different concentrations. Chlorinated organic compounds in concrete extracts were analysed by targeted gas and liquid chromatography-tandem mass spectrometry (GC-MS/MS and LC-MS/MS) and by non-targeted screening using the corresponding high-resolution techniques (GC-HRMS and LC-HRMS). Overall, different levels and species of chlorinated organic compounds namely chlorophenols, chlorobenzenes, chloromethoxyphenols, chloromethylbenzenes and chloral hydrate were identified in these chlorinated concrete extracts; two examples of diagnostic markers for neat chlorine exposure were trichloromethylbenzene and tetrachlorophenol. The old concrete samples from the 1930s and 1950s had the most chlorinated organic compounds after exposure to neat chlorine gas. Lignin or lignin degradation products were identified as probable candidates for phenolic precursor molecules in the concrete samples. Multivariate data analysis (OPLS-DA) shows distinct patterns for bleach and chlorine exposure. The chlorinated chemicals and specific markers for chlorine gas discovered in our research assist other laboratories in forensic investigations of chlorine gas attacks.
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•Chlorinated markers were detected by non-targeted analysis after chlorine exposure.•Tetrachlorophenol and trichloromethylbenzene are main markers of neat chlorine gas.•The concrete samples from the 1930s and 1950s had the most chlorinated compounds.•Lignin or lignin degradation products are probable phenolic precursors in concrete.•Multivariate data analysis shows distinct patterns for bleach and chlorine exposure.
Exposure science, in its broadest sense, studies the interactions between stressors (chemical, biological, and physical agents) and receptors (e.g. humans and other living organisms, and non-living ...items like buildings), together with the associated pathways and processes potentially leading to negative effects on human health and the environment. The aquatic environment may contain thousands of compounds, many of them still unknown, that can pose a risk to ecosystems and human health. Due to the unquestionable importance of the aquatic environment, one of the main challenges in the field of exposure science is the comprehensive characterization and evaluation of complex environmental mixtures beyond the classical/priority contaminants to new emerging contaminants.
The role of advanced analytical chemistry to identify and quantify potential chemical risks, that might cause adverse effects to the aquatic environment, is essential. In this paper, we present the strategies and tools that analytical chemistry has nowadays, focused on chromatography hyphenated to (high-resolution) mass spectrometry because of its relevance in this field. Key issues, such as the application of effect direct analysis to reduce the complexity of the sample, the investigation of the huge number of transformation/degradation products that may be present in the aquatic environment, the analysis of urban wastewater as a source of valuable information on our lifestyle and substances we consumed and/or are exposed to, or the monitoring of drinking water, are discussed in this article. The trends and perspectives for the next few years are also highlighted, when it is expected that new developments and tools will allow a better knowledge of chemical composition in the aquatic environment. This will help regulatory authorities to protect water bodies and to advance towards improved regulations that enable practical and efficient abatements for environmental and public health protection.
•The role of modern analytical chemistry is essential in exposure science.•Hyphenation of chromatography and HRMS allows the identification of many organic contaminants in the aquatic environment.•Different strategies (target, suspect, non-target) are used for the broad investigation of emerging chemical risks in water.•Monitoring programs and risks assessments are normally focused on parent contaminants.•Little information exists on occurrence and (eco)toxicological effects of transformation products/metabolites in water.
Plastics have become an essential part of modern society. Their properties can be easily manipulated by incorporating additives to impart desirable attributes, such as colour, flexibility, or ...stability. However, many additives are classified as hazardous substances. To better understand the risk of plastic pollution within marine ecosystems, the type and concentration of additives in plastic debris needs to be established. We report the quantification of thirty-one common plastic additives (including plasticisers, antioxidants, and UV stabilisers) in beached plastic debris collected across Aotearoa New Zealand. Additives were isolated from the plastic debris by solvent extraction and quantified using high-resolution liquid chromatography-mass spectrometry. Twenty-five of the target additives were detected across 200 items of debris, with plasticisers detected at the highest frequency (99 % detection frequency). Additives were detected in all samples, with a median of four additives per debris item. A significantly higher number of additives were detected per debris item for polyvinyl chloride (median = 7) than polyethylene or polypropylene (median = 4). The additives bis(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, and antioxidant 702 were detected at the highest concentrations (up to 196,930 μg/g). The sum concentration of additives per debris item (up to 320,325 μg/g) was significantly higher in polyvinyl chloride plastics (median 94,716 μg/g) compared to other plastic types, primarily due to the presence of phthalate plasticisers. Non-target analysis was consistent with the targeted analysis, indicating a higher number and concentration of additives in polyvinyl chloride debris items compared to all other polymer types. Feature identification indicated the presence of more additives than previously detected in the targeted analysis, including plasticisers (phthalate and non-phthalate), processing aids, and nucleating agents. This study highlights phthalates and polyvinyl chloride as key targets for consideration in ecotoxicology and risk assessments, and the development of policies to reduce the impacts of plastic pollution.
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•Beached plastic debris was collected from twenty sites in Aotearoa New Zealand.•Target quantification of plastic additives and non-target analysis was performed.•Phthalate additives were identified at highest concentration (up to 196,930 μg/g).•PVC debris contained a significantly higher number and concentrations of additives.•Non-target analysis underscored the diversity and multiplicity of additives.
Liquid chromatography coupled to quadrupole‐based tandem mass spectrometry (QqQ) is termed the “gold standard” for bioanalytical applications because of its unpreceded selectivity, sensitivity, and ...the ruggedness of the technology. More recently, however, high‐resolution mass spectrometry (HRMS) has become increasingly popular for bioanalytical applications. Nonetheless, this technique is still viewed, either as a screening technology or as a research tool. Although HRMS is actively discussed during scientific conferences, it is yet to be widely utilised in routine laboratory settings and there remains a reluctance to use HRMS for quantitative measurements in regulated environments. This paper does not aim to comprehensively describe the potential of the latest HRMS technology, but rather, it focuses on what results can be obtained and outlines the author's experiences over a period of many years of the routine application of various forms of HRMS instrumentation. Fifteen years ago, some nine different QqQ methods were used in the author's laboratory to analyse a variety of different veterinary drug resides. Today, many more analytes are quantified by seven HRMS methods and just three QqQ methods remain in use for the analysis of a small set of compounds yet to be upgraded to HRMS analysis. This continual upgrading and migration of analytical methods were accompanied by regularly participating in laboratory proficiency tests (PTs). The PT reports (covering a range of analytes and analytical methods) were used to compare the accuracy of HRMS‐ versus QqQ‐based measurements. In the second part of this paper, the particular strengths and limitations of HRMS for both method development and routine measurements are critically discussed. This also includes some anecdotal experiences encountered when replacing QqQ assays with HRMS methods.
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•SUPRAS tailoring enhances their applicability in biomass valorization.•Sponge-like SUPRAS of 1,2-octanediol were optimal for extraction of phenolics.•Both highly polar glycoside ...conjugates and less polar polyphenols were extracted.•Total phenolic content was 3 times higher than with ethanol (9.6 ± 0.2 mg GAE/g FW).•SUPRAS were made up of cosmetic authorized ingredients.
Polyphenols are one of the most appreciated antioxidants nowadays. Industry has an enormous interest in their efficient extraction from vegetal biomass, but most of current methods are neither eco-friendly nor cost-effective. Supramolecular solvents (SUPRAS), made up of self-assembled amphiphilic aggregates, have shown a great potential for the extraction of bioactives from biomass as well as for the compliance with many green chemistry criteria. Comparative studies on the extraction capability of different types of SUPRAS are essential for their application-oriented tailoring. In this study, seven SUPRAS made up of reverse hexagonal aggregates and sponge-like structures were synthesized in a variety of hydro-organic mixtures from 1-octanol and 1,2-octanediol, respectively, and their capability for the extraction of polyphenols from raspberries was evaluated. SUPRAS were characterized in terms of formation phase diagrams, composition and structure. Sponge-like SUPRAS of 1,2-octanediol, which had abundant aqueous interconnected channels (35.5–39% w/w), showed excellent solubilisation properties for both the highly polar polyphenol glycoside conjugates and the less polar polyphenols. Optimal values were obtained with SUPRAS of 1,2-octanediol and 1,3-propanediol that provided a total polyphenolic content of 9.57 ± 0.19 mg GAE/g FW sample. This value was up to three times higher than that obtained with ethanolic extracts. Polyphenol glycosides (from quercetin, naringenin, kaempferol, coumaric acid and catechin) were the predominant identified metabolites.
Endocrine disrupting chemicals are of concern because of possible human health effects, thus they are frequently included in biomonitoring studies. Current analytical methods are focused on known ...chemicals and are incapable of identifying or quantifying other unknown chemicals and their metabolites. Non-targeted analysis (NTA) methods are advantageous since they allow for broad chemical screening, which provides a more comprehensive characterization of human chemical exposure, and can allow elucidation of metabolic pathways for unknown chemicals. There are still many challenges associated with NTA, which can impact the results obtained. The chemical space, i.e., the group of known and possible compounds within the scope of the method, must clearly be defined based on the sample preparation, as this is critical in identifying chemicals with confidence. Data acquisition modes and mobile phase additives used with liquid chromatography coupled to high-resolution mass-spectrometry can affect the chemicals ionized and structural identification based on the spectral quality. In this study, a sample preparation method was developed using a novel clean-up approach with CarbonS cartridges, for endocrine-disrupting chemicals in urine, including new bisphenol A analogues and benzophenone-based UV filters, like methyl bis (4-hydroxyphenyl acetate). The study showed that data dependent acquisition (DDA) had a lower identification rate (40%) at low spiking levels, i.e., 1 ng/mL, compared to data independent acquisition (DIA) (57%), when Compound Discoverer was used. In DDA, more compounds were identified using Compound Discoverer, with an identification rate of 95% when ammonium acetate was compared to acetic acid (82%) as a mobile phase additive. TraceFinder software had an identification rate of 53% at 1 ng/mL spiking level using the DDA data, compared to 40% using the DIA data. Using the developed method, 2,4 bisphenol F was identified for the first time in urine samples. The results show how NTA can provide human exposure information for risk assessment and regulatory action but standardized reporting of procedures is needed to ensure study results are reproducible and accurate.
His Majesty the King in Right of Canada, as represented by the Minister of Health, 2024
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•A robust non-targeted analysis (NTA) method was developed to screen for endocrine disruptors in urine.•Influence of data acquisition modes on identification rate was investigated.•Influence of LC mobile phase additives on data acquisition and identification rate was investigated.•Influence of sample preparation on non-targeted analysis chemical space was studied.•Data acquisition and LC mobile phase additives in NTA need to be standardized to provide reliable and reproducible data.
Non-targeted analysis and suspect screening of per- and polyfluoroalkyl substances (PFAS) in various matrices have gained traction with advancements in accurate mass analytical instruments. This ...study employed ultra-high performance liquid chromatography coupled to quadrupole orbitrap high-resolution mass spectrometry for PFAS suspect screening of paper grades used in the paper recycling chain. The samples were prepared using two extraction techniques; selective accelerated solvent extraction with weak anionic exchange solid-phase extraction and non-selective ultrasonic-assisted extraction. A suspect screening protocol was established to tentatively identify suspected PFAS against spectral databases using a systematic approach of peak filtering and study-specific thresholds for reporting, linked to a confidence level. The possible prevalence of previously unreported PFAS in several paper materials across the various collection sites in the paper recycling chain was inferred by the common detection of short-chain polyfluoroalkyl ketones and diketones in the paper recycling chain. The suspect screening tentatively identified 41 unique PFAS, with 3 common to both pre-treatment techniques. The detection of unique PFAS by the two sample pre-treatment techniques highlighted the significance of both selective and non-selective extraction in PFAS screening endeavours. Further, it showed the importance of understanding the acquisition mechanisms employed in mass spectrometry where data-dependent acquisition triggered fragmentation in certain identified compounds, and not in others. The tentatively identified PFAS indicated that there were several previously unreported PFAS in the paper recycling chain and that additional studies were required to investigate their abundance, possible persistence, bioaccumulation and toxicity, in relation to their functional groups and carbon chains.
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•Two extraction techniques were employed for PFAS suspect screening of paper.•ASE with WAX SPE for selective extraction and UAE for non-selective extraction.•41 unique PFAS tentatively identified with 3 common to both pre-treatment techniques.•Per- and polyfluoroalkyl ketones, diketones and amines were predominantly identified.•Study showed the influence of method selectivity in the detected PFAS.
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