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This study compares the PM10 (particulate matter of diameter smaller than 10 μm) organic aerosol composition between urban and suburban stations in Heraklion, Crete, during winter 2024 in order to highlight the impact of local anthropogenic activities on urban atmospheric particulate matter pollution. Using an HPLC-ESI-MS Orbitrap analyzer (High Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometry) in full MS scan mode at a resolution of 140,000, 48 daily aerosol filter extracts were analyzed in both positive and negative modes, resulting in the detection of 2809 and 3823 features, respectively. Features with at least five times higher intensity in the urban environment compared to the suburban, and p < 0.05, were deemed significant. A correlation with black carbon (r > 0.6) was observed for 71% of significant urban features in positive mode. These features showed a predominance of low O:C ratios (<0.2) and the majority were classified as intermediate volatility organic compounds (IVOCs), indicating fresh primary emissions. A clear urban–suburban distinction was shown by PCA of positive mode features, unlike the negative mode features. Regarding the total intensity of the features, urban samples were on average 55% higher than suburban samples in positive mode and 39% higher in negative mode. This study reveals the molecular profile of locally emitted combustion related organics observed in positive mode in an urban environment. [ABSTRACT FROM AUTHOR]

Non-targeted analysis (NTA) was conducted to identify semi-volatile organic compounds (SVOCs) in a museum in China using the gas chromatography (GC)-Orbitrap-mass spectrometer (MS). Approximately 160 SVOCs were detected, of which 93 had not been reported in previous studies of museum environments. Many of the detected SVOCs were found to be associated with the chemical agents applied in conservation treatment and the materials used in furnishings. The results of hierarchical cluster analysis (HCA) indicated a spatial variation of SVOCs in the indoor air in the museum, but there were no obvious temporal differences of SVOCs observed in indoor dust. Spearman's correlation analysis showed that several classes of SVOCs were well correlated, suggesting their common sources. Fragrances and plasticizers were found to be the primary sources of SVOC pollution detected in the museum. Compared with compounds in outdoor air, indoor SVOCs had a lower level of unsaturation and more portions of chemically reduced compounds. This study is the first of its kind to comprehensively characterize SVOCs in a museum using an automated NTA approach with GC-Orbitrap-MS. The SVOCs identified in the current study are likely to be present in other similar museums; therefore, further examination of their potential impacts on cultural heritage artifacts, museum personnel, and visitors may be warranted. [ABSTRACT FROM AUTHOR]

Cotton is used for the production of textiles, hygiene and cosmetic materials. During cultivation and technological processes, various types of substances (surfactants, softeners, lubricants, etc.) penetrate cotton, which can have a harmful effect on both the human body and the environment. The aim of this study was to analyze selected cotton products in order to identify the substances contained and to describe the potential possibilities of inducing textile contact dermatitis (CD). The impact of the identified compounds on the aquatic environment was also taken into account. Nine samples of cotton clothing and seven samples of cotton pads from various manufacturers were tested. Samples after extraction using the FUSLE (Focused Ultrasonic Liquid Extraction) technique were analyzed with GC/MS. Qualitative analysis was based on comparing mass spectra with library spectra using the following mass spectra deconvolution programs: MassHunter (Agilent), AMDIS (NIST), and PARADISE (University of Copenhagen). The parameter confirming the identification of the substance was the retention index. Through the non-target screening process, a total of 36 substances were identified, with an average AMDIS match factor of approximately 900 ("excellent match"). Analyzing the properties of the identified compounds, it can be concluded that most of them have potential properties that can cause CD, also due to the relatively high content in samples. This applies primarily to long-chain alkanes (C25–C31), saturated fatty acids, fatty alcohols (e.g., oleyl alcohol), and fatty acid amides (e.g., oleamide). However, there are not many reports describing cases of cotton CD. Information on the identified groups of compounds may be helpful in the case of unexplained sources of sensitization when the skin comes into contact with cotton materials. Some of the identified compounds are also classified as dangerous for aquatic organisms, especially if they can be released during laundering. [ABSTRACT FROM AUTHOR]

Wine quality and safety is affected by the food contact materials (FCMs) used. These materials are expected to protect the beverage from any chemical, physical, or biological hazard and preserve its composition stable throughout its shelf-life. However, the migration of chemical substances from FCMs is a known phenomenon and requires monitoring. This review distinguishes the migrating chemical substances to those of (i) industrial origin with potential safety effects and those of (ii) natural occurrence, principally in cork (ex. tannins) with organoleptic quality effects. The review focuses on the migration of industrial chemical contaminants. Migration testing has been applied only for cork stoppers and tops, while other materials like polyethylene terephthalate (PET) bottles with aluminum cups, paperboard cartons, stainless steel vats, and oak casks have been examined for the presence of chemical migrating substances only by wine analysis without migration testing. The dominant analytical techniques applied are gas and liquid chromatography coupled to mass spectrometry (MS) for the determination of organic compounds and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and ICP-MS for elemental analysis. Targeted approaches are mostly applied, while limited non-target methodologies are reported. The identified migrating substances include authorized substances like phthalate plasticizers, monomers (bisphenol A), antioxidants (Irganox 1010), known but non-authorized substances (butylparaben), break-down products, oxidation products (nonylphenol), polyurethane adhesive by-products, oligomers, ink photoinitiators, and inorganic elements. A preliminary investigation of microplastics' migration has also been reported. It is proposed that further research on the development of comprehensive workflows of target, suspect, and non-target analysis is required to shed more light on the chemical world of migration for the implementation of an efficient risk assessment and management of wine contact materials. [ABSTRACT FROM AUTHOR]

Food contact materials (FCMs) from three countries were analysed for all extractable organofluorines (EOFs) from the materials and subsequently by target and non-target analysis for per- and polyfluoroalkyl substances (PFAS). The EOF varied by two orders of magnitude for FCM from UK and Saudi Arabia ranging between 2.14 and 483 ng cm−2 (0.2–48 ng g−1) showing that one quarter of all samples were above the Danish regulation for PFAS in FCM. Target PFAS showed high variability in composition and accounted for less than 1% of the EOF. Non-target PFAS screening using HPLC–ICP-MS and coupled simultaneously to HRMS showed the occurrence of organofluorines which were identified by neither LC–MS/MS nor LC–HRMS. This illustrates that the current target PFAS approaches fail to identify EOFs from FCM, which would be a problem with the new EU proposal to ban all PFAS. [ABSTRACT FROM AUTHOR]

The safety of drinking water is a significant environmental issue of great concern for human health since numerous contaminants are often detected in drinking water and its sources. Boiling is a common household method used to produce relatively high-quality drinking water in some countries and regions. In this study, with the aid of an integrated approach of in vitro bioassays and non-target analysis based on high-resolution mass spectrometry coupled with liquid chromatography, alterations in endocrine-disrupting activities in tap water samples without and with boiling were revealed, as well as the potential endocrine-disrupting chemicals (EDCs) contributing to these alterations were identified. The organic extracts of tap water had no significant (ant)agonistic activities against an estrogen receptor (ER), progesterone receptor (PR), glucocorticoid receptor (GR), and mineralocorticoid receptor (MR) at enrichment concentrations of ≤10 times, posing no immediate or acute health risk to humans. However, the presence of agonistic activities against PR and MR and antagonistic activities against ER, PR, GR, and MR in OEs of tap water at relatively higher enrichment concentrations still raise potential health concerns. Boiling effectively reduced antagonistic activities against these steroid hormone receptors (SHRs) but increased estrogenic and glucocorticoid activities in drinking water. Four novel potential EDCs, including one UV filter (phenylbenzimidazole sulfonic acid, PBSA) and three natural metabolites of organisms (beta-hydroxymyristic acid, 12-hydroxyoctadecanoic acid, and isorosmanol) were identified in drinking water samples, each of which showed (ant)agonistic activities against different SHRs. Given the widespread use of UV filters in sunscreens to prevent skin cancer, the health risks posed by PBSA as an identified novel EDC are of concern. Although boiling has been thought to reduce the health risk of drinking water contamination, our findings suggest that boiling may have a more complex effect on the endocrine-disrupting activities of drinking water and, therefore, a more comprehensive assessment is needed. [ABSTRACT FROM AUTHOR]

The main techniques, approaches, methods, and information products used in recent years for the identification of chemical compounds are summarized. The methodology used in target analysis has largely remained unchanged; only the identification criteria have undergone some adjustments. The scope of research in non-target analysis has been significantly expanded. In this case, the main problems lie in revealing candidates for identification. These versions are tested against typical criteria of target analysis. Effective search for suitable candidate compounds has become possible with the apearance of modern high-resolution chromatography–mass spectrometers and progress in informatics. The latter includes the development of algorithms and programs for processing chromatographic and mass spectrometric data; comparing them with reference values; and predicting mass spectra, retention parameters, and other quantities. Chemical databases enable the assessment of the prevalence of chemical compounds and, correspondingly, their potential as candidates for identification. [ABSTRACT FROM AUTHOR]

Non-target analyses were conducted to characterize and compare the molecular profiles (UHPLC-HRMS fingerprint) of water samples from a wastewater treatment plant (WWTP). Inlet and outlet samples were collected from three campaigns spaced 6 months apart in order to highlight common trends. A significant impact of the treatment on the sample fingerprints was shown, with a 65–70% abatement of the number of features detected in the effluent, and more polar, smaller and less intense molecules found overall compared to those in WWTP influent waters. Multivariate analysis (PCA) associated with variations of the features between inlets and outlets showed that features appearing or increasing were correlated with effluents while those disappearing or decreasing were correlated with influents. Finally, effluent features considered as relevant to a potentially adverse effect on aqueous media (i.e. those which appeared or increased or slightly varied from the influent) were highlighted. Three hundred seventy-five features common with the 3 campaigns were thus selected and further characterized. For most of them, elementary composition was found to be C, H, N, O (42%) and C, H, N, O, P (18%). Considering the MS2 spectra and several reference MS2 databases, annotations were proposed for 35 of these relevant features. They include synthetic products, pharmaceuticals and metabolites. [ABSTRACT FROM AUTHOR]

Brown carbon (BrC) absorption impacts radiative forcing and climate change. Quantifying radiative forcing of BrC requires understanding its molecular composition and absorption characteristics. While organic molecules surrounding BrC may impact its absorption, their effects have not yet been investigated. This research determined matrix effect on BrC absorption by comparing individual BrC molecules and BrC within an organic matrix. Over 20,000 water‐soluble organic molecules constituted the water‐soluble BrC and associated organic matrix. The matrix enhanced aliphatic BrC absorption but suppressed aromatic BrC, especially with higher matrix O/C ratios indicating greater polarity and acidity. By directly measuring and modeling organic matrix effect on BrC, we can improve climate prediction precision and aerosol‐radiation interaction comprehension. Plain Language Summary: In the atmosphere, organic carbon that absorb light are called brown carbon. Brown carbon can impact climate change. It is critical to understand potential factors affecting brown carbon's absorption of light. Our study proposed another potential influencing light absorbing of brown carbon, effect from organic matrix formed by co‐existing organic molecules. The matrix effect on brown carbon absorption was simulated by the absorption properties of individual molecules and the absorption contributions from the same molecules embedded within organic matrix. We found over 20,000 molecules in all samples, separating them into major contributing brown carbon molecules and co‐existing organic molecules. We found CHO and CHON formed the majority of these molecules. The organic matrix showed the different behavior to effect light absorption to different portion for organic molecules, namely aliphatic and aromatic brown carbon molecules. The brown carbon absorption was suppressed during the nighttime, with the high O/C ratio co‐existing organics. Through the direct measurement and modeling of organic matrix effect on brown carbon, the finding could improve the precision of climate predictions and enhance our comprehension of aerosol‐radiation interactions. Key Points: Organic molecules co‐existing around brown carbon constituted the organic matrixThe organic matrix enhanced aliphatic but suppressed aromatic brown carbon absorptionHigher matrix O/C ratios indicating greater polarity and acidity especially suppressed aromatic brown carbon absorption [ABSTRACT FROM AUTHOR]

Introduction: Population growth and increasing water demand have exacerbated water resource scarcity. Treated wastewater (TWW) is a valuable alternative resource, but its complex composition, including micropollutants, raises concerns about reuse risks. Reactive barriers (RB) made with natural materials offer a solution to remove TWW contaminants. Evaluating RB process effectiveness and comprehending contaminant fate remain challenging. Recent advances in High-Resolution Mass Spectrometry (HRMS) and non-target analysis (NTA) provide an opportunity to identify contaminants and evaluate RB processes. The study aims to develop an NTA approach to assess RB effectiveness and understand the NTA contribution for broadening perspectives on the impact of reactive barrier treatment.Methods: In a serie of batch experiments, TWW was mixed with a RB under two conditions: TWW in contact with RB (TWW+RB) and TWW alone (TWW). After 1 h of contact, samples were extracted and analyzed using HPLC-HRMS. NTA workflow and statistical comparison between the two sample conditions were applied for data treatment. Additionally, a quantitative method was applied to 28 pharmaceutical residues. Sorption (%) was calculated by comparing concentrations in TWW+RB and TWW experiments. NTA’s applicability for sorption estimation was investigated using intensities from differential analysis.Results: Differential analysis shows significant differences in compounds that decrease or increase after contact with BR. A prioritization workflow identified and annotated 115 compounds. Natural products predominantly increased after RB contact, while compounds exhibited a significant 75% decrease in peak area are mainly pharmaceuticals. Notably, 61% of these molecules were sorbed at more than 50%. The sorption of emerging contaminants (ECs) estimated by NTA correlated satisfactorily with sorption quantified through target analysis, although caution regarding the matrix effect is necessary.Discussion: NTA provides a comprehensive view of RB treatment performance, giving information on the compounds released by the barrier and its sorption capacity. NTA emphasizes the benefits of RB treatment while highlighting the need to study compounds reloaded by RB. It is a powerful tool for understanding the advantages of nature-based reactive barrier treatment in improving the quality of TWW.

The contamination characteristics, migration patterns and health risks of per- and polyfluoroalkyl substances (PFAS) were investigated in 66 Chinese paper products by using target and non-target screening methods. Among 57 target PFASs, 5 and 6 PFASs were found in the hygiene paper products (

Abstract Background Non-target screening of surface water samples collected over an extended period can reveal interesting temporal patterns in exposome-related pollutants. Additionally, geographical data on pollution sources close to the sampling sites, chemical classification data and the consideration of flow paths can provide valuable information on the origins and potential threat of tentatively identified chemical compounds. In this study, 271 surface water samples from 20 sampling sites across Luxembourg were analysed using high-resolution mass spectrometry, complementing routine target monitoring efforts in 2019–2022. Data analysis was performed using the open source R-package patRoon, which offers a customizable non-target workflow. By employing open source workflows featuring scoring terms, like spectral match and applying identification levels, tentative identifications can be prioritized, e.g. based on spectral similarity. Furthermore, by utilizing supplementary database information such as PubChemLite annotation categories and classification software such as classyFire, an overall assessment of the potential threats posed by the tentatively identified chemicals was conducted, enabling the prioritization of chemicals for future confirmation through targeted approaches. Results The study tentatively identified 378 compounds associated with the exposome including benzenoids, organoheterocyclic compounds, and organic phosphoric acids and derivatives (11 classyFire superclasses, 50 subclasses). The classification analysis not only revealed temporal variations in agrochemicals, with the majority of identifications occurring in May to July, but also highlighted the prevalence of pharmaceuticals such as venlafaxine in surface waters. Furthermore, potential sources of pollutants, like metallurgic industry or household products were explored by considering common uses and geographical information, as commercial uses of almost 100% of the identified chemicals are known. 41 chemicals were suggested for potential inclusion to governmental monitoring lists for further investigation. Conclusions The findings of this study complement existing knowledge on the pollution status of surface water in Luxembourg and highlight the usefulness of non-target screening for identifying temporal and spatial trends in pollutant levels. This approach, performed in a complementary manner to routine monitoring, can help to tentatively identify chemicals of concern for potential inclusion in target monitoring methods following additional confirmation and quantification efforts.

Wine quality and safety is affected by the food contact materials (FCMs) used. These materials are expected to protect the beverage from any chemical, physical, or biological hazard and preserve its composition stable throughout its shelf-life. However, the migration of chemical substances from FCMs is a known phenomenon and requires monitoring. This review distinguishes the migrating chemical substances to those of (i) industrial origin with potential safety effects and those of (ii) natural occurrence, principally in cork (ex. tannins) with organoleptic quality effects. The review focuses on the migration of industrial chemical contaminants. Migration testing has been applied only for cork stoppers and tops, while other materials like polyethylene terephthalate (PET) bottles with aluminum cups, paperboard cartons, stainless steel vats, and oak casks have been examined for the presence of chemical migrating substances only by wine analysis without migration testing. The dominant analytical techniques applied are gas and liquid chromatography coupled to mass spectrometry (MS) for the determination of organic compounds and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and ICP-MS for elemental analysis. Targeted approaches are mostly applied, while limited non-target methodologies are reported. The identified migrating substances include authorized substances like phthalate plasticizers, monomers (bisphenol A), antioxidants (Irganox 1010), known but non-authorized substances (butylparaben), break-down products, oxidation products (nonylphenol), polyurethane adhesive by-products, oligomers, ink photoinitiators, and inorganic elements. A preliminary investigation of microplastics’ migration has also been reported. It is proposed that further research on the development of comprehensive workflows of target, suspect, and non-target analysis is required to shed more light on the chemical world of migration for the implementation of an efficient risk assessment and management of wine contact materials.

Cotton is used for the production of textiles, hygiene and cosmetic materials. During cultivation and technological processes, various types of substances (surfactants, softeners, lubricants, etc.) penetrate cotton, which can have a harmful effect on both the human body and the environment. The aim of this study was to analyze selected cotton products in order to identify the substances contained and to describe the potential possibilities of inducing textile contact dermatitis (CD). The impact of the identified compounds on the aquatic environment was also taken into account. Nine samples of cotton clothing and seven samples of cotton pads from various manufacturers were tested. Samples after extraction using the FUSLE (Focused Ultrasonic Liquid Extraction) technique were analyzed with GC/MS. Qualitative analysis was based on comparing mass spectra with library spectra using the following mass spectra deconvolution programs: MassHunter (Agilent), AMDIS (NIST), and PARADISE (University of Copenhagen). The parameter confirming the identification of the substance was the retention index. Through the non-target screening process, a total of 36 substances were identified, with an average AMDIS match factor of approximately 900 (“excellent match”). Analyzing the properties of the identified compounds, it can be concluded that most of them have potential properties that can cause CD, also due to the relatively high content in samples. This applies primarily to long-chain alkanes (C25–C31), saturated fatty acids, fatty alcohols (e.g., oleyl alcohol), and fatty acid amides (e.g., oleamide). However, there are not many reports describing cases of cotton CD. Information on the identified groups of compounds may be helpful in the case of unexplained sources of sensitization when the skin comes into contact with cotton materials. Some of the identified compounds are also classified as dangerous for aquatic organisms, especially if they can be released during laundering.

Water-soluble organic molecules (WSOMs) in inhaled PM2.5 can readily translocate from the lungs into the blood circulation, facilitating their distribution to and health effects on distant organs and tissues in the human body. Human serum albumin (HSA), the most abundant protein carrier in the blood, readily binds exogenous substances to form non-covalent adducts and subsequently transports them throughout the circulatory system, thereby indicating their internal exposure. The direct internal exposure of WSOMs in PM2.5 needs to be understood. In this study, the non-covalent HSA-WSOM adductome was developed as a dosimeter to evaluate the internal exposure potential of WSOMs in urban PM2.5. The WSOM composition was acquired from non-target high-resolution mass spectrometry analysis coupled with multiple ionizations. The binding level of HSA-WSOM non-covalent adducts was obtained from surface plasma resonance. Machine learning combined WSOM composition and the binding level of HSA-WSOM non-covalent adducts to screen bindable (also internalizable) WSOMs. The concentration of WSOM ranged from 4 to 13 μg/m3 during our observation period. Of the 17,513 mass spectral features detected, 9,484 contributed to the non-covalent adductome and possessed the internal exposure potential. 102 major contributors accounted for 90.6 % of the HSA-WSOM binding level. The fraction of internalizable WSOMs in PM2.5 varied from 11.9 % to 61.3 %, averaging 26.2 %. WSOMs that have internal exposure potential were primarily lignin-like and lipid-like substances. The HSA-WSOMs non-covalent adductome represents direct internal exposure potential, which can provide crucial insights into the molecular diagnosis of PM2.5 exposure and precise assessments of PM2.5 health effects.

Abstract Brown carbon (BrC) absorption impacts radiative forcing and climate change. Quantifying radiative forcing of BrC requires understanding its molecular composition and absorption characteristics. While organic molecules surrounding BrC may impact its absorption, their effects have not yet been investigated. This research determined matrix effect on BrC absorption by comparing individual BrC molecules and BrC within an organic matrix. Over 20,000 water‐soluble organic molecules constituted the water‐soluble BrC and associated organic matrix. The matrix enhanced aliphatic BrC absorption but suppressed aromatic BrC, especially with higher matrix O/C ratios indicating greater polarity and acidity. By directly measuring and modeling organic matrix effect on BrC, we can improve climate prediction precision and aerosol‐radiation interaction comprehension.

Widespread use of spray-type consumer products can raise significant concerns regarding their effects on indoor air quality and human health. In this study, we conducted non-target screening using gas chromatography-mass spectrometry (GC-MS) to analyze VOCs in 48 different spray-type consumer products. Using this approach, we tentatively identified a total of 254 VOCs from the spray-type products. Notably, more VOCs were detected in propellant-type products which are mostly solvent-based than in trigger-type ones which are mostly water-based. The VOCs identified encompass various chemical classes including alkanes, cycloalkanes, monoterpenoids, carboxylic acid derivatives, and carbonyl compounds, some of which arouse concerns due to their potential health effects. Alkanes and cycloalkanes are frequently detected in propellant-type products, whereas perfumed monoterpenoids are ubiquitous across all product categories. Among the identified VOCs, 12 compounds were classified into high-risk groups according to detection frequency and signal-to-noise (S/N) ratio, and their concentrations were confirmed using reference standards. Among the identified VOCs, D-limonene was the most frequently detected compound (freq. 21/48), with the highest concentration of 1.80 mg/g. The risk assessment was performed to evaluate the potential health risks associated with exposure to these VOCs. The non-carcinogenic and carcinogenic risks associated with the assessed VOC compounds were relatively low. However, it is important not to overlook the risk faced by occupational exposure to these VOCs, and the risk from simultaneous exposure to various VOCs contained in the products. This study serves as a valuable resource for the identification of unknown compounds in the consumer products, facilitating the evaluation of potential health risks to consumers.

Background: Non-target screening of surface water samples collected over an extended period can reveal interesting temporal patterns in exposome-related pollutants. Additionally, geographical data on pollution sources close to the sampling sites, chemical classification data and the consideration of flow paths can provide valuable information on the origins and potential threat of tentatively identified chemical compounds. In this study, 271 surface water samples from 20 sampling sites across Luxembourg were analysed using high-resolution mass spectrometry, complementing routine target monitoring efforts in 2019–2022. Data analysis was performed using the open source R-package patRoon, which offers a customizable non-target workflow. By employing open source workflows featuring scoring terms, like spectral match and applying identification levels, tentative identifications can be prioritized, e.g. based on spectral similarity. Furthermore, by utilizing supplementary database information such as PubChemLite annotation categories and classification software such as classyFire, an overall assessment of the potential threats posed by the tentatively identified chemicals was conducted, enabling the prioritization of chemicals for future confirmation through targeted approaches. Results: The study tentatively identified 378 compounds associated with the exposome including benzenoids, organoheterocyclic compounds, and organic phosphoric acids and derivatives (11 classyFire superclasses, 50 subclasses). The classification analysis not only revealed temporal variations in agrochemicals, with the majority of identifications occurring in May to July, but also highlighted the prevalence of pharmaceuticals such as venlafaxine in surface waters. Furthermore, potential sources of pollutants, like metallurgic industry or household products were explored by considering common uses and geographical information, as commercial uses of almost 100% of the identified chemicals are known. 41 chemicals were suggested for potential inclusion to governmental monitoring lists for further investigation. Conclusions: The findings of this study complement existing knowledge on the pollution status of surface water in Luxembourg and highlight the usefulness of non-target screening for identifying temporal and spatial trends in pollutant levels. This approach, performed in a complementary manner to routine monitoring, can help to tentatively identify chemicals of concern for potential inclusion in target monitoring methods following additional confirmation and quantification efforts. [ABSTRACT FROM AUTHOR]

Anatoxins (ATXs) are a potent class of cyanobacterial neurotoxins for which only a handful of structural analogues have been well characterized. Here, we report the development of an LC–HRMS/MS method for the comprehensive detection of ATXs. Application of this method to samples of benthic cyanobacterial mats and laboratory cultures showed detection of several new ATXs. Many of these result from nucleophilic addition to the olefinic bond of the α,β-unsaturated ketone functional group of anatoxin-a (ATX) and homoanatoxin-a (hATX), analogous to the conjugation chemistry of microcystins, which contain similar α,β-unsaturated amide functionality. Conjugates with glutathione, γ-glutamylcysteine, methanethiol, ammonia, methanol and water were detected, as well as putative C-10 alcohol derivatives. Structural confirmation was obtained by simple and selective analytical-scale semisynthetic reactions starting from available ATX standards. Methanol, water and ammonia conjugates were found to result primarily from sample preparation. Reduction products were found to result from enzymatic reactions occurring primarily after cell lysis in laboratory cultures of Kamptonema formosum and Cuspidothrix issatschenkoi. The relative contributions of the identified analogues to the anatoxin profiles in a set of 22 benthic-cyanobacterial-mat field samples were estimated, showing conjugates to account for up to 15% of total ATX peak area and 10-hydroxyanatoxins up to 38%. The developed methodology, new analogues and insight into the chemical and enzymatic reactivity of ATXs will enable a more comprehensive study of the class than possible previously. [ABSTRACT FROM AUTHOR]

The safety of drinking water is a significant environmental issue of great concern for human health since numerous contaminants are often detected in drinking water and its sources. Boiling is a common household method used to produce relatively high-quality drinking water in some countries and regions. In this study, with the aid of an integrated approach of in vitro bioassays and non-target analysis based on high-resolution mass spectrometry coupled with liquid chromatography, alterations in endocrine-disrupting activities in tap water samples without and with boiling were revealed, as well as the potential endocrine-disrupting chemicals (EDCs) contributing to these alterations were identified. The organic extracts of tap water had no significant (ant)agonistic activities against an estrogen receptor (ER), progesterone receptor (PR), glucocorticoid receptor (GR), and mineralocorticoid receptor (MR) at enrichment concentrations of ≤10 times, posing no immediate or acute health risk to humans. However, the presence of agonistic activities against PR and MR and antagonistic activities against ER, PR, GR, and MR in OEs of tap water at relatively higher enrichment concentrations still raise potential health concerns. Boiling effectively reduced antagonistic activities against these steroid hormone receptors (SHRs) but increased estrogenic and glucocorticoid activities in drinking water. Four novel potential EDCs, including one UV filter (phenylbenzimidazole sulfonic acid, PBSA) and three natural metabolites of organisms (beta-hydroxymyristic acid, 12-hydroxyoctadecanoic acid, and isorosmanol) were identified in drinking water samples, each of which showed (ant)agonistic activities against different SHRs. Given the widespread use of UV filters in sunscreens to prevent skin cancer, the health risks posed by PBSA as an identified novel EDC are of concern. Although boiling has been thought to reduce the health risk of drinking water contamination, our findings suggest that boiling may have a more complex effect on the endocrine-disrupting activities of drinking water and, therefore, a more comprehensive assessment is needed.

Abstract Non-target analysis combined with liquid chromatography high resolution mass spectrometry is considered one of the most comprehensive strategies for the detection and identification of known and unknown chemicals in complex samples. However, many compounds remain unidentified due to data complexity and limited number structures in chemical databases. In this work, we have developed and validated a novel machine learning algorithm to predict the retention index (r $$_i$$ i ) values for structurally (un)known chemicals based on their measured fragmentation pattern. The developed model, for the first time, enabled the predication of r $$_i$$ i values without the need for the exact structure of the chemicals, with an $$R^2$$ R 2 of 0.91 and 0.77 and root mean squared error (RMSE) of 47 and 67 r $$_i$$ i units for the NORMAN ( $$n=3131$$ n = 3131 ) and amide ( $$n=604$$ n = 604 ) test sets, respectively. This fragment based model showed comparable accuracy in r $$_i$$ i prediction compared to conventional descriptor-based models that rely on known chemical structure, which obtained an $$R^2$$ R 2 of 0.85 with an RMSE of 67.

Of the different quality parameters of any food commodity or beverage, color is the most important, attractive and choice-affecting sensory factor to consumers and customers. Nowadays, food industries are interested in making the appearance of their food products attractive and interesting in order to appeal to consumers/customers. Natural green colorants have been accepted universally due to their natural appeal as well as their nontoxic nature to consumers. In addition, several food safety issues mean that natural green colorants are preferable to synthetic food colorants, which are mostly unsafe to the consumers but are less costly, more stable, and create more attractive color hues in food processing. Natural colorants are prone to degradation into numerous fragments during food processing, and thereafter, in storage. Although different hyphenated techniques (especially high-performance liquid chromatography (HPLC), LC-MS/HRMS, and LC/MS-MS are extensively used to characterize all these degradants and fragments, some of them are not responsive to any of these techniques, and some substituents in the tetrapyrrole skeleton are insensitive to these characterization tools. Such circumstances warrant an alternative tool to characterize them accurately for risk assessment and legislation purposes. This review summarizes the different degradants of chlorophylls and chlorophyllins under different conditions, their separation and identification using various hyphenated techniques, national legislation regarding them, and the challenges involved in their analysis. Finally, this review proposes that a non-targeted analysis method that combines HPLC and HR-MS assisted by powerful software tools and a large database could be an effective tool to analyze all possible chlorophyll and chlorophyllin-based colorants and degradants in food products in the future. [ABSTRACT FROM AUTHOR]

Unsymmetrical dimethylhydrazine (UDMH) is a widely used rocket propellant. Entering the environment or being stored in uncontrolled conditions, UDMH easily forms an enormous variety (at least many dozens) of transformation products. Environmental pollution by UDMH and its transformation products is a major problem in many countries and across the Arctic region. Unfortunately, previous works often use only electron ionization mass spectrometry with a library search, or they consider only the molecular formula to propose the structures of new products. This is quite an unreliable approach. It was demonstrated that a newly proposed artificial intelligence-based workflow allows for the proposal of structures of UDMH transformation products with a greater degree of certainty. The presented free and open-source software with a convenient graphical user interface facilitates the non-target analysis of industrial samples. It has bundled machine learning models for the prediction of retention indices and mass spectra. A critical analysis of whether a combination of several methods of chromatography and mass spectrometry allows us to elucidate the structure of an unknown UDMH transformation product was provided. It was demonstrated that the use of gas chromatographic retention indices for two stationary phases (polar and non-polar) allows for the rejection of false candidates in many cases when only one retention index is not enough. The structures of five previously unknown UDMH transformation products were proposed, and four previously proposed structures were refined. [ABSTRACT FROM AUTHOR]

Background: Per- and polyfluorinated alkyl substances (PFAS) have received increasing scientific and political attention in recent years. Several thousand commercially produced compounds are used in numerous products and technical processes. Due to their extreme persistence in the environment, humans and all other life forms are, therefore, increasingly exposed to these substances. In the following review, PFAS will be examined comprehensively. Results: The best studied PFAS are carboxylic and sulfonic acids with chain lengths of C4 to C14, particularly perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). These substances are harmful to aquatic fauna, insects, and amphibians at concentrations of a few µg/L or less, accumulate in organisms, and biomagnify in food webs. Humans, as the final link in numerous food chains, are subjected to PFAS uptake primarily through food and drinking water. Several PFAS have multiple toxic effects, particularly affecting liver, kidney, thyroid, and the immune system. The latter effect is the basis for the establishment of a tolerable weekly dose of only 4.4 ng/kg body weight for the sum of the four representatives PFOA, PFOS, perfluorononanoic acid (PFNA) and perfluorohexane sulfonic acid (PFHxS) by the European Food Safety Authority (EFSA) in 2020. Exposure estimates and human biomonitoring show that this value is frequently reached, and in many cases exceeded. PFAS are a major challenge for analysis, especially of products and waste: single-substance analyses capture only a fragment of the large, diverse family of PFAS. As a consequence, sum parameters have gained increasing importance. The high mobility of per and polyfluorinated carboxylic and sulfonic acids makes soil and groundwater pollution at contaminated sites a problem. In general, short-chain PFAS are more mobile than long-chain ones. Processes for soil and groundwater purification and drinking water treatment are often ineffective and expensive. Recycling of PFAS-containing products such as paper and food packaging leads to carryover of the contaminants. Incineration requires high temperatures to completely destroy PFAS. After PFOA, PFOS and a few other perfluorinated carboxylic and sulfonic acids were regulated internationally, many manufacturers and users switched to other PFAS: short-chain representatives, per- and polyfluorinated oxo carboxylic acids, telomeric alcohols and acids. Analytical studies show an increase in environmental concentrations of these chemicals. Ultra-short PFAS (chain length C1–C3) have not been well studied. Among others, trifluoroacetic acid (TFA) is present globally in rapidly increasing concentrations. Conclusions: The substitution of individual PFAS recognized as hazardous by other possibly equally hazardous PFAS with virtually unknown chronic toxicity can, therefore, not be a solution. The only answer is a switch to fluorine-free alternatives for all applications in which PFAS are not essential. [ABSTRACT FROM AUTHOR]

Non-target analysis combined with liquid chromatography high resolution mass spectrometry is considered one of the most comprehensive strategies for the detection and identification of known and unknown chemicals in complex samples. However, many compounds remain unidentified due to data complexity and limited number structures in chemical databases. In this work, we have developed and validated a novel machine learning algorithm to predict the retention index (r i ) values for structurally (un)known chemicals based on their measured fragmentation pattern. The developed model, for the first time, enabled the predication of r i values without the need for the exact structure of the chemicals, with an R 2 of 0.91 and 0.77 and root mean squared error (RMSE) of 47 and 67 r i units for the NORMAN ( n = 3131 ) and amide ( n = 604 ) test sets, respectively. This fragment based model showed comparable accuracy in r i prediction compared to conventional descriptor-based models that rely on known chemical structure, which obtained an R 2 of 0.85 with an RMSE of 67. [ABSTRACT FROM AUTHOR]

An important task of physical chemistry is to predict the properties of chemical compounds from their structure. Prediction of the chromatographic retention allows one to reject false candidates in gas chromatography/mass spectrometry analysis and to elucidate structures of unknown compounds. Immediately after establishing the structure of an unknown analyte, the next task is to predict its properties, in particular, toxicity. In this work, the problem of prediction of gas chromatographic retention is considered in detail. A new method for predicting the retention indices on different stationary phases using regression learning is demonstrated in relation to flavors and fragrances. The achieved accuracy is higher than the accuracy of previously published methods. The median absolute error does not exceed 14 units. In addition, prediction of acute toxicity from the molecular structure is considered. The efficiency of various regression learning methods for predicting retention indices and acute toxicity (median lethal dose) of chemical compounds is compared. [ABSTRACT FROM AUTHOR]

[Display omitted] • Non-target PAEs found in raw leachate could transform to target PAEs in SCWO. • The suggested pathway for PAEs includes substitution and binding reactions. • The temperature was the most important variable for PAEs and macro organics removal. • DEHP, DNOP and BBP were eliminated 100%, 92% and 36%, respectively in SCWO. • Maximum mineralization rate for total PAEs was found as 97% in sub-critical conditions. The hypothesis of this study is that the complex organic load of landfill leachate could be reduced by supercritical water oxidation (SCWO) in a single stage, but this operation could lead to the formation of some undesired by-products of phthalate esters (PAEs). In this context, the fate of selected PAEs, butyl benzyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP) and di-n-octyl phthalate (DNOP), was investigated during the oxidation of leachate under subcritical and supercritical conditions. Experiments were conducted at various temperatures (250–500 °C), pressures (10–35 MPa), residence times (2–18 min) and dimensionless oxidant doses (DOD: 0.2–2.3). The SCWO process decreased the leachate's chemical oxygen demand (COD) from 34,400 mg/L to 1,120 mg/L (97%). Removal efficiencies of DEHP and DNOP with longer chains were higher than BBP. The DEHP, DNOP and BBP compounds were removed in the range of −35 to 100%, −18 to 92%, and 28 to 36%, respectively, by the SCWO process. Many non-target PAEs were qualitatively detected in the raw leachate apart from the selected PAEs. Besides, 97% of total PAEs including both target and non-target PAEs was mineralized at 15 MPa, 300 °C and 5 min. Although PAEs were highly mineralized during SCWO of the leachate, aldehyde, ester, amide and amine-based phthalic substances were frequently detected as by-products. These by-products have transformed into higher molecular weight by-products with binding reactions as a result of complex SCWO process chemistry. It has also been determined that some non-target PAEs such as 1,2-benzenedicarboxylic acid bis(2-methylpropyl)ester and bis(2-ethylhexyl) isophthalate can transform to the DEHP. Therefore, the suggested pathway in this study for PAEs degradation during the SCWO of the leachate includes substitution and binding reactions as well as an oxidation reaction. [ABSTRACT FROM AUTHOR]

The development of analytical methodologies to monitor different antibiotic families in water and the implementation of alternatives for their efficient elimination are a great challenge. The aim of this research was to develop a method based on solid-phase extraction followed by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry to analyse multi-class antibiotics, including macrolides, cephalosporins, fluoroquinolones, sulfonamides and diaminopyrimidines, in waters. Several parameters affecting the extraction such as the sample pH, type of sorbent and cartridge, elution volume and breakthrough volume were optimized. The method was validated in real samples, and matrix effect was assessed, demonstrating that the use of isotopically labelled surrogate compounds was mandatory to avoid standard addition calibration for each individual samples. Urban and hospital wastewater samples, as well as natural waters, were analysed, confirming the presence of 12 of the 14 target compounds at concentrations up to 3.5 µg L−1. Non-target analysis based on data-independent workflow was also performed, enabling the identification of 94 pollutants. Preliminary photodegradation experiments were also assessed, revealing the total removal of many target compounds after the first 5–10 min of UVC irradiation. In addition, 20 by-products formed after photolysis could be identified using a non-target approach. [ABSTRACT FROM AUTHOR]

The cucurbitane-type triterpenoids of Momordica charantia Linn. have blood lipid lowering effect and thereby improving non-alcoholic fatty liver. In this study, microwave-assisted extraction efficiently obtained these compounds which were further confirmed by the use of UPLC-MS/MS for target analysis and LC-HRMS for non-target analysis, combining GNPS techniques. The results indicated that the content of cucurbitane-type triterpenoids in bitter melon Hualien No. 5 was the highest among the others. Except for the immature whole fruit, the other plant parts such as fruits, seeds, vines and the whole plant of Hualien No. 5 with different maturity levels of immature, mature and overripe can significantly inhibit lipid accumulation in hepatocytes induced by oleic acid. The vines were proven as the most significant among the others where the active components for improving non-alcoholic fatty liver were rapidly screened and identified as 3β,7β,25-trihydroxycucurbita-5,23 (E)-dien-19-al and Momordicine II through non-target analysis, multivariate analysis and molecular network. [Display omitted] • M. charantia cultivars can help alleviate non-alcoholic fatty liver. • Cucurbitane-type triterpenoids are major phytochemicals in M. charantia. • 3β,7β,25-trihydroxycucurbita-5,23 (E)-dien-19-al and Momordicine II target non-alcoholic fatty liver. • Molecular networking and analysis can explore functional compounds widely. [ABSTRACT FROM AUTHOR]

Increasing use of scrubbers on vessels for reduction of SOx emissions has led to environmental concerns due to discharge of partly persistent and toxic substances such as polycyclic aromatic compounds (PAC) into the sea. A comprehensive analysis of the dissolved and particulate phases of the discharge water from open and closed loop operations on four ships was performed. 71 PAC in the discharge waters varied in concentration and were associated with those of the fuels used, as they mainly originate in unburnt fuel. Closed loop discharge water showed higher PAC concentrations, especially of HMW PAC, which partly explains the larger toxic effects reported for this discharge. Alkylnaphthalenes and -phenanthrenes dominated in dissolved and particulate fractions, respectively. 14 NSO-PAC concentrations were relatively low. Alkylated derivatives of 4 H -cyclopenta[4,5- def ]phenanthrene and/or phenylnaphthalene were for the first time tentatively identified using GC-APLI-MS. The use of low-PAC fuels could significantly reduce PAC ship emissions. [Display omitted] • Open and closed loop scrubber discharge water and fuels from four ships were studied. • Dissolved and particulate fractions of discharge and fuels were analyzed for 85 PAC. • Closed Loop concentrations of (particulate) PAC were higher than open loop scrubber. • Alkylated cyclopenta[ def ]phenanthrene/phenylnaphthalene were tentatively identified. • Dioxin-like effects and concentration of certain PAC correlate strongly. [ABSTRACT FROM AUTHOR]

This study utilized liquid chromatography (LC) alongside Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to explore the dyes and chemical contaminants in Loji River, Indonesia. We tentatively identified a total of 655 contaminants at various confidence level, subsequently classifying them into 22 distinct categories. Of the 54 dyes we detected, 12 corresponded with entries in our specialized in-house database. These 12 dyes were further confirmed by reference standards, matching both retention time (RT) and MS/MS spectra. LC-FT-ICR MS data showed that dyes from printing batik and textile industries are key contributors to river pollution. Particularly noteworthy were two sample locations that displayed substantial contamination, predominantly from azoic and reactive dyes. Additionally, pharmaceuticals were identified as one of the most frequently occurring contaminants, underscoring the inadequacies in the area's sewage management. To corroborate these findings, we conducted physicochemical, phytotoxicity, and acute toxicity tests, all of which verified the harmful effects of the Loji River's water on both the local flora and human populations. Notably, water samples that tested positive for dye contamination exhibited elevated toxicity levels. To the best of our knowledge, this study is pioneering in its molecular-level investigation of dye contamination in Southeast Asian rivers. Our results accentuate the pressing need for both targeted and non-targeted screening methods to identify contaminants in the surface waters of developing nations. [Display omitted] • Screening of dyes and potential contaminants in the Loji River with LC-FT-ICR MS. • A total of 655 contaminants were tentatively identified and classified into 22 categories. • Out of 54 dyes, with 12 of them matching entries in an in-house dye database. • Batik textile industries were major contributors to the river's dye pollution. • Toxicity tests confirmed the detrimental effects of Loji River surface water. [ABSTRACT FROM AUTHOR]

Various industries produce a myriad of synthetic molecules used to satisfy our needs, but all these molecules are likely to reach aquatic environments. The number of organic contaminants found in rivers and lakes continues to rise, and part of this contamination gets transferred into sediments. Analytical methods to detect problematic substances in the environment often use mass spectrometry coupled with chromatography. Here we reviewed a set of 163 articles and compiled the relevant information into a comprehensive database for analysing organic contaminants in continental sediments including suspended particulate matter and surface and bottom sediments in lakes, rivers and estuaries. We found 1204 compounds detected at least once in sediments, and classified them into 11 categories, i.e. hydrocarbons, flame retardants, polychlorinated biphenyls (PCB), plasticizers, per- and poly-fluoroalkyl substances (PFAS), organochlorines (OCP) and other pesticides, pharmaceuticals, hormones, personal care products (PCP), and other contaminants. Concentrations of these compounds varied from a few ng to several mg/kg of dry sediment. Even hydrophilic compounds were detected in high concentrations. Well-known hydrophobic and persistent contaminants tend to be analysed with mass spectrometry coupled to gas chromatography (GC-MS) whereas contaminants of emerging concern (CEC) are usually analysed with liquid chromatography– mass spectrometry (LC-MS). Suspect screening and non-target analysis (NTA), which use high-resolution mass spectrometry, are still scarcely used on sediment but hold promise for gaining deeper knowledge of organic contamination in aquatic environments. [Display omitted] • Continental sediments store a wide array of organic contaminants. • Even highly hydrophilic compounds have been detected at high concentrations. • LC-HRMS is the method of choice to explore contaminants of emerging concerns. • Non-target analysis can help gain deeper knowledge of aquatic contaminants. [ABSTRACT FROM AUTHOR]

In an attempt to discover and characterize the plethora of xenobiotic substances, this study investigates chemical compounds released into the environment with wastewater effluents. A novel non-targeted screening methodology based on ultra-high resolution Orbitrap mass spectrometry and nanoflow ultra-high performance liquid chromatography together with a newly optimized data-processing pipeline were applied to effluent samples from two state-of-the-art and one small wastewater treatment facility. In total, 785 molecular structures were obtained, of which 38 were identified as single compounds, while 480 structures were identified at a putative level. Most of these substances were therapeutics and drugs, present as parent compounds and metabolites. Using R packages Phyloseq and MetacodeR, originally developed for bioinformatics, significant differences in xenobiotic presence in the wastewater effluents between the three sites were demonstrated. • The study characterizes a wide spectrum of xenobiotics detected in Danish effluents. • An optimized data-processing pipeline, previously used in microbial ecology, was employed for analysis of chemical data. • 785 chemical structures were identified in the analysis, with the majority classified as therapeutics and drugs. • Several compounds identified are known or suspected endocrine disruptors. • The data reveals significant difference in compound diversity between wastewater effluent at the three sites. [ABSTRACT FROM AUTHOR]

Organophosphate esters (OPEs) are emerging contaminants that serve as alternatives to regulated substances in aquatic environments. A nationwide large-scale assessment for OPEs, including point sources, remains insufficient. To address this issue, we aimed to investigate OPEs occurrence and novel OPEs via comprehensive target, suspect and non-target analysis. Among the 11 target OPEs, 10 were detected at sampling sites distributed evenly nationwide. The highest mean concentrations were measured for tris-(2-butoxyethyl) phosphate (TBOEP) and tris(2-chloroisopropyl) phosphate (TCIPP). The multivariate statistical analysis revealed that TBOEP and TCIPP are essential components for assessing total OPEs pollution. The systematic risk assessment results evaluated the overall risk contribution of TBOEP and the significant risk impact of 2-ethylhexyl diphenyl phosphate. Promising suspect and non-target analysis enabled frequent detection and identification of 6 antioxidant transformation products (TPs), as well as the tentative identification of 14 OPEs and TPs, including 3 di-OPEs. Based on sampling site classification, we confirmed that major OPEs are significantly discharged near point sources. We believe that this is the first attempt to assess the nationwide risk and potential sources of OPEs in Korean surface waters, providing insights that could support further prioritization and regulation efforts., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Junho Jeon reports financial support was provided by Changwon National University. If there are other authors, they 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 Elsevier Ltd. All rights reserved.)

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.)

The routine use of chemicals in polar regions contributes to unexpected occurrence of micropollutants, with sewage discharge as a prominent pollution source. The aim of this study was to identify and quantify micropollutants in polar environments near potential point sources using non-target analysis (NTA) with liquid chromatography high-resolution mass spectrometry. Seawater samples were collected from Ny-Ålesund, Svalbard and Marian Cove, King George Island, in 2023. We tentatively identified 32 compounds with NTA, along with 105 homologous series substances. Of these, 18 substances were confirmed, and 13 were quantified using the internal standard method. Most quantified substances in the Ny-Ålesund, including caffeine, naproxen, and polyethylene glycols (PEGs), exhibited concentrations ranged from 0.9 to 770,000 ng/L. In Marian Cove, the analysis predominantly detected acetaminophen, with concentrations ranging from 13 to 35 ng/L. The findings underscore the presence and spatial distribution of emerging micropollutants resulting from wastewater discharge in polar regions., 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 Ltd.)

Producers of drinking water (DW) occasionally require chemical identification of new or unexpected contamination, e.g., caused by an incident. The state-of-the-art technique for the identification of organic compounds is High-Resolution Mass Spectrometry (HRMS). The ability to discover unexpected compounds at low concentrations in any sample by HRMS is facilitated by comparison to non-contaminated reference samples. Samples of raw and drinking water were collected regularly over one whole year from six Swedish drinking water treatment plants (DWTPs). The samples were analyzed by LC-HRMS together with spiked samples mimicking an incident. This setup enabled evaluation of the significance of having access to a collection of matrix-matched reference samples. The main variation in the organic compound profile in the data set was explained by the uniqueness of the raw water and purification steps in the individual DWTPs. Seasonal variations were also significant but subordinate. This subject was further explored by the analysis of drinking water sampled once from 90 of the 1750 Swedish DWTPs, where a similarity between DW originating from rock aquifers was observed. No other significant correlation between samples was observed—e.g., other types of raw water, which types of purification steps were involved, or which additives or process chemicals were added—which could aid in the selection of relevant reference samples. The conclusion from the study is that it would be imperative for the DWTPs to have access to their individual reference samples for use in the investigation of an incident. A library of such reference samples, e.g., collected monthly and covering the last 12 months, could be stored and used together with a fresh "suspected sample" for non-target HRMS investigations as described. [ABSTRACT FROM AUTHOR]

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Copyright of Journal of Ecology & Rural Environment is the property of Journal of Ecology & Rural Environment Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Of the different quality parameters of any food commodity or beverage, color is the most important, attractive and choice-affecting sensory factor to consumers and customers. Nowadays, food industries are interested in making the appearance of their food products attractive and interesting in order to appeal to consumers/customers. Natural green colorants have been accepted universally due to their natural appeal as well as their nontoxic nature to consumers. In addition, several food safety issues mean that natural green colorants are preferable to synthetic food colorants, which are mostly unsafe to the consumers but are less costly, more stable, and create more attractive color hues in food processing. Natural colorants are prone to degradation into numerous fragments during food processing, and thereafter, in storage. Although different hyphenated techniques (especially high-performance liquid chromatography (HPLC), LC-MS/HRMS, and LC/MS-MS are extensively used to characterize all these degradants and fragments, some of them are not responsive to any of these techniques, and some substituents in the tetrapyrrole skeleton are insensitive to these characterization tools. Such circumstances warrant an alternative tool to characterize them accurately for risk assessment and legislation purposes. This review summarizes the different degradants of chlorophylls and chlorophyllins under different conditions, their separation and identification using various hyphenated techniques, national legislation regarding them, and the challenges involved in their analysis. Finally, this review proposes that a non-targeted analysis method that combines HPLC and HR-MS assisted by powerful software tools and a large database could be an effective tool to analyze all possible chlorophyll and chlorophyllin-based colorants and degradants in food products in the future.

Japanese radish (Raphanus sativus var. longipinnatus) plants grown under laboratory conditions were individually exposed to the same doses of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, ATR) or its main degradation products: either 2-amino-4-chloro-6-isopropylamino-1,3,5-triazine (DEA) or 2-amino-4-chloro-6-ethylamino-1,3,5-triazine (DIA) or desethyl-desisopropyl-atrazine (DEDIA) or 4-(ethylamino)-2-hydroxy-6-(isopropylamino)-1,3,5-triazine (HA), respectively. One week after treatment in plants exposed to ATR, DIA, and DEA, their concentrations were 7.8 μg/g, 9.7 μg/g, and 14.5 μg/g, respectively, while those treated with DEDIA and HA did not contain these compounds. These results were correlated with plant amino acid profile obtained by suspect screening analysis and metabolomic "fingerprint" based on non-target analysis, obtained by liquid chromatography coupled with QTRAP triple quadrupole mass spectrometer. In all cases, both ATR and its by-products were found to interfere with the plant's amino acid profile and modify its metabolic "fingerprint". Therefore, we proved that the non-target metabolomics approach is an effective tool for investigating the hidden effects of pesticides and their transformation products, which is particularly important as these compounds may reduce the quality of edible plants. [Display omitted] • Atrazine and its degradation products disrupt the plant's amino acid profile. • Metabolic changes induced by atrazine may influence protein quality of crop plants. • ATR and its metabolites content in plants varies despite the same exposure dose. [ABSTRACT FROM AUTHOR]

• UV-327 was the major traditional BZT-UVs in surface water from TL and QR. • A characteristic fragment ion-based strategy was developed to screen unknown BZT-UVs. • Seven novel BZT-UVs were discovered in surface water from TL and QR. • Four novel BZT-UVs were further confirmed with their native standards. The comprehensive understanding of the occurrence of benzotriazole UV stabilizers (BZT-UVs) in environmental surface water is imperative due to their widespread application and potential aquatic toxicity. We conducted an analysis of 13 traditional BZT-UVs in surface water samples collected from Taihu Lake (TL, n = 23) and Qiantang River (QR, n = 22) in China. The results revealed that 5‑chloro-2-(3,5-di-tertbutyl-2-hydroxyphenyl)-benzotriazole (UV-327) was consistently the predominant BZT-UV in water samples from TL (mean 16 ng/L; detection frequency 96 %) and QR (14 ng/L; 91 %). Furthermore, we developed a characteristic fragment ion-based strategy to screen and identify unknown BZT-UVs in collected surface water, utilizing a high-resolution mass spectrometer. A total of seven novel BZT-UVs were discovered in water samples, and their chemical structures were proposed. Four of these novel BZT-UVs were further confirmed with standards provided by industrial manufacturers. Semi-quantitative analysis revealed that among discovered novel BZT-UVs, 2-(2‑hydroxy-3‑tert‑butyl‑5-methylphenyl)-benzotriazole was consistently the predominant novel BZT-UV in TL (mean 4.1 ng/L, detection frequency 70 %) and QR (2.8 ng/L, 77 %) water. In TL water, the second predominant novel BZT-UV was 2-(3-allyl-2‑hydroxy-5-methylphenyl)-2H-benzotriazole (mean 3.9 ng/L,

Compared to metabolomics, exposomics imposes more stringent requirements for analytical methods, owing to the trace concentrations of exposure chemicals and their complex biotransformation processes. A promising strategy to overcome the challenges in exposomic analysis is suspect screening analysis (SSA). This approach enhances the selectivity, efficiency, and accuracy of analysis by identifying specific parent-product pairs using tandem mass spectrometry (MS/MS). Based on the spectrum information employed in SSA, we have classified the current methods into four primary categories in this review. These include spectral database-based screening, substructure-guided screening, experimental spectrum-based screening, and derivatization-assisted screening. These strategies have evolved into the multiple reaction monitoring (MRM) method through the selection of characteristic fragment ions, optimization of collision energy (CE) and determination of retention time (RT). Furthermore, we evaluated their scope of application and highlighted that advancements in spectral prediction, the acquisition of high-quality MS/MS data, and the computational establishment of robust MS/MS features for SSA. • Suspect screening analysis (SSA) is a pivotal methodology in exposome research. • Substructure-guided suspect screening is a good way to identify exposure biomarkers. • Derivatization is used to develop a robust multiple reaction monitoring (MRM) method. • MS/MS data mining strategy shows promising potential in further advancement of SSA. [ABSTRACT FROM AUTHOR]

Unsymmetrical dimethylhydrazine (UDMH) is a widely used rocket propellant. Entering the environment or being stored in uncontrolled conditions, UDMH easily forms an enormous variety (at least many dozens) of transformation products. Environmental pollution by UDMH and its transformation products is a major problem in many countries and across the Arctic region. Unfortunately, previous works often use only electron ionization mass spectrometry with a library search, or they consider only the molecular formula to propose the structures of new products. This is quite an unreliable approach. It was demonstrated that a newly proposed artificial intelligence-based workflow allows for the proposal of structures of UDMH transformation products with a greater degree of certainty. The presented free and open-source software with a convenient graphical user interface facilitates the non-target analysis of industrial samples. It has bundled machine learning models for the prediction of retention indices and mass spectra. A critical analysis of whether a combination of several methods of chromatography and mass spectrometry allows us to elucidate the structure of an unknown UDMH transformation product was provided. It was demonstrated that the use of gas chromatographic retention indices for two stationary phases (polar and non-polar) allows for the rejection of false candidates in many cases when only one retention index is not enough. The structures of five previously unknown UDMH transformation products were proposed, and four previously proposed structures were refined.

We review the main techniques, procedures, and information products used in non-target analysis (NTA) to reveal the composition of substances. Sampling and sample preparation methods are preferable that ensure the extraction of analytes from test samples in a wide range of analyte properties with the most negligible loss. The necessary techniques of analysis are versions of chromatography–high-resolution tandem mass spectrometry (HRMS), yielding individual characteristics of analytes (mass spectra, retention properties) to accurately identify them. The prioritization of the analytical strategy discards unnecessary measurements and thereby increases the performance of the NTA. Chemical databases, collections of reference mass spectra and retention characteristics, algorithms, and software for processing HRMS data are indispensable in NTA. [ABSTRACT FROM AUTHOR]

Abstract Mass spectrometry based non-target analysis is increasingly adopted in environmental sciences to screen and identify numerous chemicals simultaneously in highly complex samples. However, current data processing software either lack functionality for environmental sciences, solve only part of the workflow, are not openly available and/or are restricted in input data formats. In this paper we present patRoon, a new R based open-source software platform, which provides comprehensive, fully tailored and straightforward non-target analysis workflows. This platform makes the use, evaluation and mixing of well-tested algorithms seamless by harmonizing various common (primarily open) software tools under a consistent interface. In addition, patRoon offers various functionality and strategies to simplify and perform automated processing of complex (environmental) data effectively. patRoon implements several effective optimization strategies to significantly reduce computational times. The ability of patRoon to perform time-efficient and automated non-target data annotation of environmental samples is demonstrated with a simple and reproducible workflow using open-access data of spiked samples from a drinking water treatment plant study. In addition, the ability to easily use, combine and evaluate different algorithms was demonstrated for three commonly used feature finding algorithms. This article, combined with already published works, demonstrate that patRoon helps make comprehensive (environmental) non-target analysis readily accessible to a wider community of researchers.