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Isolation of complex dissolved organic matter (DOM) from environmental water is a major challenge for unknown screening analysis by high-resolution mass spectrometry. In this study, DOM in process water during advanced drinking water treatment was fractionated sequentially by three solid-phase extraction (SPE) cartridges based on the polarity and charge of DOM molecules. By sequential SPE with unknown screening analysis, over 3000 DOM features were found in raw water, whereas around 2000 were obtained by a single SPE. The hydrophobic neutral (HPON) fraction contained CHO features with highest averaged molecular weight followed by hydrophobic acid (HPOA) and then hydrophilic acid (HPIA). The average degree of carbon double bond equivalents and carbon oxidation states indicated that the HPON fraction contained molecules that were more unsaturated and less oxidized than those of the HPOA and HPIA fractions. Ozone selectively decomposed (1) more unsaturated and less oxidized HPON features, (2) more unsaturated HPOA compounds, and (3) less oxidized HPIA molecules. Oxidation by-products were mostly HPON and HPIA compounds that were more oxidized than the decomposed molecules. During biological activated carbon (BAC) filtration, less oxidized HPON were preferentially removed, whereas HPOA were removed without selectivity. HPON and HPIA molecules with more oxidized character were found to be refractory to BAC treatment. HPON with more unsaturated and HPIA with more oxidized characters were decomposed by chlorine. Many types of HPIA decomposed during chlorination were the oxidation by-products of ozonation that were refractory to BAC treatment. Sequential SPE with unknown screening analysis provided previously unknown details of the molecular characteristics of DOM and its changes during advanced water treatment. • Sequential solid-phase extraction effectively recovers dissolved organic matter (DOM). • Ozone preferentially decomposes more unsaturated and less oxidized DOM. • Ozone oxidation by-products are found as highly oxidized hydrophobic neutral (HPON) and hydrophilic acid (HPIA). • Biological activated carbon filtration removes less oxidized HPON and hydrophobic acid (HPOA). • Chlorine selectively reacts with HPON and HPIA species. [ABSTRACT FROM AUTHOR]

The increasing organic contamination of surface water hinders the conventional tap water treatment process. Membrane bioreactors (MBRs) are a promising alternative technology for recovering water from polluted surface water. In this study, the composition changes of dissolved organic matters (DOMs) in MBR and ultraviolet/ozone (UV/O 3)-MBR systems for polluted surface water treatment were investigated using Orbitrap mass spectrometry analysis with unknown screening. The intense DOM ions within a mass-to-charge ratio range of 100–500 was detected, and 2340 molecular formulae from 5743 peaks were assigned to the two systems. The most abundant components were formulae with C, H, O, N, and CHO only classes. The highest formulae decrease including CHO, CHON, CHOS, and CHONS were attributed to the bio-carrier used in both systems. Results showed that bioprocess was the main contributor in the DOM reduction, and the integration of UV/O 3 into the MBR improved the DOM composition changes. Biodegradable components with low O/C ratio in the CHO and CHON classes remarkably increased in the UV/O 3 -MBR system. The integration of UV/O 3 as a polishing step in the recirculation stream of MBR system was effective in improve the DOM removal. Image 1 • Orbitrap MS was used to detect dissolved organic matter changes in membrane bioreactor for treating polluted surface water. • 2340 molecular formulae out of total peaks 5743 were assigned. • The main change was taken place in carrier side of membrane bioreactor system. [ABSTRACT FROM AUTHOR]

Dissolved organic matter (DOM) have been reported as precursors of disinfection byproducts (DBPs) and its molecular characteristics are rarely investigated due to its complexity. In this study, changes in the characteristics of DOM were investigated in the lower Phong River in Thailand in dry season and after the first rain in rainy season, using a non-targeted analysis with Orbitrap mass spectrometry. The river was rich with CHO features dominated by lignin-like molecules, while lipid-like molecules increase after domestic wastewater discharges. Wastewater discharge released DOM with higher molecular weight (MW) that was less oxygenated (low O/C) and less oxidized (low carbon oxidation state [C os ]). A lake affected by anthropogenic activities contributed more oxidized DOM into the river, while surface runoff carried DOM that is more oxygenated (high O/C), less hydrogenated (low H/C), and more oxidized (high C os) to the stream. Water treatment further modified DOM to be lower MW. Approximately three hundred Cl-containing features (CHOCl) detected upstream were also found downstream. Disinfection by chlorine (Cl 2) or chlorine dioxide (ClO 2) formed both CHO and CHOCl DBPs. Low chlorine dosage applied to upstream and downstream samples resulted in many common unknown DBPs while increasing chlorine dosage resulted in more unique DBPs. At the same dosage, Cl 2 reacted with DOM more than ClO 2 , including more oxidized molecules that are refractory to ClO 2. Both Cl 2 and ClO 2 produced chlorinated and non-chlorinated DBPs, and some DBPs were commonly found by both disinfections. Cl 2 -produced DBPs were more unsaturated (higher [DBE–O]/C) and oxidized (higher C os) than ClO 2 -DBPs. Image 1 • Molecular changes in dissolved organic matter (DOM) along the river were tracked. • Domestic discharges release DOM with high molecular weight (MW) and less oxidized. • A natural lake contributed more oxidized DOM into the river. • Water treatment further modified DOM to be lower MW. • Unique and shared CHO and CHOCl disinfection byproducts (DBPs) were found by chlorine or chlorine dioxide. [ABSTRACT FROM AUTHOR]

An improved assessment of environmental risks to public water bodies requires screening a large number of micropollutants. This study reports the development of a novel target screening method based on solid-phase extraction (SPE), HPLC, and high-resolution Orbitrap MS for the analysis of micropollutants with diverse chemical properties. First, target compounds were screened for their detectability by Orbitrap MS. An optimized SPE cartridge and HPLC column maximized recovery and separated most target compounds. The sensitivity and repeatability of the method was validated by determining the detection limits and relative standard deviation (RSD). Eighty-four compounds with highly diverse properties were simultaneously detected with detection limits of 0.1–100 ng/L. Of these compounds, 52 were quantitated, with R2 ≥ 0.99 by linearity analysis and SPE recovery ratios of ≥50%. The remaining 32 compounds were qualitatively detected, with R2 < 0.99 or SPE recovery ratio of <50%. Satisfactory repeatability was obtained (RSD < 13.5%). This method was applied to the surveillance of the Arakawa River in Japan in 2019. Thirty-two compounds, including pesticides, surfactants, plasticizers, adhesives, and industrial solvents, were detected in the river. The measured concentrations of 13 compounds were compared with their predicted no effect concentrations (PNECs). Decanoic acid showed a higher concentration than the corresponding PNEC value, suggesting that its risk to the Arakawa water environment required further evaluation. The concentrations of dicyclohexylamine, 1,3-diphenylguanidine, and 2,4-dichlorophenoxyacetic acid were higher than their corresponding PNEC/10 values, demonstrating that these compounds were of higher priority than other compounds. [Display omitted] • Development of a quantification method using SPE-HPLC-Orbitrap MS. • Simultaneous detection of 84 micropollutants with high reliability. • Mostly lower method quantification limits than conventional analytical methods. • Method applicability: screening analysis of micropollutants in water environment. [ABSTRACT FROM AUTHOR]

This study aimed to classify the possible molecular formulas of precursors for disinfection by-products (DBPs) in raw, coagulated, and chlorinated water samples from the U-Tapao Canal, Songkhla, Thailand. The molecular formulas of DBPs in chlorinated water were investigated. Polyaluminum chloride (PACl) was employed as a coagulant. Orbitrap Fourier transform-mass spectrometry was able to estimate the composition of dissolved organic matter (DOM) with the carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and sulfur (S) elements contained and DBPs at the molecular level. The molecular formulas of the DOM in the raw water primarily consisted of CHO and CHON when extracted by lichrolut EN. The CHO and CHON species were rich in lignin-, tannin-, and condensed aromatic-like substances. The DOM with high-molecular-weight from 300 to 500 Da were preferentially removed by coagulation. The PACl coagulation decreased the abundances of lignin-, tannin-, and condensed aromatic-like substances in the CHO formulas, while lignin- and condensed aromatic-like substances in the CHON formulas remained. The remaining precursors corresponded to CHON molecules in the coagulated water, which may result in the formation of some chlorine (Cl)-containing molecules. Several DBPs among the CHOCl and CHONCl species were produced in the chlorinated water through the addition reaction of chlorine. New chlorinated N-DBPs of 21 formulas were detected. Image 1 • The LiEN is selective for trapping DOM in a wide mass range (100–500 Da). • The non-targeted DBP precursors were evaluated by the Orbitrap mass spectrometry. • PACl coagulation mostly removed DOM with MW ranging from 300 to 500 Da. • Formation of CHOCl and CHONCl species corresponded to their putative precursors. [ABSTRACT FROM AUTHOR]

Isotope dilution techniques (IDT) and sequential extraction procedures (SEPs) were compared to apprehend the differences between two techniques in determining metal exchangeability and vulnerability to pollute the urban groundwater. For this purpose, soil (n = 2), "soakaway" sediment deposited in the artificial infiltration facilities (AIF) (n = 4), and road dust (n = 2) were sampled from Tokyo metropolitan. Sorption coefficients of four metals (Cu, Zn, Cd and Pb) were assessed through isotopic exchangeability (E-value) and potential mobile pool i.e. addition of exchangeable, reducible and oxidizable fraction obtained by Community Bureau of Reference (BCR)-procedures. The E-value for the three samples were found smaller than the potential mobile pool but were higher than BCR-exchangeable fractions. The use of strong extractants are likely to play an active role in the disagreement between SEPs and IDT. IDT accounts for the isotopic exchangeability while BCR provides information of vulnerability of metals associated with different fractions that can leach under different environmental conditions. Sorption coefficients measured in soakaway sediment was found comparable to soil thus likely to retain metals. However, as variability in environmental conditions is likely to affect Kd, the soakaway sediment may become an active metal source in future rather than acting as the permanent sink. The study concludes that there is the possibility of errors while predicting metal vulnerability to groundwater with both techniques and thus a model compliance integrating the virtue of both techniques will be a way forward. Image 1 • Better compliance amid isotope dilution and sequential extraction for high metal loading. • Isotopic exchangeability (E-value) was smaller than extracted potential mobile pool. • Coupling of IDT with BCR provide better estimate of leaching vulnerability for metals. • IDT accounts for actual exchangeability while SEPs provide leaching vulnerability. [ABSTRACT FROM AUTHOR]

An improved assessment of environmental risks to public water bodies requires screening a large number of micropollutants. This study reports the development of a novel target screening method based on solid-phase extraction (SPE), HPLC, and high-resolution Orbitrap MS for the analysis of micropollutants with diverse chemical properties. First, target compounds were screened for their detectability by Orbitrap MS. An optimized SPE cartridge and HPLC column maximized recovery and separated most target compounds. The sensitivity and repeatability of the method was validated by determining the detection limits and relative standard deviation (RSD). Eighty-four compounds with highly diverse properties were simultaneously detected with detection limits of 0.1-100 ng/L. Of these compounds, 52 were quantitated, with R 2  ≥ 0.99 by linearity analysis and SPE recovery ratios of ≥50%. The remaining 32 compounds were qualitatively detected, with R 2  < 0.99 or SPE recovery ratio of <50%. Satisfactory repeatability was obtained (RSD < 13.5%). This method was applied to the surveillance of the Arakawa River in Japan in 2019. Thirty-two compounds, including pesticides, surfactants, plasticizers, adhesives, and industrial solvents, were detected in the river. The measured concentrations of 13 compounds were compared with their predicted no effect concentrations (PNECs). Decanoic acid showed a higher concentration than the corresponding PNEC value, suggesting that its risk to the Arakawa water environment required further evaluation. The concentrations of dicyclohexylamine, 1,3-diphenylguanidine, and 2,4-dichlorophenoxyacetic acid were higher than their corresponding PNEC/10 values, demonstrating that these compounds were of higher priority than other compounds., 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 © 2020 Elsevier Ltd. All rights reserved.)