Discovering transformation products of pharmaceuticals in domestic wastewaters and receiving rivers by using non-target screening and machine learning approaches.

Wastewater treatment plants (WWTPs) are an important source of pharmaceuticals in surface water, but information about their transformation products (TPs) is very limited. Here, we investigated occurrence and transformation of pharmaceuticals and TPs in WWTPs and receiving rivers by using suspect and non-target analysis as well as target analysis. Results showed identification of 113 pharmaceuticals and 399 TPs, including mammalian metabolites (n = 100), environmental microbial degradation products (n = 250), photodegradation products (n = 44) and hydrolysis products (n = 5). The predominant parent pharmaceuticals (n = 37) and transformation products (n = 68) were mainly derived from antimicrobials, accounting for 32.7 % and 17.0 %, respectively. The identified compounds were found in the influent (387-428) and effluent (227-400) of WWTPs, as well as upstream (290-451) and downstream (322-416) of receiving rivers, most predominantly from antimicrobials, followed by analgesic and antipyretic drugs. A total of 399 identified TPs were transformed by 110 pathways, of which the oxidation reaction was predominant (27.0 %), followed by photodegradation reaction (10.7 %). Of the 399 TPs, 49 (with lower PNECs) were predicted to be more toxic than their parents. Compounds with potential high risks (hazard quotient >1 and risk index (RI) > 0.1) were found in the WWTP influent (126), effluent (53) and river (61), and the majority were from the antimicrobial and antihypertensive classes. In particular, the potential risks (RI) of TPs from roxithromycin and irbesartan were found higher than those for their corresponding parents. The findings from this study highlight the need to monitor TPs from pharmaceuticals in the environment.

Determination of total extractable organofluorine (EOF) in food contact materials and target and non-target analysis of per- and polyfluoroalkyl substances using LC-MS/MS and LC-HRMS simultaneously coupled to ICP-MS.

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.

Discovery of novel benzotriazole ultraviolet stabilizers in surface water.

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 5­chloro-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-(2­hydroxy-3­tert­butyl­5-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-2­hydroxy-5-methylphenyl)-2H-benzotriazole (mean 3.9 ng/L,

Non-target metabolomics approach for the investigation of the hidden effects induced by atrazine and its degradation products on plant metabolism.

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.

Non-target analysis of Danish wastewater treatment plant effluent: Statistical analysis of chemical fingerprinting as a step toward a future monitoring tool.

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.

Endocrine disrupting chemicals in children's and their parents' urine: Is the exposure related to the Chinese and Western lifestyle?

Children are known to be more vulnerable to exposure to endocrine-disrupting chemicals (EDCs) compared to adults, but evaluating the exposure pathways can be challenging. This research employed target and non-target analysis (NTA) to examine the exposure characteristics of EDCs in spot urine samples collected from 46 children's (aged 3-12 years) and their parents in Hong Kong (Chinese/Western lifestyle) and Guangzhou (mainly Chinese lifestyle). The results revealed that the geometric mean concentrations of phthalate esters metabolites (mPAEs) and bisphenols (BPs) in children's urine were 127.3 µg/gcrea and 2.5 µg/gcrea in Guangzhou, and 93.7 µg/gcrea and 2.9 µg/gcrea in Hong Kong, respectively, which were consistent with global levels. NTA identified a total of 1069 compounds, including 106 EDCs, commonly detected in food, cosmetics, and drugs. Notable regional differences were observed between Guangzhou and Hong Kong with potential sources of EDCs including dietary and cosmetic additives, toys, flooring and dust, as well as differences in lifestyles, diet, and living environment. However, age was found to significantly impact EDC exposure. The quantified EDCs (mPAEs and BPs) posed possible health risks to 60% of the children. Moreover, the presence of caffeine in children's urine, which exhibited higher detection rates in children from Hong Kong (95.6%) and Guangzhou (44.4%), warrants further attention. The sources of EDCs exposure in these regions need to be fully confirmed.

An Integrated Approach of Bioassays and Non-Target Screening for the Assessment of Endocrine-Disrupting Activities in Tap Water and Identification of Novel Endocrine-Disrupting Chemicals.

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.

Unveiling per- and polyfluoroalkyl substance contamination in Chinese paper products and assessing their exposure risk.

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 (

Transformation mechanisms of the antidepressant citalopram in a moving bed biofilm reactor: Substrate-depended pathways, eco-toxicities and enantiomeric profiles.

Citalopram (CIT) is one of the most consumed antidepressants and frequently detected in aquatic environments worldwide. Conventional wastewater treatment cannot remove this neuronal active pharmaceutical efficiently. Past studies showed that moving bed biofilm reactors (MBBRs) can degrade CIT but the exact transformation pathways and toxicity reduction remained unclear. In this study, the effects of substrate stimulation on CIT transformation in an MBBR were systematically investigated. The results showed that a co-metabolic stimulation by acetate increased the transformation rate by 54 % and 24 % at high (300 µg/L) and environmental concentration (1.8 µg/L) of CIT, respectively. Conversely, the complex substrates in raw wastewater reduced the reaction rates by 44 %, suggesting a competitive inhibition on the enzymatic sites. The substrate stimulation changed the enantiomeric fraction (EF) of CIT from racemic (EF=0.5) to 0.60 at the high CIT concentrations, while those at lower concentrations resulted in an EF of 0.33, indicating that probably different enantioselective enzymes degraded CIT at high concentrations than at low concentrations, i.e., the presence of 300 µg/L CIT was possibly sufficient to induce the synthesis of different enantioselective enzymes, than those originally present. Through non-target and target analysis, in total 19 transformation products (TPs) including 7 TPs that were hitherto not mentioned in the literature were identified. Among these were quaternary amines, alkenes and conjugate TPs. The major transformation pathways were a) nitrile hydrolysis (up to 43 %), b) amide hydrolysis, and c) N-oxidation. Dosing acetate up-regulated significantly the amide hydrolysis, N-oxidation and conjugation pathways but inhibited the N-demethylation and α-carbon hydroxylation pathways. The in-silico toxicity assessment of CIT and its TPs suggested the overall eco-toxic potential of TPs was reduced by MBBR. Furthermore, the degradation under carbon-limited (famine) conditions favored the formation of the more toxic carboxamide, N-desmethyl and alkene TPs, while carbon-rich conditions, promoted the production of the less toxic carboxylic acid, N-oxide and ester TPs. Therefore, this study demonstrated that a) the co-metabolic stimulation of CIT metabolization by dosing a simple carbon source or b) inhibition of CIT metabolization by complex substrates; c) substrate stimulation made a difference on CIT transformation rates, enantiomeric profiles, pathways and toxic potentials. Overall, a simple-carbon co-metabolic stimulated MBBR was an efficient up-regulation strategy to minimize hazardous CIT and CIT-TPs as much as possible.

Internal exposure potential of water-soluble organic molecules in urban PM2.5 evaluated by non-covalent adductome of human serum albumin.

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.

Profiling emerging micropollutants in urban stormwater runoff using suspect and non-target screening via high-resolution mass spectrometry.

Urban surface runoff contains chemicals that can negatively affect water quality. Urban runoff studies have determined the transport dynamics of many legacy pollutants. However, less attention has been paid to determining the first-flush effects (FFE) of emerging micropollutants using suspect and non-target screening (SNTS). Therefore, this study employed suspect and non-target analyses using liquid chromatography-high resolution mass spectrometry to detect emerging pollutants in urban receiving waters during stormwater events. Time-interval sampling was used to determine occurrence trends during stormwater events. Suspect screening tentatively identified 65 substances, then, their occurrence trend was grouped using correlation analysis. Non-target peaks were prioritized through hierarchical cluster analysis, focusing on the first flush-concentrated peaks. This approach revealed 38 substances using in silico identification. Simultaneously, substances identified through homologous series observation were evaluated for their observed trends in individual events using network analysis. The results of SNTS were normalized through internal standards to assess the FFE, and the most of tentatively identified substances showed observed FFE. Our findings suggested that diverse pollutants that could not be covered by target screening alone entered urban water through stormwater runoff during the first flush. This study showcases the applicability of the SNTS in evaluating the FFE of urban pollutants, offering insights for first-flush stormwater monitoring and management.

Influence of extraction windows for data-independent acquisition on feature annotation during suspect screening.

Non-target analysis (NTA) using high-resolution mass spectrometry is becoming a useful approach to screen for suspect and unknown chemicals. For comprehensive analyses, data-independent acquisition (DIA), like Sequential Windowed Acquisition of all THeoretical Mass Spectra (SWATH-MS) on Sciex instruments, is necessary, usually followed by library matching for feature annotation. The choice of parameters, such as acquisition window number and size, may influence the comprehensiveness of the suspect features detected. The goal of this study was to assess how mass spectrometric DIA settings may influence the ability to obtain confident annotations and identifications of features in environmental (river water, passive sample extract (PSE)), wastewater (unpreserved and acidified) and biological (urine) sample matrices. Each matrix was analysed using 11 different MS methods, with 5-15 variable size acquisition windows. True positive (TP) annotation (i.e., matching experimental and library spectra) rates were constant for PSE (40%) and highest for urine (18%), wastewater (34% and 36%, unpreserved and acidified, respectively) and river water (8%) when using higher numbers of windows (15). The number of annotated features was highest for PSE (12%) and urine (8.5%) when using more acquisition windows (9 and 14, respectively). Less complex matrices (based on average total ion chromatogram intensities) like river water, unpreserved and acidified wastewater have higher annotation rates (7.5%, 8% and 13.2%, respectively) when using less acquisition windows (5-6), indicating matrix dependency of optimum settings. Library scores varied widely for correct (scores between 6 and 100) as well as incorrect annotations (scores between 2 and 100), making it hard to define specific ideal cut-off values. Results highlight the need for properly curated libraries and careful optimization of SWATH-MS and other DIA methods for each individual matrix, finding the best ratio of total annotations to true positive, (i.e., correct) annotations to achieve best NTA results.

Unraveling the chemical fingerprint of the Miami River sources: Insights from high-resolution mass spectrometry and nontarget analysis.

This study investigated the chemical composition of waters in the heavily urbanized and historically polluted Miami River, Florida. The goal was to assess the different water sources and anthropogenic influence in this managed area using nontarget analysis (NTA) combined with high-resolution mass spectrometry (HRMS). Surface water samples were collected from 10 sites during five sampling events in the wet season of 2021 and 2022. The HRMS data was processed using Compound Discoverer™ version 3.3, and the results were analyzed using techniques including Principal Component Analysis and Kendrick Mass Defect plots. Results showed a gradient change in the chemical composition from the Everglades to Biscayne Bay endmembers. The Seybold Canal, an adjacent canal, was consistently identified as a unique source of contaminants, contributing its own specific set of tracers. Increased presence and intensity of organic contaminants along the waterway was observed, indicating significant anthropogenic influence in the area. The NTA and post-processing were evaluated for reproducibility, demonstrating robustness with a 71.2% average reproducibility for compounds detected in 3 out of 5 sampling trips. A detection frequency of 80% (4 out of 5) was the set criterion for detected compounds suggested as tracers. To prioritize samples, hierarchical cluster analysis was employed, and potential tracers for each water source were determined. Tracers included natural products and agricultural herbicides and insecticides for the Everglades, anthropogenic contaminants for the Seybold Canal, and a lack of unique tracers for Biscayne Bay. Additionally, urban-influenced contaminants such as flame retardants, insect repellents, pharmaceuticals, and non-agricultural herbicides were identified along the river. This study highlights the impact of human activities on the Miami River and demonstrates the effectiveness of NTA in differentiating and tracking water sources. The results emphasize the importance of reproducibility in NTA and provide guidance on implementing monitoring strategies by prioritizing samples based on chemical compositions.

Novel PFAS-specific monitoring approach for highly impacted surface waters.

In regulatory environmental monitoring programs, only a very small fraction of the vast number of per- and polyfluoroalkyl substances (PFAS) are investigated by target analysis. Therefore, non-target analysis (NTA) studies are increasingly conducted to detect unknown or unnoticed PFAS. These studies are often based on a few grab samples. Thus, discontinuously emitted PFAS from industrial batch processes might be easily overlooked. To address this deficiency and obtain in-depth information on the occurrence and temporal trend of PFAS in surface water impacted by treated industrial waste water, a comprehensive target and NTA study was implemented for 29 months. Elevated PFAS concentrations with up to 10.8 µg L-1 were detected in the river water by target analysis. In addition to PFAS target analysis, the water samples were analyzed by liquid chromatography-high-resolution tandem mass spectrometry (LC-HRMS/MS). Data processing strategies and various filtering steps were applied to prioritize PFAS. Substances were identified by comparing data to available internal and external PFAS suspect lists, a fragment ion and neutral loss list, and spectral libraries. Several compounds were unequivocally identified based on reference standards. Fifty-five PFAS were (tentatively) identified using NTA. Of those, 43 could be assigned to 13 different homologous series. Partly fluorinated short-chain carboxylic acids (H-PFCA) and sulfonic acids (H-PFSA) were predominantly found in addition to perfluoroalkyl carboxylic acids (PFCA) and the alkyl ether carboxylic acid DONA. To the best of our knowledge, 12 PFAS were reported in surface water for the first time. Signal intensities of individual PFAS and signal ratios varied widely over time, which may indicate batch operations leading to discontinuous emission. Results and insights from this screening approach on PFAS can be used to optimize forthcoming surface water monitoring programs by including newly identified PFAS and selecting appropriate sampling intervals.

Leaching and transformation of chemical additives from weathered plastic deployed in the marine environment.

Plastic pollution causes detrimental environmental impacts, which are increasingly attributed to chemical additives. However, the behaviour of plastic additives in the marine environment is poorly understood. We used a marine deployment experiment to examine the impact of weathering on the extractables profile, analysed by liquid chromatography-mass spectrometry, of four plastics at two locations over nine months in Aotearoa/New Zealand. The concentration of additives in polyethylene and oxo-degradable polyethylene were strongly influenced by artificial weathering, with deployment location and time less influential. By comparison, polyamide 6 and polyethylene terephthalate were comparatively inert with minimal change in response to artificial weathering or deployment time. Non-target analysis revealed extensive differentiation between non-aged and aged polyethylene after deployment, concordant with the targeted analysis. These observations highlight the need to consider the impact of leaching and weathering on plastic composition when quantifying the potential impact and risk of plastic pollution within receiving environments.

Toxicity and chemical characterization of shale gas wastewater discharged to the receiving water: Evidence from toxicity identification evaluation.

Flowback and produced water (FPW) generated from shale gas extraction is a complex mixture consisting of injected drilling fluid, deep formation water, and byproducts of downhole reactions. Limited knowledge is available regarding the impact of discharged FPW on surface water in China. With the development of shale gas exploitation, this emphasizes an urgent need for comprehensive assessments and stringent regulations to ensure the safe disposal of shale gas extraction-related wastewater. Herein, we explored potential impacts of treated shale gas wastewater discharged into a local river in southwest China through toxicity identification evaluation (TIE). Results revealed that organics and particulates significantly contributed to the overall toxicity of the treated FPW wastewater. Through target and suspect chemical analyses, various categories of organic contaminants were detected, including alkanes, aromatic hydrocarbons, biocides, phenols, and phthalates. Furthermore, non-target analysis uncovered the presence of surfactant-related contaminants in tissues of exposed organisms, but their contribution to the observed toxicity was unclear due to the lack of effect data for these compounds. Higher toxicity was found at the discharge point compared with upstream sites; however, the toxicity was rapidly mitigated due to dilution in the receiving river, posing little impact on downstream areas. Our study highlighted the importance of monitoring toxicity and water quality of FPW effluent even though dilution could be a viable approach when the water volume in the discharge was small.

Non-target analysis for water characterization: wastewater treatment impact and selection of relevant features.

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.

What is in the fish? Collaborative trial in suspect and non-target screening of organic micropollutants using LC- and GC-HRMS.

A collaborative trial involving 16 participants from nine European countries was conducted within the NORMAN network in efforts to harmonise suspect and non-target screening of environmental contaminants in whole fish samples of bream (Abramis brama). Participants were provided with freeze-dried, homogenised fish samples from a contaminated and a reference site, extracts (spiked and non-spiked) and reference sample preparation protocols for liquid chromatography (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS). Participants extracted fish samples using their in-house sample preparation method and/or the protocol provided. Participants correctly identified 9-69 % of spiked compounds using LC-HRMS and 20-60 % of spiked compounds using GC-HRMS. From the contaminated site, suspect screening with participants' own suspect lists led to putative identification of on average ∼145 and ∼20 unique features per participant using LC-HRMS and GC-HRMS, respectively, while non-target screening identified on average ∼42 and ∼56 unique features per participant using LC-HRMS and GC-HRMS, respectively. Within the same sub-group of sample preparation method, only a few features were identified by at least two participants in suspect screening (16 features using LC-HRMS, 0 features using GC-HRMS) and non-target screening (0 features using LC-HRMS, 2 features using GC-HRMS). The compounds identified had log octanol/water partition coefficient (KOW) values from -9.9 to 16 and mass-to-charge ratios (m/z) of 68 to 761 (LC-HRMS and GC-HRMS). A significant linear trend was found between log KOW and m/z for the GC-HRMS data. Overall, these findings indicate that differences in screening results are mainly due to the data analysis workflows used by different participants. Further work is needed to harmonise the results obtained when applying suspect and non-target screening approaches to environmental biota samples.

Exploring Human Metabolome after Wine Intake-A Review.

Wine has a rich history dating back to 2200 BC, originally recognized for its medicinal properties. Today, with the aid of advanced technologies like metabolomics and sophisticated analytical techniques, we have gained remarkable insights into the molecular-level changes induced by wine consumption in the human organism. This review embarks on a comprehensive exploration of the alterations in human metabolome associated with wine consumption. A great number of 51 studies from the last 25 years were reviewed; these studies systematically investigated shifts in metabolic profiles within blood, urine, and feces samples, encompassing both short-term and long-term studies of the consumption of wine and wine derivatives. Significant metabolic alterations were observed in a wide variety of metabolites belonging to different compound classes, such as phenolic compounds, lipids, organic acids, and amino acids, among others. Within these classes, both endogenous metabolites as well as diet-related metabolites that exhibited up-regulation or down-regulation following wine consumption were included. The up-regulation of short-chain fatty acids and the down-regulation of sphingomyelins after wine intake, as well as the up-regulation of gut microbial fermentation metabolites like vanillic and syringic acid are some of the most important findings reported in the reviewed literature. Our results confirm the intact passage of certain wine compounds, such as tartaric acid and other wine acids, to the human organism. In an era where the health effects of wine consumption are of growing interest, this review offers a holistic perspective on the metabolic underpinnings of this centuries-old tradition.

Non-target screening of volatile organic compounds in spray-type consumer products and their potential health risks.

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.