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The increasing recognition of the health impacts from human exposure to per- and polyfluorinated alkyl substances (PFAS) has surged the need for sophisticated analytical techniques and advanced data analyses, especially for assessing exposure by food of animal origin. Despite the existence of nearly 15,000 PFAS listed in the CompTox chemicals dashboard by the US Environmental Protection Agency, conventional monitoring and suspect screening methods often fall short, covering only a fraction of these substances. This study introduces an innovative automated data processing workflow, named PFlow, for identifying PFAS in environmental samples using direct infusion Fourier transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). PFlow's validation on a bream liver sample, representative of low-concentration biota, involves data pre-processing, annotation of PFAS based on their precursor masses, and verification through isotopologues. Notably, PFlow annotated 17 PFAS absent in the comprehensive targeted approach and tentatively identified an additional 53 compounds, thereby demonstrating its efficiency in enhancing PFAS detection coverage. From an initial dataset of 30,332 distinct m/z values, PFlow thoroughly narrowed down the candidates to 84 potential PFAS compounds, utilizing precise mass measurements and chemical logic criteria, underscoring its potential in advancing our understanding of PFAS prevalence and of human exposure. [ABSTRACT FROM AUTHOR]

Modern gas chromatography-mass spectrometry (GC–MS) allows for the analysis of complex samples, such as fragrances. However, identifying all the constituents in natural fragrance mixtures, especially allergens that need to be listed on product labels, is a significant challenge. This is primarily due to the high complexity of the sample and the fact that electron ionization, the most commonly used ionization method in GC–MS, produces numerous nonspecific fragment ions, often resulting in the absence or very low abundance of the molecular ion. These factors affect confidence in assigning the analyte. In this study, we demonstrate that the combination of GC × GC separation, with high mass resolution and accurate mass measurements, as well as chemical ionization in addition to traditional electron ionization, becomes an efficient tool for reliable qualitative analysis of a mixture containing 100 fragrance allergens, even when many of them are closely related species or isomers. The proposed approach expands the applicability of the comprehensive GC × GC-HRMS method, which includes complementary ionization techniques, from studies on anthropogenic priority pollutants and emerging contaminants to the analysis of natural products. Although targeted qualitative and quantitative analysis of allergens in the modern laboratories is well organized, GC × GC-HRMS, being a useful complement to routine quality control of volatile allergens in fragrances, definitely gives an additional contribution to the analytical cases when conventional 1D-GC–MS faces some problems or uncertainties. [ABSTRACT FROM AUTHOR]

A liquid chromatography method coupled with an Orbitrap analyser was used to detect nisin A and its variants in partially skimmed and raw cow milk. A suspect screening method enabled the identification of F, Q and Z variants. Adequate linearity was achieved (r2 = 0.9998–1 up to 250 μg/L) with a limit of quantitation for nisin A of 2.5 μg/L. Method accuracy (at 2.5, 25 and 250 μg/L) in milk ranged from 94 to 98% and precision in the range 0.4–1.9%. Nisin Z was abundant in partially skimmed samples. The method was suitable for determining these bacteriocins in cow milk. [ABSTRACT FROM AUTHOR]

Antioxidants are ubiquitous in various environmental samples, leading to increasing concern regarding their potential risk to environments or humans. However, there is dearth of information regarding the environmental fate of antioxidants and unknown/unexpected antioxidants in the environment. Here, we established a compound database (CDB) containing 320 current-used antioxidants by collecting the chemicals from EPA's functional use database and published documents. Physical–chemical characteristics of these antioxidants were estimated, and 19 ones were considered as persistent and bioaccumulative (P&B) substances. This CDB was further coupled with high resolution mass spectrometry (HRMS) technique, which was employed for suspect screening of antioxidants in extracts of sediments (n = 88) collected from Taihu Lake basin. We screened 119 HRMS features that can match 135 chemical formulas in the CDB, and 20 out of them exhibited the detection frequencies ≥ 90%. The total concentrations of suspect antioxidants in sediments ranged from 6.41 to 830 ng/g dw. Statistical analysis demonstrated that concentrations of suspect antioxidants in Taihu Lake were statistically significantly lower than those in Shihu and Jiulihu Lake, but greater than those from other small lakes. Collectively, this study provided a CDB that could be helpful for further monitoring studies of antioxidant in the environments, and also provided the first evidence regarding the ubiquity of antioxidants in aquatic environment of Taihu Lake basin. [ABSTRACT FROM AUTHOR]

Organophosphorus compounds (OPs) are widely used as flame retardants (FRs) and plasticizers, yet strategies for comprehensively screening of suspect OPs in environmental samples are still lacking. In this work, a neoteric, robust, and general suspect screening technique was developed to identify novel chemical exposures by use of ultra-high performance liquid chromatography-Q Exactive hybrid quadrupole-Orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS). We firstly established a suspect chemical database which had 7,922 OPs with 4,686 molecular formulas, and then conducted suspect screening in n = 50 indoor dust samples, n = 76 sediment samples, and n = 111 water samples. By use of scoring criteria such as retention time prediction models, we successfully confirmed five compounds by comparison with their authentic standards, and prioritized three OPs candidates including a nitrogen/fluorine-containing compound, that is dimethyl {1H-indol-3-yl[3-(trifluoromethyl)anilino]methyl} phosphonate (DMITFMAMP). Given that the biodegradation half-life values in water (t1/2,w) of DMITFMAMP calculated by EPI Suite is 180 d, it is considered to be potentially persistent. This strategy shows promising potential in environmental pollution assessment, and can be expected to be widely used in future research.

Abstract Background Per- and polyfluoroalkyl substances (PFAS) are considered ‘contaminants of emerging concern’ due to their environmental persistence, bio-accumulative potential, and adverse effects on human health. They are widely employed in producing various goods used in daily life, such as non-stick cookware, cleaning agents, and many industrial applications in aerospace, automotive, construction, electronics, and military, all of which ultimately end up in different environmental matrices. India’s rapid economic growth necessitates a comprehensive understanding of its PFAS contamination levels and potential human and ecological exposure. Results The present study reports the quantification of one long-chain and two short-chain perfluoroalkyl acids and three long-chain and two short-chain perfluorosulfonic acids and qualitative analysis using suspect screening in the waters of Chennai, Tamil Nadu, India. Samples were collected from surface and groundwater sources, including the Adyar river, Buckingham canal, Chembarambakkam lake, and the water treatment plant. The concentrations analyzed in all the samples ranged from 0.10 ng/L to 136.27 ng/L. Groundwater had some of the highest concentrations of PFAS. L-PFBS (up to 136.27 ng/L) and PFOA (up to 77.61 ng/L) are present in all the samples. The concentrations of all the target PFAS increased in the 5 to 103% range in the final treated water compared to the raw water of the water treatment plant. This treated water is distributed as a source of drinking water for the residents of Chennai. Additionally, the dominance of short-chain compounds (4–7 carbons) over long-chain compounds (> 7 carbons) was observed. Suspect screening revealed numerous precursors and other fluorinated compounds abundantly present in the samples. Conclusions Our study revealed PFAS levels up to 136.27 ng/L in both surface and groundwater samples from Chennai. These findings raise concerns about potential risks to ecosystems and human well-being. The dominance of short-chain PFAS coupled with abundant precursors and unidentified fluorinated compounds indicates an ongoing shift toward alternatives. Conventional water treatment is ineffective in eliminating these chemicals from the water system; rather, increasing the PFAS concentrations from raw water to treated water necessitates advanced polishing steps. Industrial emissions, untreated domestic wastewater discharge, and open dump sites have been suspected as the significant sources of contamination, highlighting the need for further investigation to fully assess the extent of PFAS contamination in Chennai. Graphical Abstract

Background: Per- and polyfluoroalkyl substances (PFAS) are considered 'contaminants of emerging concern' due to their environmental persistence, bio-accumulative potential, and adverse effects on human health. They are widely employed in producing various goods used in daily life, such as non-stick cookware, cleaning agents, and many industrial applications in aerospace, automotive, construction, electronics, and military, all of which ultimately end up in different environmental matrices. India's rapid economic growth necessitates a comprehensive understanding of its PFAS contamination levels and potential human and ecological exposure. Results: The present study reports the quantification of one long-chain and two short-chain perfluoroalkyl acids and three long-chain and two short-chain perfluorosulfonic acids and qualitative analysis using suspect screening in the waters of Chennai, Tamil Nadu, India. Samples were collected from surface and groundwater sources, including the Adyar river, Buckingham canal, Chembarambakkam lake, and the water treatment plant. The concentrations analyzed in all the samples ranged from 0.10 ng/L to 136.27 ng/L. Groundwater had some of the highest concentrations of PFAS. L-PFBS (up to 136.27 ng/L) and PFOA (up to 77.61 ng/L) are present in all the samples. The concentrations of all the target PFAS increased in the 5 to 103% range in the final treated water compared to the raw water of the water treatment plant. This treated water is distributed as a source of drinking water for the residents of Chennai. Additionally, the dominance of short-chain compounds (4–7 carbons) over long-chain compounds (> 7 carbons) was observed. Suspect screening revealed numerous precursors and other fluorinated compounds abundantly present in the samples. Conclusions: Our study revealed PFAS levels up to 136.27 ng/L in both surface and groundwater samples from Chennai. These findings raise concerns about potential risks to ecosystems and human well-being. The dominance of short-chain PFAS coupled with abundant precursors and unidentified fluorinated compounds indicates an ongoing shift toward alternatives. Conventional water treatment is ineffective in eliminating these chemicals from the water system; rather, increasing the PFAS concentrations from raw water to treated water necessitates advanced polishing steps. Industrial emissions, untreated domestic wastewater discharge, and open dump sites have been suspected as the significant sources of contamination, highlighting the need for further investigation to fully assess the extent of PFAS contamination in Chennai. Highlights: Groundwater and surface waters showed predominant presence of PFOA and L-PFBS. Concentrations of target PFAS increased from raw water to treated water in a conventional WTP. Numerous precursors and other fluorinated compounds are abundantly present in the collected samples. Open dump sites, untreated domestic wastewater discharge, and industrial emissions have been suspected as the contributing sources. [ABSTRACT FROM AUTHOR]

Simultaneous identification and quantification of per- and polyfluoroalkyl substances (PFAS) were evaluated for three quadrupole time-of-flight mass spectrometry (QTOF) acquisition methods. The acquisition methods investigated were MS-Only, all ion fragmentation (All-Ions), and automated tandem mass spectrometry (Auto-MS/MS). Target analytes were the 25 PFAS of US EPA Method 533 and the acquisition methods were evaluated by analyte response, limit of quantification (LOQ), accuracy, precision, and target-suspect screening identification limit (IL). PFAS LOQs were consistent across acquisition methods, with individual PFAS LOQs within an order of magnitude. The mean and range for MS-Only, All-Ions, and Auto-MS/MS are 1.3 (0.34–5.1), 2.1 (0.49–5.1), and 1.5 (0.20–5.1) pg on column. For fast data processing and tentative identification with lower confidence, MS-Only is recommended; however, this can lead to false-positives. Where high-confidence identification, structural characterisation, and quantification are desired, Auto-MS/MS is recommended; however, cycle time should be considered where many compounds are anticipated to be present. For comprehensive screening workflows and sample archiving, All-Ions is recommended, facilitating both quantification and retrospective analysis. This study validated HRMS acquisition approaches for quantification (based upon precursor data) and exploration of identification workflows for a range of PFAS compounds. [ABSTRACT FROM AUTHOR]

In this study, 31 household spray-type cleaning products from 10 categories were examined to identify the substances contained in these products and evaluate their resulting toxicities. After substance detection via LC-QTOF-MS, suspect and non-target screenings were performed using UNIFI software. A total of 48 substances were identified during suspect screening. Among them, surfactant (freq. 22/31(71.0%)), plasticizer (freq. 23/31(74.2%)), antioxidant (freq. 20/31(64.5%)) were detected with high frequencies. Among the 48 compounds, tributyl citrate acetate was the most frequently detected (frequency 13/31, 41.9%). In addition, 51 substances were identified via non-target analysis. Among them, oleamide, a type of surfactant, showed a high frequency of detection (22/31(71.0%)). The toxicities of the 98 substances (suspect: 47 (except for confidence level 5) and non-target: 51) identified were evaluated using the European Chemicals Agency (ECHA) database and Toxtree. Among them, 20 substances were classified as a substance of caution. The risk assessment for 3 substances identified with references standards was also performed. The suspect and non-target screening technique proved to be a useful method that can be applied when there are many non-specific chemicals and their components in the consumer products are not well known. [ABSTRACT FROM AUTHOR]

High-resolution mass spectrometry (HRMS) has become an important tool for monitoring chemical residues in food, but the time and effort required to evaluate the large amount of data generated by HRMS can be a limiting factor in the widespread application of this tool. Suspect screening, i.e., searching HRMS data against large compound databases or mass lists, represents a practical compromise between using HRMS data to only look for target compounds and performing full non-target analysis. Several different approaches for suspect screening using HRMS data were tested using data from shrimp and eel spiked with veterinary drugs and pesticides as well as from imported aquaculture samples. Most of the analytes (>70%) in the spiked samples were detected and identified by searching against compound databases. To query larger databases and on-line resources such as mzCloud, it was necessary to use software capable of differential analysis and selective filtering, such as Compound Discoverer. Using selective filtering, the number of compounds detected in fish sample extracts could be reduced from tens of thousands to a few hundred by subtracting method blanks and comparing to matrix blank extracts. This smaller list of potential compounds could be further evaluated and compared to available databases and libraries. Analysis of imported aquaculture samples resulted in detection of unexpected contaminants including the dewormer levamisole, the insecticide buprofezin, and potentially the plant alkaloid ricinine. [ABSTRACT FROM AUTHOR]

There is growing concern about the prevalence and impact of contaminants of emerging concern (CECs). The environmental monitoring of CECs has, however, been limited in low‐ and middle‐income countries due to the lack of advanced analytical instrumentation locally. In the present study we employed a nontargeted and suspect screening workflow via liquid chromatography coupled with high‐resolution mass spectrometry (HRMS) to identify known and unknown pollutants in the Glen Valley wastewater treatment plant, Botswana, complemented by analysis of groundwater samples. The present study represents the first HRMS analysis of CECs in water samples obtained in Botswana. Suspect screening of 5942 compounds qualitatively identified 28 compounds, including 26 pharmaceuticals and two illicit drugs (2‐ethylmethcathinone and 11‐nor‐9‐carboxy‐Δ9‐tetrahydrocannabinol). Nontargeted analysis tentatively identified the presence of 34 more compounds including (5ξ)‐12,13‐dihydroxypodocarpa‐8,11,13‐trien‐7‐one, 12‐aminododecanoic acid, atenolol acid, brilliant blue, cyclo leucylprolyl, decanophenone, DL‐carnitine, N,N′‐dicyclohexylurea, N4‐acetylsulfamethoxazole, NP‐003672, and 24 polyethylene glycol polymers. The highest number of detections were in influent wastewater (26 CECs) followed by effluent wastewater (10 CECs) and, lastly, groundwater (4 CECs). Seventeen CECs detected in the influent water were not detected in the effluent waters, suggesting reduced emissions due to wastewater treatment. Two antiretroviral compounds (abacavir and tenofovir) were detected in the influent and effluent sources. This suggests that wastewater treatment plants are a major pathway of chemical pollution to the environment in Botswana and will help inform prioritization efforts for monitoring and remediation that is protective of these key ecosystems. Environ Toxicol Chem 2024;43:52–61. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. [ABSTRACT FROM AUTHOR]

Abstract Increasing production and use of chemicals and awareness of their impact on ecosystems and humans has led to large interest for broadening the knowledge on the chemical status of the environment and human health by suspect and non-target screening (NTS). To facilitate effective implementation of NTS in scientific, commercial and governmental laboratories, as well as acceptance by managers, regulators and risk assessors, more harmonisation in NTS is required. To address this, NORMAN Association members involved in NTS activities have prepared this guidance document, based on the current state of knowledge. The document is intended to provide guidance on performing high quality NTS studies and data interpretation while increasing awareness of the promise but also pitfalls and challenges associated with these techniques. Guidance is provided for all steps; from sampling and sample preparation to analysis by chromatography (liquid and gas—LC and GC) coupled via various ionisation techniques to high-resolution tandem mass spectrometry (HRMS/MS), through to data evaluation and reporting in the context of NTS. Although most experience within the NORMAN network still involves water analysis of polar compounds using LC–HRMS/MS, other matrices (sediment, soil, biota, dust, air) and instrumentation (GC, ion mobility) are covered, reflecting the rapid development and extension of the field. Due to the ongoing developments, the different questions addressed with NTS and manifold techniques in use, NORMAN members feel that no standard operation process can be provided at this stage. However, appropriate analytical methods, data processing techniques and databases commonly compiled in NTS workflows are introduced, their limitations are discussed and recommendations for different cases are provided. Proper quality assurance, quantification without reference standards and reporting results with clear confidence of identification assignment complete the guidance together with a glossary of definitions. The NORMAN community greatly supports the sharing of experiences and data via open science and hopes that this guideline supports this effort.

In this study, consumer and lab grade plastic food storage bags were subjected to a variety of analytical techniques to investigate the presence and levels of per- and polyfluoroalkyl substances (PFAS). Samples were extracted and analyzed by both targeted and non-targeted analyses using liquid chromatography tandem mass spectrometry and Orbitrap high resolution mass spectrometry. Of the 18 bags tested, 57 % had detectable levels of PFAS ranging from 0.5 – 26.6 ng/g. Perflurorobutane sulfonic acid (PFBS) was detected at the highest concentration while 6:2 fluorotelomer phosphate diester (6:2 diPAP) was the most frequently detected. No other PFAS were found in the targeted method. Non-targeted analysis resulted in six potential new PFAS candidates not found within the targeted method, however the lack of available analytical standards did not allow for confirmation. Eight samples with detectable PFAS were chosen for both migration and total oxidizable precursor (TOP) assay experiments to understand the potential impact to dietary exposure. No 6:2 diPAP was found to migrate however migration of PFBS was found to be rapid (2 h) and with relatively high migration efficiencies (22 – 75 %). To estimate potential exposure to PFBS migrating from food storage bags, tolerable weekly intake (TWI) values were calculated at 2.12 ng/kg body weight/week, and were below the regulatory TWI value of 4.4 ng/kg established by the European Food Safety Authority (EFSA).

The determination of volatile compounds is essential for the chemical characterisation of honey's aroma and its correlation to its sensory profile and botanical origin. The present study describes the development, optimization and validation of a new, simple and reliable method for the determination of volatile compounds in honey using headspace solid-phase microextraction combined with gas chromatography/mass spectrometry (HS-SPME-GC-MS). The optimization of the SPME conditions showed that the ratio of honey: water (2:1) and the incubation temperature (60 °C) are the most critical parameters. Gas chromatography was performed with medium polar Varian CP-Select 624 column and the experimental Retention Index for a number of compounds was determined as an additional identification feature for suspect analysis. The simultaneous use of four internal standards chlorobenzene, benzophenone, 2-pentanol and 4-methyl-2-pentanone and matrix matched calibration enhanced method accuracy achieving recoveries 73–114 % and repeatability ranging between 3.9 and 19 % relative standard deviations. Furthermore, the superiority of the HS-SPME to static head space technique was verified exhibiting four-to nine-fold higher sensitivity. Target and suspect screening were applied to 30 Greek honey samples and 53 volatile compounds belonging to different chemical classes, such as alkanes, aldehydes, ketones, alcohols, and esters were identified with quantified concentrations ranging between 3.1 μg kg−1 (Limonene) up to 20 mg kg−1 (Benzeneacetaldehyde). Among the new findings is the detection of Myrtenol in Greek pine honey and 2,3-butanediol in Greek oak honey. The developed analytical protocol can be a valuable tool in order to chemically characterize honey based on the volatile content.

Increasing production and use of chemicals and awareness of their impact on ecosystems and humans has led to large interest for broadening the knowledge on the chemical status of the environment and human health by suspect and non-target screening (NTS). To facilitate effective implementation of NTS in scientific, commercial and governmental laboratories, as well as acceptance by managers, regulators and risk assessors, more harmonisation in NTS is required. To address this, NORMAN Association members involved in NTS activities have prepared this guidance document, based on the current state of knowledge. The document is intended to provide guidance on performing high quality NTS studies and data interpretation while increasing awareness of the promise but also pitfalls and challenges associated with these techniques. Guidance is provided for all steps; from sampling and sample preparation to analysis by chromatography (liquid and gas—LC and GC) coupled via various ionisation techniques to high-resolution tandem mass spectrometry (HRMS/MS), through to data evaluation and reporting in the context of NTS. Although most experience within the NORMAN network still involves water analysis of polar compounds using LC–HRMS/MS, other matrices (sediment, soil, biota, dust, air) and instrumentation (GC, ion mobility) are covered, reflecting the rapid development and extension of the field. Due to the ongoing developments, the different questions addressed with NTS and manifold techniques in use, NORMAN members feel that no standard operation process can be provided at this stage. However, appropriate analytical methods, data processing techniques and databases commonly compiled in NTS workflows are introduced, their limitations are discussed and recommendations for different cases are provided. Proper quality assurance, quantification without reference standards and reporting results with clear confidence of identification assignment complete the guidance together with a glossary of definitions. The NORMAN community greatly supports the sharing of experiences and data via open science and hopes that this guideline supports this effort. [ABSTRACT FROM AUTHOR]

Many food contact materials (FCMs) and reusable plastics in the food industry contain poly- and perfluoroalkyl substances (PFAS), a group of synthetic pollutants that are known to be potentially harmful for wildlife, humans, and the environment. PFAS may migrate from FCMs to food consumed by humans. As a replacement for plastics, often paper and other plant-based materials are used in commercial settings. This also applies to drinking straws, where plant-based and other presumably eco-friendly straws are increasingly used to reduce plastic pollution. In order to make these materials water-repellent, PFAS are added during manufacturing but can also already be present early in the supply chain due to the use of contaminated raw materials. In the present study, we examined the PFAS concentrations in 39 different brands of straws, made from five materials (i.e. paper, bamboo, glass, stainless steel, and plastic) commercially available on the Belgian market. We combined both targeted and suspect-screening approaches to evaluate a wide range of PFAS. PFAS were found to be present in almost all types of straws, except for those made of stainless steel. PFAS were more frequently detected in plant-based materials, such as paper and bamboo. We did not observe many differences between the types of materials, or the continents of origin. The presence of PFAS in plant-based straws shows that they are not necessarily biodegradable and that the use of such straws potentially contributes to human and environmental exposure of PFAS. [ABSTRACT FROM AUTHOR]

The proliferation of new psychoactive substances (NPSs) in recent years has posed a significant challenge to public health. Traditional monitoring methods have proven insufficient in tracking these constantly evolving substances, leading to the development of alternative approaches such as wastewater-based epidemiology (WBE). The present study aims to utilize high-resolution mass spectrometry (HRMS)-based targeted and suspect screening to profile NPS, other illicit drugs, and drug-related compounds in a Taiwanese wastewater sample. For the targeted analysis, 8 out 18 standards of illicit drugs have been identified. The suspect screening approach based on approximately 3600 substances in the SWGDRUG library can further identify 92 compounds, including opiate analgesics, synthetic cathinones, phenylalkylamines derivatives, phenethylamine derivatives, tryptamine derivatives, steroids, and ephedrine-related compounds. Additionally, the presence of 5-methoxy-2-aminoindane (MEAI) in the wastewater indicates that drug dealers have recently sold this potential NPS to evade drug regulations. This study firstly reports the HRMS-based comprehensive profile of NPS, other illicit drugs, and drug-related compounds in Taiwan, which could be applied as biomarkers for estimating the consumption of drugs. [ABSTRACT FROM AUTHOR]

Our proof-of-concept study develops a suspect screening workflow to identify and prioritize potentially ubiquitous chemical exposures in matched maternal/cord blood samples, a critical period of development for future health risks. We applied liquid chromatography-quadrupole time-of-flight tandem mass spectrometry (LC-QTOF/MS) to perform suspect screening for ∼3500 industrial chemicals on pilot data from 30 paired maternal and cord serum samples (n = 60). We matched 662 suspect features in positive ionization mode and 788 in negative ionization mode (557 unique formulas overall) to compounds in our database, and selected 208 of these for fragmentation analysis based on detection frequency, correlation in feature intensity between maternal and cord samples, and peak area differences by demographic characteristics. We tentatively identified 73 suspects through fragmentation spectra matching and confirmed 17 chemical features (15 unique compounds) using analytical standards. We tentatively identified 55 compounds not previously reported in the literature, the majority which have limited to no information about their sources or uses. Examples include (i) 1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-3-dodecylpyrrolidine-2,5-dione (known high production volume chemical) (ii) methyl perfluoroundecanoate and 2-perfluorooctyl ethanoic acid (two PFAS compounds); and (iii) Sumilizer GA 80 (plasticizer). Thus, our workflow demonstrates an approach to evaluating the chemical exposome to identify and prioritize chemical exposures during a critical period of development.

Drinking water contaminated by fluorosurfactant-based aqueous film-forming foams (AFFF) is a source of human exposure to poly- and perfluoroalkyl substances (PFAS). However, assessment of bioaccumulation potentials of diverse PFAS in commercial products such as AFFF have been insufficient and challenging, especially due to a lack of analytical standards. Here we explore the value of suspect screening, equilibrium dialysis, and molecular-docking simulations to identify potentially bioaccumulative PFAS. We exposed human serum albumin (HSA) protein to dilutions of a legacy AFFF produced by 3M in 1999 using equilibrium dialysis and screened in-vitro protein-binding affinities using high-resolution mass spectrometry (HRMS). Through suspect screening, we identified 32 PFAS and 18 hydrocarbon surfactants in the AFFF that bound to HSA. Quantification of noncovalent association constants for 26 PFAS standards confirmed that many PFAS, including the short-chain perfluoropropane sulfonic acid (log Ka= 4.1 ± 0.2 M-1), exhibit strong binding affinities with HSA. At least five PFAS in AFFF (including three PFAS with less than five perfluorocarbons) remained bound to the precipitated HSA pellet after extensive solvent washing-an indication of high PFAS binding potential. Three PFAS (PFBS, PFOS, and PFOA) were confirmed in the protein pellet with analytical standards and quantified after acid digestion-this sample fraction accounted for 5 to 20% of each compound mass in the sample. We calculated pseudo-bioconcentration factors (BCFpseudo) for PFAS that suspect screening flagged as noncovalently bound or potentially covalently bound. Most PFAS exhibiting high BCFpseudo, especially those with seven perfluorocarbons, contained a carboxylic acid or a sulfonic acid. Finally, we used molecular docking to simulate HSA binding affinities for 62 ligands (26 PFAS targets, 18 PFAS qualified in AFFF, and 18 hydrocarbon surfactants qualified in AFFF). We found that molecular docking can effectively separate HSA-binding and -nonbinding compounds in AFFF. In-vitro and in-silico approaches described in this study provide replicable, high-throughput workflows for assessing bioaccumulation potentials of diverse PFAS in commercial products.

Quaternary ammonium compounds (QACs) are a class of surfactants commonly used in disinfecting and cleaning products. Their use has substantially increased during the COVID-19 pandemic leading to increasing human exposure. QACs have been associated with hypersensitivity reactions and an increased risk of asthma. This study introduces the first identification, characterization and semi-quantification of QACs in European indoor dust using ion-mobility high-resolution mass spectrometry (IM-HRMS), including the acquisition of collision cross section values (DTCCSN2) for targeted and suspect QACs. A total of 46 indoor dust samples collected in Belgium were analyzed using target and suspect screening. Targeted QACs (n = 21) were detected with detection frequencies ranging between 4.2 and 100 %, while 15 QACs showed detection frequencies > 90 %. Semi-quantified concentrations of individual QACs showed a maximum of 32.23 µg/g with a median ∑QAC concentration of 13.05 µg/g and allowed the calculation of Estimated Daily Intakes for adults and toddlers. Most abundant QACs matched the patterns reported in indoor dust collected in the United States. Suspect screening allowed the identification of 17 additional QACs. A dialkyl dimethyl ammonium compound with mixed chain lengths (C16:C18) was characterized as a major QAC homologue with a maximum semi-quantified concentration of 24.90 µg/g. The high detection frequencies and structural variabilities observed call for more European studies on potential human exposure to these compounds. For all targeted QACs, drift tube IM-HRMS derived collision cross section values (DTCCSN2) are reported. Reference DTCCSN2 values allowed the characterization of CCS-m/z trendlines for each of the targeted QAC classes. Experimental CCS-m/z ratios of suspect QACs were compared with the CCS-m/z trendlines. The alignment between the two datasets served as an additional confirmation of the assigned suspect QACs. The use of the 4bit multiplexing acquisition mode with consecutive high-resolution demultiplexing confirmed the presence of isomers for two of the suspect QACs.

Household dust is a reservoir of various consumer product chemicals. Thus, characterizing comprehensive chemical profiles of house dust may help improve our understanding of residential chemical exposure. We have previously developed a method for detecting a broad spectrum of chemicals in dust by applying a combination of target, suspect screening, and non-target methods with mass spectrometry preceded by liquid chromatography and gas chromatography. Building upon a previous study that detected 271 compounds in 38 dust samples, we presented concentrations of 144 compounds that were confirmed and quantified by standards in the same set of samples. Ten compounds were measured with median concentrations greater than 10 000 ng/g of dust: cis-hexadec-6-enoic acid, squalene, cholesterol, vitamin E, bis(2-ethylhexyl) phthalate, dioctyl terephthalate, linoleic acid, tricaprylin, tris(1-chloroisopropyl) phosphate, and oxybenzone. We also reviewed in vitro toxicity screening data to identify compounds that were not previously detected in indoor dust but have potential for adverse health effects. Among 119 newly detected compounds, 13 had endocrine-disrupting potential and 7 had neurotoxic potential. Toxicity screening data were not available for eight biocides, which may adversely affect health. Our results strive to provide more comprehensive chemical profiles of house dust and identified information gaps for future health studies.

The River Itchen and River Test, two chalk streams in Southern England, are sites of special scientific interest. These ecosystems face a number of environmental pressures from anthropogenic inputs of organic pollutants. Hence, we investigated the occurrence of these chemicals within the two catchments. Spot water samples (1 L) were collected at nineteen sites along the catchment on two occasions (March and June 2019). Samples were extracted (HLB-L sorbent disks) and analysed using high-resolution liquid chromatography-quadrupole-time-of-flight mass spectrometry and gas chromatography-mass spectrometry. Compounds were identified against commercially available databases. Using this approach, we found 115 pharmaceutical and personal care products, 81 plant protection products and 35 industrial chemicals. This complex mixture of pollutants covered a range of physico-chemical properties and included priority substances in the EU Water Framework Directive or currently on the third Watch List. Both rivers had similar chemical profiles for both months. Herbicides and fungicides were dominant in the spring, whereas insecticides occurred more frequently in the summer. Point discharges from wastewater treatment plants were the main source of pharmaceutical and personal care products. Agricultural activities were the main contributor to the presence of plant protection products. The impact of these organic chemicals on the ecology, particularly on macroinvertebrate biodiversity, is unknown and warrants further investigation. Our suspect screening approach could guide future toxicological investigations to assess the environmental impacts of these diverse chemicals. [ABSTRACT FROM AUTHOR]

The increasing number of contaminants in the environment has pushed water monitoring programs to find out the most hazardous known and unknown chemicals in the environment. Sample treatment-simplification methods and non-target screening approaches can help researchers to not overlook potential chemicals present in complex aqueous samples. In this work, an effect-directed analysis (EDA) protocol using the sea urchin embryo test (SET) as a toxicological in vivo bioassay was used as simplified strategy to identify potential unknown chemicals present in a very complex aqueous matrix such as hospital effluent. The SET bioassay was used for the first time here to evaluate potential toxic fractions in hospital effluent, which were obtained after a two-step fractionation using C18 and aminopropyl chromatographic semi-preparative columns. The unknown compounds present in the toxic fractions were identified by means of liquid chromatography coupled to a Q Exactive Orbitrap high-resolution mass spectrometer (LC-HRMS) and using a suspect analysis approach. The results were complemented by gas chromatography-mass spectrometry analysis (GC-MS) in order to identify the widest range of chemical compounds present in the sample and the toxic fractions. Using EDA as sample treatment simplification method, the number of unknown chemicals (>446 features) detected in the raw sample was narrowed down to 94 potential toxic candidates identified in the significantly toxic fractions. Among them, the presence of 25 compounds was confirmed with available chemical standards including 14 pharmaceuticals, a personal care product, six pesticides and four industrial products. The observations found in this work emphasize the difficulties in identifying potential toxicity drivers in complex water samples, as in the case of hospital wastewater. [ABSTRACT FROM AUTHOR]

A novel method was developed and optimized for the fast-screening analysis of additives in electronics and plastic consumer products using atmospheric pressure matrix-assisted laser desorption ionization (AP-MALDI) coupled with a high-resolution quadrupole time-of-flight (qTOF) mass spectrometer (MS). To simplify sample preparation and increase sample throughput, an innovative 48 well graphene nanoplatelets (GNP) doped AP-MALDI target plate was developed. The GNP incorporated in the target plate fulfilled the role of the MALDI matrix and, therefore, sample extracts could be directly transferred to the AP-MALDI 48 well target plate and analyzed without a subsequent matrix addition. The homogeneously dispersed and immobilized GNP target plates also provided increased signal intensity and reproducibility. Furthermore, analytical standards of various plastic additives and plastic products with known concentrations of additives were studied to assess the AP-MALDI ionization mechanisms and method capability. The analysis time was 15 s per measurement using an automated sequence. The GNP-doped target plates exhibited high desorption/ionization of low molecular weight molecules (<1000 Da) and can be used in both positive and negative ionization modes. The AP-MALDI-qTOF-MS method was applied to screen for additives in various electronics and plastic consumer products. Suspect screening was performed using a database containing 1366 compounds. A total of 56 additives including antioxidants, flame retardants, plasticizers, UV-stabilizers, and UV-filters were identified (confidence level 4). Identification of certain plastic additives in plastic children's toys may indicate that they are recycled from waste electronic and electronic equipment (WEEE). [ABSTRACT FROM AUTHOR]

One of the main routes of fish exposure to micro- and nanoplastics (MNPLs) is their ingestion. MNPLs can act as reservoirs of organic contaminants that are adsorbed onto their surfaces, or that can leach from their complex formulations, with potential impacts on biota and along the aquatic food chain. While MNPLs have been reported in fishes worldwide, complete information on MNPL compositions, polymers and additives continues to be scarce. In this work, the presence of MNPLs in the gastrointestinal tracts (GIT) of fish from the Ebro River (Spain) was investigated using a double suspected screening approach to assess and quantify polymers and additives. The sample-preparation procedure consisted of sequential alkaline and acidic digestions with KOH and HNO3, followed by ultrasonic-assisted extraction (USAE) with toluene. The analysis of polymers was carried out with size-exclusion chromatography followed by high-resolution mass spectrometry using an atmospheric pressure photoionization source, operating in negative and positive ionisation modes (SEC-(±)-APPI-HRMS) using full-scan acquisition (FS). Plastic additives were assessed using high-performance liquid chromatography with a C18 analytical column coupled to HRMS equipped with an electrospray ionisation source operating under positive and negative conditions (LC-(±ESI)-HRMS). The acquisition was performed in parallel with full-scan (FS) and data-dependent scan (ddMS2) modes, working under positive and negative ionisation modes. The polymers most frequently detected and quantified in fish GITs were polysiloxanes, polyethylene (PE), polypropylene (PP) and polystyrene (PS). PE was detected in 84% of the samples, with a concentration range from 0.55 to 3545 µg/g. On the other hand, plasticisers such as phthalates and stabilisers such as benzotriazoles were the most frequently identified plastic additives. [ABSTRACT FROM AUTHOR]

Liquid chromatography–high-resolution mass spectrometry (LC/HRMS) is a powerful tool for detecting chemicals that are present in low concentrations [...]

Contaminants of emerging concerns (CECs) include numerous chemicals that may pose known and unknown risks to the ecosystem, and identification and risk ranking of these compounds is essential for the environmental management. In this study, liquid and gas chromatography time-of-flight mass spectrometry (LC-QTOF-MS and GC-QTOF-MS) were used to characterize the occurrence of CECs in the surface water of the Yellow River Estuary (YRE). A total of 295 and 315 chemicals were identified by LC-QTOF-MS and GC-QTOF-MS, respectively. The occurrence of two compounds, erucamide and 2-phenylquinoline, was for the first time reported in the aquatic environment in YRE. The concentrations of 121 CECs, including 35 antibiotics, 49 pesticides and veterinary, 16 polycyclic aromatic hydrocarbons and 21 phthalic acid esters were further quantified by target analysis, which showed the detection of 99 compounds in the surface water in the range of 7.07–4611.26 ng/L. Ecological risks of pollutants based on the risk quotient (RQ) method revealed that 13 pollutants posed ecological risks to the aquatic ecosystem (RQ > 1), and pesticides (n = 12) were the main risk contributors. Here, all CECs data sets were finally transformed and ranked in the framework of the toxicological priority index (ToxPi), and a total of 81 priority control pollutants were identified in the surface water of YRE. This study highlighted the necessity of suspect and nontarget screening for CECs in estuaries, and revealed the importance of localized contamination sources in urban and agricultural environment.

Background: The NORMAN Association (https://www.norman-network.com/) initiated the NORMAN Suspect List Exchange (NORMAN-SLE; https://www.norman-network.com/nds/SLE/) in 2015, following the NORMAN collaborative trial on non-target screening of environmental water samples by mass spectrometry. Since then, this exchange of information on chemicals that are expected to occur in the environment, along with the accompanying expert knowledge and references, has become a valuable knowledge base for "suspect screening" lists. The NORMAN-SLE now serves as a FAIR (Findable, Accessible, Interoperable, Reusable) chemical information resource worldwide. Results: The NORMAN-SLE contains 99 separate suspect list collections (as of May 2022) from over 70 contributors around the world, totalling over 100,000 unique substances. The substance classes include per- and polyfluoroalkyl substances (PFAS), pharmaceuticals, pesticides, natural toxins, high production volume substances covered under the European REACH regulation (EC: 1272/2008), priority contaminants of emerging concern (CECs) and regulatory lists from NORMAN partners. Several lists focus on transformation products (TPs) and complex features detected in the environment with various levels of provenance and structural information. Each list is available for separate download. The merged, curated collection is also available as the NORMAN Substance Database (NORMAN SusDat). Both the NORMAN-SLE and NORMAN SusDat are integrated within the NORMAN Database System (NDS). The individual NORMAN-SLE lists receive digital object identifiers (DOIs) and traceable versioning via a Zenodo community (https://zenodo.org/communities/norman-sle), with a total of > 40,000 unique views, > 50,000 unique downloads and 40 citations (May 2022). NORMAN-SLE content is progressively integrated into large open chemical databases such as PubChem (https://pubchem.ncbi.nlm.nih.gov/) and the US EPA's CompTox Chemicals Dashboard (https://comptox.epa.gov/dashboard/), enabling further access to these lists, along with the additional functionality and calculated properties these resources offer. PubChem has also integrated significant annotation content from the NORMAN-SLE, including a classification browser (https://pubchem.ncbi.nlm.nih.gov/classification/#hid=101). Conclusions: The NORMAN-SLE offers a specialized service for hosting suspect screening lists of relevance for the environmental community in an open, FAIR manner that allows integration with other major chemical resources. These efforts foster the exchange of information between scientists and regulators, supporting the paradigm shift to the "one substance, one assessment" approach. New submissions are welcome via the contacts provided on the NORMAN-SLE website (https://www.norman-network.com/nds/SLE/). [ABSTRACT FROM AUTHOR]

BACKGROUND: Plant protection products (PPPs) are used extensively in agriculture to control crops. These PPPs, which may be found in different types of formulations, are composed of a designated pesticide (active principle) and other inactive ingredients as co‐formulants. They perform specific functions in the formulation, as solvents, preservatives or antifreeze agents, among others. RESULTS: A research technique based on ultra‐high‐performance liquid chromatography (UHPLC) coupled to a Quadrupole‐Orbitrap mass analyzer was successfully applied to characterize the composition of six different PPPs in terms of the presence of co‐formulants and types of formulations: emulsifiable concentrate (EC), emulsion in water (EW), suspension concentrate and water‐dispersible granule. These PPPs (FLINT MAX, MASSOCUR 12.5 EC, IMPACT EVO, TOPAS, LATINO and IMPALA STAR) had antifungal activity, containing one triazole compound as active principle (tebuconazole, penconazole, myclobutanil, flutriafol or fenbuconazole, respectively). Non‐targeted approaches, applying suspect and unknown analysis, were carried out and ten compounds were identified as potential co‐formulants. Six (glyceryl monostearate, 1‐monopalmitin, dimethyl sulfoxide, N,N‐dimethyldecanamide, hexaethylene glycol and 1,2‐benzisothiazol‐3(2H)‐one) were confirmed by injecting analytical standards. Finally, these compounds were quantified in the PPPs. CONCLUSION: The current study allowed for detecting co‐formulants in a wide range of concentrations, between 0.04 (dimethyl sulfoxide) and 19.00 g L−1 (glyceryl monostearate), highlighting the feasibility of the proposed analytical methodology. Moreover, notable differences among the types of formulations of PPPs were achieved, revealing that EC and EW were the formulations that contained the largest number of co‐formulants (four out of six detected compounds). © 2022 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Pancreatic lipase (PNLIP, EC 3.1.1.3) plays a pivotal role in the digestion of dietary lipids, a metabolic pathway directly related to obesity. One of the effective strategies in obesity treatment is the inhibition of PNLIP, which is possible to be achieved by specific phenolic compounds occurring in high abundance in some plants. In this study, a multidisciplinary approach is presented investigating the PNLIP inhibitory effect of 33 plants belonging in the Asteraceae botanical family. In the first stage of the study, a rapid and cost-efficient PNLIP assay in a 96-microwell plate format was developed and important parameters were optimized, e.g., the enzyme substrate. Upon PNLIP assay optimization, aqueous and dichloromethane Asteraceae plant extracts were tested and a cut-off inhibition level was set to further analyze only the samples with a significant inhibitory effect (inhibitory rate > 40%), using an ultra-high-performance liquid chromatography hybrid quadrupole time-of-flight mass spectrometry (UHPLC-q-TOF-MS) method. Specifically, a metabolomic suspect screening was performed and 69 phenolic compounds were tentatively identified, including phenolic acids, flavonoids, flavonoid-3-O-glycosides, and flavonoid-7-O-glycosides, amongst others. In the case of aqueous extracts, phytochemicals known for inducing PNLIP inhibitory effect, e.g., compounds containing galloyl molecules or caffeoylquinic acids, were monitored in Chrysanthemum morifolium, Grindella camporum and Hieracium pilosella extracts. All in all, the presented approach combines in vitro bioactivity measurements to high-end metabolomics to identify phenolic compounds with potential medicinal and/or dietary applications. [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]

The monitoring of legacy contaminants in sentinel northern marine mammals has revealed some of the highest concentrations globally. However, investigations into the presence of chemicals of emerging Arctic concern (CEACs) and other lesser-known chemicals are rarely conducted, if at all. Here, we used a nontarget/suspect approach to screen for thousands of different chemicals, including many CEACs and plastic-related compounds (PRCs) in blubber/adipose from killer whales (Orcinus orca), narwhals (Monodon monoceros), long-finned pilot whales (Globicephala melas), and polar bears (Ursus maritimus) in East Greenland. 138 compounds were tentatively identified mostly as PRCs, and four were confirmed using authentic standards: di(2-ethylhexyl) phthalate (DEHP), diethyl phthalate (DEP), di(2-propylheptyl) phthalate (DPHP), and one antioxidant (Irganox 1010). Three other PRCs, a nonylphenol isomer, 2,6-di- tert -butylphenol, and dioctyl sebacate, exhibited fragmentation patterns matching those in library databases. While phthalates were only above detection limits in some polar bear and narwhal, Irganox 1010, nonylphenol, and 2,6-di- tert -butylphenol were detected in >50% of all samples. This study represents the first application of a nontarget/suspect screening approach in Arctic cetaceans, leading to the identification of multiple PRCs in their blubber. Further nontarget analyses are warranted to comprehensively characterize the extent of CEAC and PRC contamination within Arctic marine food webs. [Display omitted] • Marine mammal blubber was nontarget/suspect screened for environmental contaminants. • Suspect screening revealed 138 compounds, mostly plastic-related compounds (PRCs). • Phthalates were only detected in a few individuals, but concentrations ranged up to ∼7 mg/kg. • Irganox 1010, an antioxidant, and alkylphenols were detected in >50% of all samples. • Biomagnification of these PRCs is likely limited relative to legacy persistent organic pollutants. [ABSTRACT FROM AUTHOR]

In a rapidly evolving agri-food landscape fraught with unforeseen chemical risks, the establishment of proactive analytical strategies become paramount to safeguard food safety and public health. Leveraging ultra-high-performance liquid chromatography high resolution tandem mass spectrometry (UHPLC-HRMS/MS), this study presents a comprehensive suspect screening strategy which was designed for the efficient detection of emerging contaminants in food. Employing a generic extraction protocol and an extensive suspect list, the strategy was implemented on representative food samples fortified at parts per billion (ppb) level. A notable range of the observed True Positive Rates (TPR) spanning 84%–100% underscores the strategy's robustness and versatility in accurately identifying a wide array of compounds in complex food matrices. Moreover, the integration of a python-powered graphical user interface (GUI) plays a pivotal role in automating data processing steps, streamlining data and facilitating data prioritisation through the application of a metabolomics-inspired approach. This enhancement significantly elevates the strategy's efficiency for high throughput analyses, thus reflecting a more agile approach in addressing emerging hazards. • A comprehensive suspect screening strategy was developed for the efficient detection of emerging chemical hazards in food. • A python-powered GUI that is capable of automated data processing steps was incorporated for high throughput non-targeted screening. • The strategy's robustness and versatility in accurately identifying a wide array of compounds in complex food matrices were evaluated in this study. [ABSTRACT FROM AUTHOR]

[Display omitted] • Q Exactive-Orbitrap MS used for targeted quantification and untargeted exploration. • Accuracy profile enabled HS-SPME- vs. SHS-GC-HRMS for furan quantification. • SHS-GC-HRMS was more precise and sensitive for furan quantification in infant food. • SHS-GC-HRMS was validated for quantification of furan, 2-MF and 3-MF in infant food. • Furan, 2MF and 3MF were quantified in the main classes of commercial infant food. • Untargeted screening of HS-SPME-GC-HRMS data underlined 13 more furan derivatives. The aim of the present study was to assess the performance and complementarity of methods capable of both quantifying furan, 2-Methylfuran (2-MF) and 3-Methylfuran (3-MF) in infant foods, but also to comprehensively explore other furan derivatives. It is more particularly a question of validating and comparing the couplings of the two headspace extraction methods most used for the analysis of furan compounds − Headspace Solid Phase Microextraction (HS-SPME) and Static HeadSpace (SHS) – with gas chromatography hyphenated to a high-resolution mass detector (Q Exactive-Orbitrap MS) which allows both targeted quantification and suspect screening. Firstly, the accuracy profile approach was implemented to assess, validate and compare HS-SPME- and SHS-GC-Q Exactive-Orbitrap MS for the quantification of furan in two model infant foods, apple puree and first infant formula. SHS-GC-Q Exactive-Orbitrap MS, showed better accuracy (uncertainty < 17.2 % vs 22.5 % for HS-SPME GC-Q Exactive-Orbitrap MS) and better sensitivity (LOQ < 2.8 vs LOQ < 4.0 µg/kg) over a broader validation range (2–100 µg/kg vs 5–100 µg/kg in apple puree). Secondly, SHS-GC-Q Exactive-Orbitrap MS was assessed and validated by accuracy profile for the quantification of 2-MF and 3-MF, with performance close to those for furan except for 3-MF in apple puree. Thirdly, SHS-GC-Q Exactive-Orbitrap MS was used to quantify the levels of these compounds in 20 commercial samples (n = 3) belonging to the four main categories of infant food (infant formulae, fruit purees, infant cereals, vegetable/fish baby meals). Furan was quantified in 75 % of the samples, with maximum levels in the vegetable/fish-based infant foods (up to 127 µg/kg) while 2-MF and 3-MF were quantified in 45 % and 15 % of products respectively, with maximum levels of 14.1 µg/kg in follow-on formula 3rd age and 9.2 µg/kg in apple puree. Finally, SHS- and HS-SPME-GC-Q Exactive-Orbitrap MS data of the 20 infant products were processed in suspect screening mode using Compound DiscovererTM software. Coupling with HS-SPME, it made it possible to identify 13 additional furan derivatives, i.e. 5 more than with SHS. The relevance and safety status of the compounds identified are discussed. [ABSTRACT FROM AUTHOR]

Plasticizers are chemicals that make plastics flexible, and phthalates are commonly used. Due to the toxic effects of phthalates, there is increasing use of non-phthalate plasticizers like acetyl tributyl citrate (ATBC). ATBC has emerged as a safer alternative, yet concerns about its long-term safety persist due to its high leachability and potential endocrine-disrupting effects. This study aims to identify ATBC metabolites using human liver microsomes and suspect screening methods, and to explore potential urinary biomarkers for ATBC exposure. Using ultra-high-performance liquid chromatography coupled with high-resolution mass spectrometry, we identified ATBC metabolites, including acetyl dibutyl citrate (ADBC), tributyl citrate (TBC), and dibutyl citrate (DBC). Urine samples from 15 participants revealed the presence of ADBC in 5, TBC in 11, and DBC in all samples, with DBC concentrations pointedly higher than the other metabolites. These metabolites show promise as biomarkers for ATBC exposure, though further validation with human data is required. Our results underscore the need for comprehensive studies on ATBC metabolism, exposure pathways, and urinary excretion to accurately assess human exposure levels. [Display omitted] • LC-HRMS-based suspect screening method was applied to identify metabolites of ATBC. • ADBC, DBC, and TBC were identified as putative metabolites of ATBC from in vitro experiments using human liver microsomes. • Quantitative analytical methods for metabolites of ATBC in human urine were developed. • ADBC specific for ATBC exposure was detected in low concentrations and only a few, while DBCs were found in all participants. • Further research is needed on urinary excretion fractions and metabolic pathways to accurately assess human exposure to ATBC. [ABSTRACT FROM AUTHOR]

[Display omitted] Phytocannabinoids occurring in Cannabis Sativa L. are unique secondary metabolites possessing interesting pharmacological activities. In this study, the dynamics of thermally induced (60 and 120 °C) phytocannabinoid reactions in four cannabis varieties were investigated. Using UHPLC-HRMS/MS, 40 phytocannabinoids were involved in target analysis, and an additional 281 compounds with cannabinoid-like structures and 258 non-cannabinoid bioactive compounds were subjected to suspect screening. As expected, the key reaction was the decarboxylation of acidic phytocannabinoids. Nevertheless, the rate constants differed among cannabis varieties, documenting the matrix-dependence of this process. Besides neutral counterparts of acidic species, ́neẃ bioactive compounds such as hydroxyquinones were found in heated samples. In addition, changes in other bioactive compounds with both cannabinoid-like and non-cannabinoid structures were documented during cannabis heating at 120 °C. The data document the complexity of heat-induced processes and provide a further understanding of changes in bioactivities occurring under such conditions. [ABSTRACT FROM AUTHOR]

The contamination of paper products by various chemicals has been reported on a global level, but to date, no published research has investigated pharmaceutical contamination of paper-based products. In this study, pharmaceutical analysis was conducted on 42 samples collected from various points of the recycled paper value chain in Cape Town, South Africa, which included the various grades that may be included in the manufacturing of recycled paperboard. The analysis was achieved by ultrasonic-assisted extraction of paper samples before detection by UHPLC-Q Orbitrap. Quantification limits ranged from 1.15 pg/g for ketoprofen to 46.07 pg/g for methocarbamol. Pharmaceuticals identified in newspaper samples were dexamethasone, ketoprofen, and 17β-estradiol. The latter was also detected in paper shopping bags (up to 697.49 ng/g), infant bathtub packaging (280.62 ng/g), battery packaging (137.43 ng/g), and an egg carton (170.47 ng/g). Carbamazepine was also prominent with its concentration reaching 13.02 ng/g in a vegetable box. Suspect screening tentatively identified 14 additional pharmaceuticals in paper samples, with minocycline, prazepam, and anabolic steroids appearing more prominently. This pioneering study indicated that unintentional pharmaceutical exposure had expanded beyond environmental media to consumer products. [Display omitted] • The first reported occurrence of pharmaceuticals contamination in paper samples. • Targeted and suspect screening of various paper grades was performed. • Sensitive analytical method developed using UHPLC- Q Orbitrap. • Reveals the propagation of emerging contaminants beyond environmental matrices. • Consumer usage and waste management protocols contributed to pharmaceutical occurrence. [ABSTRACT FROM AUTHOR]

• Pesticide residues and mycotoxins were analyzed in infant formula by LC-MS/MS. • Less amount of solvent was used for the QuEChERS-based extraction protocol. • Pesticides were detected in 10 % of the infant formula samples. • Detected levels of pesticides do not exceed MRL established by EU and ANVISA. • Suspect screening and unknown analysis were also carried out. Infant formulas (IF) can contain harmful chemical substances, such as pesticides and mycotoxins, resulting from the contamination of raw materials and inputs used in the production chain, which can cause adverse effects to infants. Therefore, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) methodology prior ultra-high performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPL-QqQ-MS/MS) analysis was applied for the determination of 23 contaminants, in 30 samples of Brazilian IF. The method was validated in terms of limit of detection (0.2 to 0.4 μg/kg), limits of quantification (1 and 10 μg/kg), and recovery (64 % to 122 %); precision values, in terms of relative standard deviation (RSD), were ≤ 20 %. Fenitrothion, chlorpyrifos, and bifenthrin were the pesticides detected in the samples, but the values did not exceed the limit set by the European Union (EU), and ANVISA, and they were detected under their limits of quantification. Additionally, suspect screening and unknown analysis were conducted to tentatively identify 32 substances, including some compounds not covered in this study, such as pesticides, hormones, and veterinary drugs. Carbofuran was identified, confirmed and quantified in 10 % of the samples. [ABSTRACT FROM AUTHOR]

• A suspect chemical database containing 7,922 OPs were established based on the PubChem database. • A neoteric suspect screening and priority ranking strategy of typical OPs was developed. • 566, 518, and 540 molecular formulas were detected in sediment, water, and indoor dust samples, respectively. • Three OPs candidates were tentatively identified and semiquantified. Organophosphorus compounds (OPs) are widely used as flame retardants (FRs) and plasticizers, yet strategies for comprehensively screening of suspect OPs in environmental samples are still lacking. In this work, a neoteric, robust, and general suspect screening technique was developed to identify novel chemical exposures by use of ultra-high performance liquid chromatography-Q Exactive hybrid quadrupole-Orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS). We firstly established a suspect chemical database which had 7,922 OPs with 4,686 molecular formulas, and then conducted suspect screening in n = 50 indoor dust samples, n = 76 sediment samples, and n = 111 water samples. By use of scoring criteria such as retention time prediction models, we successfully confirmed five compounds by comparison with their authentic standards, and prioritized three OPs candidates including a nitrogen/fluorine-containing compound, that is dimethyl {1H-indol-3-yl[3-(trifluoromethyl)anilino]methyl} phosphonate (DMITFMAMP). Given that the biodegradation half-life values in water (t 1/2,w) of DMITFMAMP calculated by EPI Suite is 180 d, it is considered to be potentially persistent. This strategy shows promising potential in environmental pollution assessment, and can be expected to be widely used in future research. [ABSTRACT FROM AUTHOR]

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]

Fruits consistently hold a prominent position in healthy dietary habits. Pesticides are used to manage plant diseases, achieve sustainable production, and maintain high food standards. This study utilized a comprehensive analytical technique that involved both targeted analysis and suspect screening. Analysis was conducted using Ultra-high-performance liquid chromatography coupled with hybrid Linear Trap Quadrupole (LTQ)/Orbitrap High Resolution Mass Spectrometry (HRMS) to examine pesticide levels in fruits. The matrices chosen comprised fruit commodities that are commonly consumed in Greece, including table grapes, apples, pears, citrus fruits, and strawberries. The QuEChERS approach was effectively validated for 30 specific pesticides. According to the method acceptance criteria established by SANTE, the QuEChERS method have shown exceptional efficiency in extracting the chosen pesticides, with recovery rates ranging from 70% to 120% in three concentration levels (10, 50, 100 μg kg−1). It also exhibited outstanding linearity, with an R2 more than 0.99. The method exhibited exceptional precision, with relative standard deviations (RSDs) below 20%. Additionally, the combined measurement uncertainty (MU%) was found to be acceptable, remaining below 50% The quantification limits were below 10 μg kg−1 for the majority of the analytes, satisfying the Maximum Residue Levels (MRLs) established by the European Commission. Following targeted analysis, a dietary risk assessment was performed, revealing that both acute and chronic hazard quotients (aHQ and cHQ), along with chronic hazard index (cHI) were below 1, which indicated that the studied commodities are safe for human consumption. In addition, a suspect screening workflow was developed based on an in-house database comprising 355 pesticides commonly applied to the relevant commodities and related transformation products (TPs). Overall, through suspect screening, twenty-two additional pesticides and TPs not included in the target list were identified. Hence, this approach is anticipated to function as proactive alert system guaranteeing the long-term viability of agricultural production. [Display omitted] • Target analysis & suspect screening of pesticides & TPs in fruit commodities. • 50 % of the samples contained at least one pesticide residue. • 30 detections (target) and 71 tentative identifications (suspect) were reported. • The quantified concentration levels ranged between 2.4 and 795.0 μg kg−1 • Dietary risk assessment revealed that the aHQ, cHQ, and HI values were below 1. [ABSTRACT FROM AUTHOR]

The use and advantages of high-resolution mass spectrometry (MS) as a discovery tool for environmental chemical monitoring has been demonstrated for environmental samples but not for biological samples. We developed a method using liquid chromatography-quadrupole time-of-flight MS (LC-QTOF/MS) for discovery of previously unmeasured environmental chemicals in human serum. Using non-targeted data acquisition (full scan MS analysis) we were able to screen for environmental organic acids (EOAs) in 20 serum samples from second trimester pregnant women. We define EOAs as environmental organic compounds with at least one dissociable proton which are utilized in commerce. EOAs include environmental phenols, phthalate metabolites, perfluorinated compounds, phenolic metabolites of polybrominated diphenyl ethers and polychlorinated biphenyls, and acidic pesticides and/or predicted acidic pesticide metabolites. Our validated method used solid phase extraction, reversed-phase chromatography in a C18 column with gradient elution, electrospray ionization in negative polarity and automated tandem MS (MS/MS) data acquisition to maximize true positive rates. We identified "suspect EOAs" using Agilent MassHunter Qualitative Analysis software, to match chemical formulas generated from each sample run with molecular formulas in our unique database of 693 EOAs assembled from multiple environmental literature sources. We found potential matches for 282 (41%) of the EOAs in our database. Sixty-five of these suspect EOAs were detected in at least 75% of the samples; only 19 of these compounds are currently biomonitored in National Health and Nutrition Examination Survey. We confirmed two of three suspect EOAs by LC-QTOF/MS using a targeted method developed through LC-MS/MS, reporting the first confirmation of benzophenone-1 and bisphenol S in pregnant women's sera. Our suspect screening workflow provides an approach to comprehensively scan environmental chemical exposures in humans. This can provide a better source of exposure information to help improve exposure and risk evaluation of industrial chemicals.

Studies have identified hundreds of per- and polyfluoroalkyl substances (PFAS) in aqueous film forming foam (AFFF) using high resolution mass spectrometry (HRMS), and there is increasing reliance on HRMS with suspect screening in areas such as PFAS fate and transport. Characterization of active-use AFFF formulations is crucial for maintaining representative lists of PFAS for such efforts. Herein, targeted analysis, total oxidizable precursor assay (TOP), suspect screening, and non-targeted analysis were used to characterize PFAS in an AFFF currently certified for use by the U.S. military. The sum of PFAS identified during targeted analysis and suspect screening was compared to TOP, demonstrating that > 90% (20.2 mM) of the estimated total PFAS concentration (22.4 mM) was comprised of ''unknown'' PFAS. Tandem and multi-stage tandem mass spectra were used to annotate 10 PFAS within 9 classes, 8 of which have never been reported. A subset are fluorotelomer-based isomers of legacy, electrochemically synthesized PFAS. Thus, suspect screening efforts that rely solely on accurate mass matching may mis-annotate PFAS presented here as isomers that will have key differences in properties such as biotransformation pathways. The total estimated concentration of the 10 PFAS was ~20 mM, which agrees with the ''unknown'' fraction (20.2 mM) identified by TOP.

Within the Human Biomonitoring for Europe initiative (HBM4EU), a study to determine new biomarkers of exposure to pesticides and to assess exposure patterns was conducted. Human urine samples (N = 2,088) were collected from five European regions in two different seasons. The objective of the study was to identify pesticides and their metabolites in collected urine samples with a harmonized suspect screening approach based on liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) applied in five laboratories. A combined data processing workflow included comprehensive data reduction, correction of mass error and retention time (RT) drifts, isotopic pattern analysis, adduct and elemental composition annotation, finalized by a mining of the elemental compositions for possible annotations of pesticide metabolites. The obtained tentative annotations (n = 498) were used for acquiring representative data-dependent tandem mass spectra (MS2) and verified by spectral comparison to reference spectra generated from commercially available reference standards or produced through human liver S9 in vitro incubation experiments. 14 parent pesticides and 71 metabolites (including 16 glucuronide and 11 sulfate conjugates) were detected. Collectively these related to 46 unique pesticides.For the remaining tentative annotations either (i) no data-dependent MS2 spectra could be acquired, (ii) the spectral purity was too low for sufficient matching, or (iii) RTs indicated a wrong annotation, leaving potential for more pesticides and/or their metabolites being confirmed in further studies. Thus, the reported results are reflecting only a part of the possible pesticide exposure.

By use of an integrated target, suspect, and non-target screening strategy, we investigated occurrence and spatial distribution of organophosphate esters (OPEs) in four types of water (drinking water resource water, surface water, groundwater, and seawater) collected from Jiangsu Province (China) in 2021 (n = 111). Eighteen out of 23 target OPEs were detectable at least once in these analyzed samples, and the total concentrations (Σ18OPEs) of OPEs in various water samples exhibited a descending order following as: groundwater (67026 ng/L) > surface water (35803 ng/L) > drinking water resource water (21055 ng/L) > seawater (17820 ng/L). The highest concentration detected in groundwater may be ascribed to pollution from surrounding factories. Among the target OPEs, triethyl phosphate (TEP), tris(chloroethyl) phosphate (TCEP), and tris (1-chloro-2-propyl) phosphate (TCIPP) were the most abundant congeners with the average concentrations of 407 ng/L, 143 ng/L, and 475 ng/L, respectively. Besides of 18 target OPEs, we further identified 17 suspect OPEs (3 of them were fully identified by authentic standards) on the basis of in-house suspect screening OPE database, and 2 non-target organophosphates (OPs) on the basis of feature fragments. One of these 2 non-target OPs was fully identified as bis(2-chloroethyl) 2-chloroethylphosphonate (B2CE2CEPP) by matching the retention time and MS/MS data with authentic standard, and the other one was preliminarily identified as 2,4,8,10-tetra-tert-butyl-6-methoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-one (TTBMDBDOPPO). We also observed that B2CE2CEPP shared a similar structure with TCEP, suggesting that they may have similar toxicological characteristics and commercial sources. The ecological and human health risk assessments indicated that all OPEs posed a low or negligible ecological risk to aquatic organisms (algae, crustacean, and fish), and negligible risk to human health except for trimethyl phosphate (TMP) in drinking water resource water.

Monitoring data from apex predators were key drivers in the development of early chemicals legislations due to the population declines of many species during the twentieth century, which was linked to certain persistent organic pollutants (POPs). Besides triggering the development of global treaties (e.g. the Stockholm Convention), chemical monitoring data from apex predators have been particularly important for identifying compounds with bioaccumulative properties under field conditions. Many apex predators are protected species and only a few environmental specimen banks (ESBs) regularly collect samples as many ESBs were established during the 1980–1990s when apex predators were scarce. Today, many POPs have been banned, which contributed to the recovery of many apex predator populations. As a consequence, apex predator samples are now available in research collections (RCs) and natural history museums (NHMs). These samples can be used for routine analysis as well as for screening studies using novel analytical techniques and advanced data treatment workflows, such as suspect and non-target screening. The LIFE APEX project has demonstrated how these samples can be used in a cost-efficient way to generate data on legacy compounds and contaminants of emerging concern. Furthermore, it has described quality assurance/control measures to ensure high quality and comparable data, with a view to uses in chemicals risk assessment and management. To increase the visibility of available sample collections and monitoring data from apex predators we developed accessible online database systems. Additionally, the acquired high-resolution mass spectrometric data were stored in a digital sample freezing platform that allows retrospective suspect screening in previously analysed samples for substances that may be of concern/under assessment in the future. These databases provide open access to a wide range of chemical data, for use by regulators, researchers, industry and the general public, and contribute to a stronger link between science and policy. [ABSTRACT FROM AUTHOR]

Healthy dietary habits encourage vegetable consumption. Although pesticide use in crops may negatively affect human health through food intake, it can also contaminate aquatic and terrestrial environments. Thus, monitoring pesticides in high-consumption matrices is crucial. This study conducted a complete workflow of analysis, including a step of target analysis of 30 widely used pesticides and a subsequent step of suspect screening. A validated QuEChERS method was employed to analyze 61 samples of fruiting vegetables and cucurbits, packaged leafy greens, and root and tuber vegetables, commercially distributed across Greece. The method proved to be highly efficient for all validation characteristics. After target analysis, the change in the residue levels detected during sample processing was evaluated as a case study using available literature data. A health risk assessment based on diet indicated acute and chronic hazard quotients (aHQ and cHQ) and chronic hazard index (cHI) values below 1. Concerning suspect screening, 53 additional identifications of pesticides and transformation products (TPs) were revealed, totaling 86 detections. Overall, 18 parent pesticide compounds and 5 TPs were identified. Ultimately, this approach is expected to provide added value in pesticide and TPs analysis of food matrices without prior data, minimizing experimental time and costs., 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 Elsevier B.V. All rights reserved.)