High-molecular-weight disinfection byproducts in simulated drinking water: characterization and identification via matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Abstract

High-molecular-weight disinfection byproducts (HMW DBPs) have been increasingly recognized as contaminants that pose potential hazards to human health. However, reliable analytical methods for exploring the properties and structures of these DBPs remain limited. This study presents a novel approach for detecting and identifying HMW DBPs via matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The experimental conditions were optimized by selecting super-2,5-dihydroxybenzoic acid (super-DHB) as the matrix and sodium trifluoroacetate as the cationization agent and employing the sandwich deposition method in reflection-positive ion mode with 90% laser intensity, resulting in the highest peak intensity for HMW DBPs. These optimized conditions enhanced peak reproducibility, yielding a signal-to-noise ratio of 134.9 and a coefficient of variation of 3.8%. With the new approach, five HMW DBPs were detected in simulated drinking water and identified as oligosaccharide carboxylic acids via isotopic pattern analysis, tandem mass spectrometry analysis in laser-induced dissociation mode, and database verification.

Graphical abstract

Keywords

Identification / HMW DBPs / Matrix-assisted laser desorption/Ionization time-of-flight mass spectrometry / Oligosaccharides carboxylic acids

Highlight

	● Detection method of HMW DBPs using MALDI-TOF MS was established.
	● Molecular and structural identification of HMW DBPs was performed.
	● Identified HMW DBPs were oligosaccharides with oxidized end groups.

References

[1] Artifon V, Zanardi-Lamardo E, Fillmann G. (2019). Aquatic organic matter: classification and interaction with organic microcontaminants. Science of the Total Environment, 649(1): 1620–1635

[2] Chen Z M, Geng Z R, Shao D L, Mei Y H, Wang Z L. (2009). Single-crystalline EuF₃ hollow hexagonal microdisks: synthesis and application as a background-free matrix for MALDI-TOF MS analysis of small molecules and polyethylene glycols. Analytical Chemistry, 81(18): 7625–7631

[3] Coburn K M, Wang Q Z, Rediske D, Viola R E, Hanson B L, Xue Z, Seo Y. (2016). Effects of extracellular polymeric substance composition on bacteria disinfection by monochloramine: application of MALDI-TOF/TOF-MS and multivariate analysis. Environmental Science & Technology, 50(17): 9197–9205

[4] Cortés-Francisco N, Caixach J. (2013). Molecular characterization of dissolved organic matter through a desalination process by high resolution mass spectrometry. Environmental Science & Technology, 47(17): 9619–9627

[5] Dauly C, Perlman D H, Costello C E, McComb M E. (2006). Protein separation and characterization by np-RP-HPLC followed by intact MALDI-TOF mass spectrometry and peptide mass mapping analyses. Journal of Proteome Research, 5(7): 1688–1700

[6] Devarajan D, Liang L Y, Gu B H, Brooks S C, Parks J M, Smith J C. (2020). Molecular dynamics simulation of the structures, dynamics, and aggregation of dissolved organic matter. Environmental Science & Technology, 54(21): 13527–13537

[7] Dong H Y, Cuthbertson A A, Plewa M J, Weisbrod C R, McKenna A M, Richardson S D. (2023). Unravelling high-molecular-weight DBP toxicity drivers in chlorinated and chloraminated drinking water: effect-directed analysis of molecular weight fractions. Environmental Science & Technology, 57(47): 18788–18800

[8] Hao J, Lu J J, Xu N Y, Linhardt R J, Zhang Z Q. (2016). Specific oxidation pattern of soluble starch with TEMPO-NaBr-NaClO system. Carbohydrate Polymers, 146(1): 238–244

[9] Hebert A, Feliers C, Lecarpentier C, Neale P A, Schlichting R, Thibert S, Escher B I. (2018). Bioanalytical assessment of adaptive stress responses in drinking water: a predictive tool to differentiate between micropollutants and disinfection by-products. Water Research, 132: 340–349

[10] Lau S S, Bokenkamp K, Tecza A, Wagner E D, Plewa M J, Mitch W A. (2022). Toxicological assessment of potable reuse and conventional drinking waters. Nature Sustainability, 6(1): 39–46

[11] Li J F, Aziz M T, Granger C O, Richardson S D. (2021). Are disinfection byproducts (DBPs) formed in my cup of tea? Regulated, priority, and unknown DBPs. Environmental Science & Technology, 55(19): 12994–13004

[12] Li X F, Mitch W A. (2018). Drinking water disinfection byproducts (DBPs) and human health effects: multidisciplinary challenges and opportunities. Environmental Science & Technology, 52(4): 1681–1689

[13] Li Y, Jiang J Y, Li W X, Zhu X H, Zhang X R, Jiang F. (2020). Volatile DBPs contributed marginally to the developmental toxicity of drinking water DBP mixtures against Platynereis dumerilii. Chemosphere, 252: 126611

[14] Liao Y F, Tang M M, Li M Y, Shi P, Li A M, Zhang Y Y, Pan Y. (2023). Control strategies for disinfection byproducts by ion exchange resin, nanofiltration and their sequential combination. Frontiers of Environmental Science & Engineering, 17(10): 125

[15] Liao X B, Liu X Y, He Y Y, Tang X P, Xia R J J, Huang Y J, Li W H, Zou J, Zhou Z M, Zhuang M Z. (2024). Alternate disinfection approaches or raise disinfectant dosages for sewage treatment plants to address the COVID-19 pandemic? From disinfection efficiency, DBP formation, and toxicity perspectives. Frontiers of Environmental Science & Engineering, 18(9): 115

[16] Lin Y, Huang X, Liu Q, Lin Z, Jiang G B. (2020). Thermal fragmentation enhanced identification and quantification of polystyrene micro/nanoplastics in complex media. Talanta, 208(1): 120478

[17] Ling L, Xiao C S, Ma Y, Jiang L Y, Wang S, Guo L M, Jiang S M, Guo X H. (2019). 2-phenyl-3-(p-aminophenyl) acrylonitrile: a reactive matrix for sensitive and selective analysis of glycans by MALDI-MS. Analytical Chemistry, 91(14): 8801–8807

[18] Maity P, Nandi A K, Manna D K, Pattanayak M, Sen I K, Bhanja S K, Samanta S, Panda B C, Paloi S, Acharya K. . (2017). Structural characterization and antioxidant activity of a glucan from Meripilus giganteus. Carbohydrate Polymers, 157(10): 1237–1245

[19] Mitch W A, Richardson S D, Zhang X R, Gonsior M. (2023). High-molecular-weight by-products of chlorine disinfection. Nature Water, 1(4): 336–347

[20] Pan C S, Xu S Y, Zhou H J, Fu Y, Ye M Y, Zou H F. (2007). Recent developments in methods and technology for analysis of biological samples by MALDI-TOF-MS. Analytical and Bioanalytical Chemistry, 387(1): 193–204

[21] Patriarca C, Bergquist J, Sjoberg P J R, Tranvik L, Hawkes J A. (2018). Online HPLC-ESI-HRMS method for the analysis and comparison of different dissolved organic matter samples. Environmental Science & Technology, 52(4): 2091–2099

[22] Rankin K, Mabury S A. (2015). Matrix normalized MALDI-TOF quantification of a fluorotelomer-based acrylate polymer. Environmental Science & Technology, 49(10): 6093–6101

[23] RenJ F, Tang M M, WangL Y, ChuW H, ShiW, ZhouQ, Pan Y (2024). How to achieve adequate quenching for DBP analysis in drinking water? Water Research, 253: 121264

[24] Richardson S D. (2002). The role of GC-MS and LC-MS in the discovery of drinking water disinfection by-products. Journal of Environmental Monitoring, 4(1): 1–9

[25] Richardson S D, Kimura S Y. (2020). Water analysis: emerging contaminants and current issues. Analytical Chemistry, 92(1): 473–505

[26] Richardson S D, Plewa M J, Wagner E D, Schoeny R, Demarini D M. (2007). Occurrence, genotoxicity, and carcinogenicity of regulated and emerging disinfection by-products in drinking water: a review and roadmap for research. Mutation Research/Reviews in Mutation Research, 636(1−3): 178–242

[27] Stalter D, O’Malley E, von Gunten U, Escher B I. (2020). Mixture effects of drinking water disinfection by-products: implications for risk assessment. Environmental Science. Water Research & Technology, 6(9): 2341–2351

[28] Stalter D, Peters L I, O’Malley E, Tang J Y M, Revalor M, Farre M J, Watson K, von Gunten U, Escher B I. (2016). Sample enrichment for bioanalytical assessment of disinfected drinking water: concentrating the polar, the volatiles, and the unknowns. Environmental Science & Technology, 50(12): 6495–6505

[29] Tang H Y, Zhong H L, Pan Y, Zhou Q, Huo Z L, Chu W H, Xu B. (2021). A new group of heterocyclic nitrogenous disinfection byproducts (DBPs) in drinking water: role of extraction pH in unknown DBP exploration. Environmental Science & Technology, 55(10): 6764–6772

[30] Wagner E D, Plewa M J. (2017). CHO cell cytotoxicity and genotoxicity analyses of disinfection by-products: an updated review. Journal of Environmental Sciences (China), 58: 64–76

[31] Wang R G, Zhou J, Qu G, Wang T C, Jia H Z, Zhu L Y. (2022). FT-ICR/MS deciphers formation of unknown macromolecular disinfection byproducts from algal organic matters after plasma oxidation. Water Research, 218: 118492

[32] Wang Z X, Zhang Q Q, Shen H L, Yang P Y, Zhou X W. (2021). Optimized MALDI-TOF MS strategy for characterizing polymers. Frontiers in Chemistry, 9: 698297

[33] Wei Y Y, Liu Y, Ma L M, Wang H W, Fan J H, Liu X, Dai R H. (2013). Speciation and formation of iodinated trihalomethane from microbially derived organic matter during the biological treatment of micro-polluted source water. Chemosphere, 92(11): 1529–1535

[34] Whiteaker J R, Fenselau C C, Fetterolf D, Steele D, Wilson D. (2004). Quantitative determination of heme for forensic characterization of Bacillus spores using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Analytical Chemistry, 76(10): 2836–2841

[35] Wright J M, Evans A, Kaufman J A, Rivera-Nunez Z, Narotsky M G. (2017). Disinfection by-product exposures and the risk of specific cardiac birth defects. Environmental Health Perspectives, 125(2): 269–277

[36] Wu P F, Tang Y Y, Cao G D, Li J P, Wang S Q, Chang X Y, Dang M, Jin H B, Zheng C M, Cai Z W. (2020b). Determination of environmental micro(nano)plastics by matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. Analytical Chemistry, 92(21): 14346–14356

[37] Wu Q Y, Liang Z F, Wang W L, Du Y, Hu H Y, Yang L L, Huang W C. (2020a). Non-volatile disinfection byproducts are far more toxic to mammalian cells than volatile byproducts. Water Research, 183: 116080

[38] WuY, WeiW Z, LuoJ Y, Pan Y, YangM T, HuaM, ChuW H, ShuangC D, Li A M (2022). Comparative toxicity analyses from different endpoints: Are new cyclic disinfection byproducts (DBPs) more toxic than common aliphatic DBPs? Environmental Science & Technology, 56(1): 194–207

[39] Yang M T, Liberatore H K, Zhang X R. (2019). Current methods for analyzing drinking water disinfection byproducts. Current Opinion in Environmental Science & Health, 7: 98–107

[40] Yang M T, Zhang X R. (2016). Current trends in the analysis and identification of emerging disinfection byproducts. Trends in Environmental Analytical Chemistry, 10: 24–34

[41] Zhai H Y, Zhang X R. (2011). Formation and decomposition of new and unknown polar brominated disinfection byproducts during chlorination. Environmental Science & Technology, 45(6): 2194–2201

[42] Zhang X R, Minear R A. (2002). Characterization of high molecular weight disinfection byproducts resulting from chlorination of aquatic humic substances. Environmental Science & Technology, 36(19): 4033–4038

[43] Zhang X R, Minear R A. (2006). Formation, adsorption and separation of high molecular weight disinfection byproducts resulting from chlorination of aquatic humic substances. Water Research, 40(2): 221–230

[44] Zhang X R, Minear R A, Barrett S E. (2005). Characterization of high molecular weight disinfection byproducts from chlorination of humic substances with/without coagulation pretreatment using UF-SEC-ESI-MS/MS. Environmental Science & Technology, 39(4): 963–972

[45] Zhou X T, Meng X J, Cheng L M, Su C, Sun Y T, Sun L X, Tang Z H, Fawcett J P, Yang Y, Gu J K. (2017). Development and application of an MS^ALL-based approach for the quantitative analysis of linear polyethylene glycols in rat plasma by liquid chromatography triple-quadrupole/time-of-flight mass spectro-metry. Analytical Chemistry, 89(10): 5193–5200

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