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Deciphering polymer degradation chemistry integrating new database construction into suspect screening analysis
Water-soluble synthetic polymers and their environmental degradation products are overlooked but important industrial pollutants in wastewater. However, the detection of degradation products is limited to bulk solution chemistry and molecular-level analysis remains unreachable. In this work, we asse...
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| Published in: | Environmental science--processes & impacts 2024-07, Vol.26 (7), p.1184-1197 |
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| container_title | Environmental science--processes & impacts |
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| creator | Keyes, Phoebe Halimah, Noor Xiong, Boya |
| description | Water-soluble synthetic polymers and their environmental degradation products are overlooked but important industrial pollutants in wastewater. However, the detection of degradation products is limited to bulk solution chemistry and molecular-level analysis remains unreachable. In this work, we assessed the feasibility of current suspect screening and nontarget workflow using liquid chromatography-high resolution mass spectrometry (LC-HRMS) to elucidate molecular level information about polyacrylamide (PAM) and its degraded products by free radicals. Radical chain scission of PAM (10 kDa) using heat-activated persulfate was conducted to simulate hydraulic fracturing conditions in the deep subsurface. We found that the current workflows in the commercial software generated predicted formulae with low accuracy, due to limited capability of peak picking and formula prediction for high mass and charge features. By modeling literature-reported degradation pathways, we constructed a degradation product database of over 463 000 unique formulae, which improved the accuracy of the predicted formula. For the matched features, the ratio of aldehyde/ketone terminating molecule abundance was found to increase over 24 h degradation time, suggesting increasing content of aldehydes by radical-induced oxidative chain scission of PAM. This is contradictory to previously proposed ratios of carbon-centered radical position on polymer backbone initiated by hydroxyl radicals. Using
in silico
fragmentation of MS
1
features, we identified 11 structures with confidence levels 2b and 3 using their MS
2
information. This is the first attempt to resolve complex polymer degradation chemistry using HRMS that can advance our ability to detect water-soluble polymer pollutants and their transformation products in environmental samples.
For the first time, a novel suspect screening workflow enabled chemical structure identification of complex mixtures from free radical-induced oxidative chain scission of polyacrylamide used in hydraulic fracturing. |
| doi_str_mv | 10.1039/d4em00212a |
| format | article |
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in silico
fragmentation of MS
1
features, we identified 11 structures with confidence levels 2b and 3 using their MS
2
information. This is the first attempt to resolve complex polymer degradation chemistry using HRMS that can advance our ability to detect water-soluble polymer pollutants and their transformation products in environmental samples.
For the first time, a novel suspect screening workflow enabled chemical structure identification of complex mixtures from free radical-induced oxidative chain scission of polyacrylamide used in hydraulic fracturing.</description><identifier>ISSN: 2050-7887</identifier><identifier>EISSN: 2050-7895</identifier><identifier>DOI: 10.1039/d4em00212a</identifier><ispartof>Environmental science--processes & impacts, 2024-07, Vol.26 (7), p.1184-1197</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids></links><search><creatorcontrib>Keyes, Phoebe</creatorcontrib><creatorcontrib>Halimah, Noor</creatorcontrib><creatorcontrib>Xiong, Boya</creatorcontrib><title>Deciphering polymer degradation chemistry integrating new database construction into suspect screening analysis</title><title>Environmental science--processes & impacts</title><description>Water-soluble synthetic polymers and their environmental degradation products are overlooked but important industrial pollutants in wastewater. However, the detection of degradation products is limited to bulk solution chemistry and molecular-level analysis remains unreachable. In this work, we assessed the feasibility of current suspect screening and nontarget workflow using liquid chromatography-high resolution mass spectrometry (LC-HRMS) to elucidate molecular level information about polyacrylamide (PAM) and its degraded products by free radicals. Radical chain scission of PAM (10 kDa) using heat-activated persulfate was conducted to simulate hydraulic fracturing conditions in the deep subsurface. We found that the current workflows in the commercial software generated predicted formulae with low accuracy, due to limited capability of peak picking and formula prediction for high mass and charge features. By modeling literature-reported degradation pathways, we constructed a degradation product database of over 463 000 unique formulae, which improved the accuracy of the predicted formula. For the matched features, the ratio of aldehyde/ketone terminating molecule abundance was found to increase over 24 h degradation time, suggesting increasing content of aldehydes by radical-induced oxidative chain scission of PAM. This is contradictory to previously proposed ratios of carbon-centered radical position on polymer backbone initiated by hydroxyl radicals. Using
in silico
fragmentation of MS
1
features, we identified 11 structures with confidence levels 2b and 3 using their MS
2
information. This is the first attempt to resolve complex polymer degradation chemistry using HRMS that can advance our ability to detect water-soluble polymer pollutants and their transformation products in environmental samples.
For the first time, a novel suspect screening workflow enabled chemical structure identification of complex mixtures from free radical-induced oxidative chain scission of polyacrylamide used in hydraulic fracturing.</description><issn>2050-7887</issn><issn>2050-7895</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFz80OgjAMB_DFaCJRL95N9gLoBqJw9iM-gHdSR9UZ2Mg6Ynh7wRg92kubf389lLG5FEsp4mxVrLESIpIRDFgQiUSE2zRLht853Y7ZjOghukoTmSabgNk9Kl3f0Wlz47Ut2wodL_DmoACvreHqjpUm71quje9z30uDT94BuAAhV9Z0oFFv3ynLqaEaleekHKLpD8BA2ZKmKRtdoSScffqELY6H8-4UOlJ57XQFrs1_j8T_9i_59k71</recordid><startdate>20240717</startdate><enddate>20240717</enddate><creator>Keyes, Phoebe</creator><creator>Halimah, Noor</creator><creator>Xiong, Boya</creator><scope/></search><sort><creationdate>20240717</creationdate><title>Deciphering polymer degradation chemistry integrating new database construction into suspect screening analysis</title><author>Keyes, Phoebe ; Halimah, Noor ; Xiong, Boya</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_d4em00212a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><creationdate>2024</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Keyes, Phoebe</creatorcontrib><creatorcontrib>Halimah, Noor</creatorcontrib><creatorcontrib>Xiong, Boya</creatorcontrib><jtitle>Environmental science--processes & impacts</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Keyes, Phoebe</au><au>Halimah, Noor</au><au>Xiong, Boya</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Deciphering polymer degradation chemistry integrating new database construction into suspect screening analysis</atitle><jtitle>Environmental science--processes & impacts</jtitle><date>2024-07-17</date><risdate>2024</risdate><volume>26</volume><issue>7</issue><spage>1184</spage><epage>1197</epage><pages>1184-1197</pages><issn>2050-7887</issn><eissn>2050-7895</eissn><notes>https://doi.org/10.1039/d4em00212a</notes><notes>Electronic supplementary information (ESI) available. See DOI</notes><abstract>Water-soluble synthetic polymers and their environmental degradation products are overlooked but important industrial pollutants in wastewater. However, the detection of degradation products is limited to bulk solution chemistry and molecular-level analysis remains unreachable. In this work, we assessed the feasibility of current suspect screening and nontarget workflow using liquid chromatography-high resolution mass spectrometry (LC-HRMS) to elucidate molecular level information about polyacrylamide (PAM) and its degraded products by free radicals. Radical chain scission of PAM (10 kDa) using heat-activated persulfate was conducted to simulate hydraulic fracturing conditions in the deep subsurface. We found that the current workflows in the commercial software generated predicted formulae with low accuracy, due to limited capability of peak picking and formula prediction for high mass and charge features. By modeling literature-reported degradation pathways, we constructed a degradation product database of over 463 000 unique formulae, which improved the accuracy of the predicted formula. For the matched features, the ratio of aldehyde/ketone terminating molecule abundance was found to increase over 24 h degradation time, suggesting increasing content of aldehydes by radical-induced oxidative chain scission of PAM. This is contradictory to previously proposed ratios of carbon-centered radical position on polymer backbone initiated by hydroxyl radicals. Using
in silico
fragmentation of MS
1
features, we identified 11 structures with confidence levels 2b and 3 using their MS
2
information. This is the first attempt to resolve complex polymer degradation chemistry using HRMS that can advance our ability to detect water-soluble polymer pollutants and their transformation products in environmental samples.
For the first time, a novel suspect screening workflow enabled chemical structure identification of complex mixtures from free radical-induced oxidative chain scission of polyacrylamide used in hydraulic fracturing.</abstract><doi>10.1039/d4em00212a</doi><tpages>14</tpages></addata></record> |
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| source | Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list) |
| title | Deciphering polymer degradation chemistry integrating new database construction into suspect screening analysis |
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