Fragmentation Pattern-Based Screening Strategy Combining Diagnostic Ion and Neutral Loss Uncovered Novel para-Phenylenediamine Quinone Contaminants in the Environment

Environmental Science & Technology, Год журнала: 2024, Номер 58(13), С. 5921 - 5931

Опубликована: Март 21, 2024

Identifying transformed emerging contaminants in complex environmental compartments is a challenging but meaningful task. Substituted para-phenylenediamine quinones (PPD-quinones) are originating from rubber antioxidants and have been proven to be toxic the aquatic species, especially salmonids. The emergence of multiple PPD-quinones various matrices evidence their specific hazards underscore need understand occurrences. Here, we introduce fragmentation pattern-based nontargeted screening strategy combining full MS/All ion fragmentation/neutral loss-ddMS2 scans identify potential unknown different matrices. Using diagnostic fragments m/z 170.0600, 139.0502, characteristic neutral losses 199.0633, 138.0429 Da, six known three novel were recognized air particulates, surface soil, tire tissue. Their structures confirmed, concentration composition profiles clarified with self-synthesized standards. N-(1-methylheptyl)-N′-phenyl-1,4-benzenediamine quinone (8PPD-Q) N,N′-di(1,3-dimethylbutyl)-p-phenylenediamine (66PD-Q) identified quantified for first time, median concentrations found 0.02–0.21 μg·g–1 tissue, 0.40–2.76 pg·m–3 particles, 0.23–1.02 ng·g–1 soil. This work provides new presence environment, showcasing environment.

Язык: Английский

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Broad-spectrum capture of hundreds of per- and polyfluoroalkyl substances from fluorochemical wastewater

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 25, 2025

Abstract Hundreds of per- and polyfluoroalkyl substances (PFAS) are present in fluorochemical production effluents, existing adsorption devices inadequate to address this PFAS challenge given their extreme structural diversity. Here, we achieve the broad-spectrum capture 107 from effluents using a treatment-train strategy that combines Zn-based electrocoagulation (EC) with anion-exchange resin (AER) beds. The “zero-carbon” adsorbent, zinc hydroxide flocs generated insitu by EC, bulk removes log K ow > 4 through semi-micellar mechanism similar mineral flotation achieves capacities at optimal level all reported adsorbents. Technical-economic analysis life-cycle environmental impact show coupling EC reduces cost an order-of-magnitude carbon-footprint 70% compared AER beds alone. It is also observed iodinated PFAS, some fluorine atoms replaced iodine atoms, exhibit significantly improved selectivity, which may shed light on designing environmentally-friendly fluorochemicals.

Язык: Английский

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IodoFinder: Machine Learning-Guided Recognition of Iodinated Chemicals in Nontargeted LC-MS/MS Analysis

Environmental Science & Technology, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

Iodinated disinfection byproducts (I-DBPs) pose significant health concerns due to their high toxicity. Current approaches recognize unknown I-DBPs in mass spectrometry (MS) analysis rely on negative ionization mode, which the characteristic I– fragment can be observed tandem spectra (MS/MS). Still, many ionize exclusively positive where is absent. To address this gap, work developed a machine learning-based strategy iodinated compounds (I-compounds) from MS/MS both electrospray (ESI+) and (ESI−) modes. Investigating over 6000 of 381 I-compounds, we first identified five I-containing neutral losses one diagnostic ESI+ ESI– modes, respectively. We then trained Random Forest models integrated them into IodoFinder, Python program, streamline recognition I-compounds raw LC-MS data. IodoFinder accurately recognized 96% 161 I-compound standards In its application DBP mixtures, discovered 19 with annotated structures an additional 17 assigned formulas, including 12 novel 3 confirmed I-DBPs. envision that will advance identification known exposome studies.

Язык: Английский

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Development of a Nontargeted Algorithm for Per- and Polyfluoroalkyl Substances in the FT-ICR Mass Spectra of Complex Organic Mixtures

Analytical Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

The unrivaled mass resolving power and subppm error enable the application of Fourier transform ion cyclotron resonance spectrometry (FT-ICR MS) for nontargeted screening per- polyfluoroalkyl substances (PFAS). Few automated FT-ICR MS methods exist analysis PFAS in solutions containing other dissolved organic matter. In this study, isotopic pattern dynamic homologous series inspection were complementarily employed FTMSDeu algorithm to simultaneously assign chemical formulas molecules, with an overall assignment accuracy 91.2% 1,802 unique their 11,634 formulas. negative effects fluorine-related isobaric isotopes sub-mDa differences on formula natural matter addressed by empirical F/(H + X) rule adoption a threshold number plus number. There 203 one novel formula, C9H6O4S1I1F11, identified fluoropolymer industry-impacted river water sample using our analyzing spectra. Overall, results study highlighted great potential updated high-throughput spectra complex mixtures from real environmental samples.

Язык: Английский

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Characterization of halogenated organic compounds by the Fourier transform ion cyclotron resonance mass spectrometry: A critical review

Water Research, Год журнала: 2023, Номер 246, С. 120694 - 120694

Опубликована: Окт. 4, 2023

Язык: Английский

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Nontarget and Comprehensive Analyses of Halogenated Organic Additives in Electrical Product Plastics by GC-NCI-Q-Orbitrap-HRMS and Cl/Br-Screening Algorithms

Analytical Chemistry, Год журнала: 2023, Номер 95(26), С. 10052 - 10060

Опубликована: Июнь 20, 2023

Halogenated organic additives (HOAs) are used in plastic components of various electrical products, potentially causing detrimental effects on the eco-environment and humans. Besides reported HOAs, many unknown HOAs may be present product plastics urgently require identification characterization. This study performed nontarget analysis comprehensive characterization three typical by using gas chromatography–negative chemical ionization–high-resolution mass spectrometry association with in-house-developed chlorine/bromine-specific data-processing algorithms. A total 674 formulas were identified dismantled from among which 166, 362, 146 organochlorines, organobromines, mix-chlorinated/brominated compounds, respectively. The semiquantified, concentrations individual 445–1549 ng/g. Organobromines showed most species highest abundances all plastics, accounted for 86.6–98.0% HOAs. Partial (209 formulas) tentatively structurally elucidated, classified into 13 groups, i.e., halogenated alkyl phenoxyethyls (H-alkyl phenoxyethyls), H-alkylbenzenes, H-benzenes, H-bisphenol (H-BPAs), H-dioxins, H-diphenyl ethers, H-biphenyls/terphenyls, H-polycyclic aromatic hydrocarbons, H-phenols, H-phenyl esters, H-phenyl-aldehydes/ketones, H-quinones, an undefined group containing such as dechlorane plus chlordane. H-BPAs predominant showing relatively high (13–281 ng/g), tetrabromobisphenol was abundant H-BPA, 9–196 results represent a holistic picture features abundance distributions provide inventory crucial worthy concern. migrate release environment possibly important source pollutants environment, thus calling further investigation proper regulation.

Язык: Английский

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Nontarget Analysis and Comprehensive Characterization of Iodinated Polyfluoroalkyl Acids in Wastewater and River Water by LC-HRMS with Cascade Precursor-Ion Exclusions and Algorithmic Approach

Environmental Science & Technology, Год журнала: 2023, Номер 57(44), С. 17099 - 17109

Опубликована: Окт. 25, 2023

Poly- and perfluoroalkyl acids (PFAAs) are a large family of widespread contaminants worldwide concern well-known as "forever chemicals". Direct emission PFAAs from the fluorochemical industry is crucial source PFAA pollutants in environment. This study implemented nontarget analysis comprehensive characterization for category new contaminants, i.e., iodinated (IPFAAs), wastewater relevant contaminated river water by liquid chromatography–high-resolution mass spectrometry with cascade precursor ion exclusion (PIE) strategy in-house developed data extraction processing algorithms. A total 26 IPFAAs (including 2 isomers an IPFAA) were found identified tentative molecular structures. Semiquantification was implemented, concentrations 0.16–285.52 0.15–0.17 μg/L water, respectively. The high association predicted ecotoxicities environmental behaviors demonstrate that these worthy more further in-depth research. PIE along algorithms can be extended to other beyond IPFAAs. identification outcomes provide understanding on occurrence pollution status perspective.

Язык: Английский

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Nontarget Analysis and Characterization of a Group of Abundant Polyfluoroalkyl Substances─Fluorinated Benzoylurea Pesticides and Their Analogues and Transformation Products in Fish by LC-HRMS and Chemical Species-Specific Algorithms

Journal of Agricultural and Food Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

Poly- and perfluoroalkyl substances (PFASs) are a large class of fluorinated chemicals used in various industrial agrochemical products such as benzoylurea (FBU) pesticides. Initiated from an incidental preliminary finding three high-abundance FBUs fish, this study implemented nontarget analysis characterization for together with their analogues transformation (TPs) fish using liquid chromatography, high-resolution mass spectrometry, chemical species-specific algorithms. A total 23 FBU-relevant compounds were found tentatively/accurately elucidated structures, including 18 PFASs 5 non-PFAS compounds, which 4 original FBUs, 8 FBU analogues, 11 FBU-TPs. The concentrations 0.8–1919.3 ng/g the samples. strategy data-processing algorithms can be extended to other fluorine-containing pesticides, results provide new understanding PFAS pollution unveil important source pollutants, utilization FBUs.

Язык: Английский

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A new indirect method for the quantification of total organic iodine (TOI) in environmental waters by inductively coupled plasma with mass spectrometry and liquid chromatography with tandem mass spectrometry

Journal of Chromatography B, Год журнала: 2025, Номер unknown, С. 124489 - 124489

Опубликована: Янв. 1, 2025

Язык: Английский

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Durable Ti₄O₇ Heterojunction Composite Membrane Encapsulating N-Doped Graphene Nanosheets for Efficient Electro-Oxidation of GenX and Other PFAS in Fluorochemical Wastewater

Environmental Science & Technology, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

Rational interfacial engineering design of an electrocatalyst, such as a heterojunction structure, can effectively enhance its catalytic activity. This study aims to address critical challenge associated with the use carbon material@Ti4O7 composite electrodes for wastewater treatment─electrode stability over long-term operation. Herein, we report highly stabilized strategy, i.e., conductive inorganic CeO2 "cement" firmly encapsulate N-doped graphene oxide nanosheets (N-GS) on Ti4O7 surface. The defect-rich N-GS encapsulated surface significantly enhances charge transfer. enhancement results in N-GS/CeO2@Ti4O7 electrode exhibiting excellent efficiency electro-oxidation hexafluoropropylene dimer acid (HFPO-DA or GenX). Furthermore, flow-through reactive electrochemical membrane system mineralizes other 35 PFASs real fluorochemical sample, achieving high defluorination rate 70-90% and better performance PFAS destruction energy compared UV/KI-SO32- process. Results this our understanding oxidation offer valuable insight into composites. These findings are instrumental advancing development effective treatments PFAS-contaminated environments.

Язык: Английский

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