Mechanistic Aspects Regarding the Ultraviolet Degradation of Polychlorinated Biphenyls in Different Media: Insights from Carbon and Chlorine Isotope Fractionation
In this study, the carbon and chlorine isotope fractionation during ultraviolet-photolysis of polychlorinated biphenyls (PCBs, including PCB18, PCB77, PCB110, and PCB138) in n-hexane (Hex), methanol/water (MeOH/H2O), and silica gel was first investigated to explore their mechanistic processes. We ob...
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| Veröffentlicht in: | Environmental science & technology 2021-06, Vol.55 (11), p.7731-7740 |
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| creator | Huang, Chenchen Zeng, Yanhong Cao, Ya Zhu, Chuhong Ren, Zihe Liu, Yin-E Gao, Shutao Tian, Yankuan Luo, Xiaojun Mai, Bixian |
| description | In this study, the carbon and chlorine isotope fractionation during ultraviolet-photolysis of polychlorinated biphenyls (PCBs, including PCB18, PCB77, PCB110, and PCB138) in n-hexane (Hex), methanol/water (MeOH/H2O), and silica gel was first investigated to explore their mechanistic processes. We observed a significant variation in ΛCl–C (εCl/εC) for the same PCBs in different photochemical systems, implying that PCB degradation processes in various photoreaction systems could differ. Although all substrates showed normal apparent carbon/chlorine kinetic isotope effects (C–/Cl–AKIE >1), the putative inverse C-AKIE of nondechlorinated pathways was suggested by 13C depletion of the average carbon isotope composition of PCB138 and corresponding dechlorinated products in MeOH/H2O, which might originate from the magnetic isotope effect. Significant negative correlations were found between C-AKIE and relative disappearance quantum yields (“Φ”) of ortho-dechlorinated substrates (PCB18, PCB110, and PCB138) in Hex and MeOH/H2O. However, the C-AKIE and “Φ” of PCB77 (meta/para-dechlorinated congener) obviously deviated from the above correlations. Furthermore, significantly different product-related carbon isotope enrichment factors of PCB77 in Hex were found. These results demonstrated the existence of dechlorination position-specific and masking effects in carbon isotope fractionations. |
| doi_str_mv | 10.1021/acs.est.1c00726 |
| format | Article |
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We observed a significant variation in ΛCl–C (εCl/εC) for the same PCBs in different photochemical systems, implying that PCB degradation processes in various photoreaction systems could differ. Although all substrates showed normal apparent carbon/chlorine kinetic isotope effects (C–/Cl–AKIE >1), the putative inverse C-AKIE of nondechlorinated pathways was suggested by 13C depletion of the average carbon isotope composition of PCB138 and corresponding dechlorinated products in MeOH/H2O, which might originate from the magnetic isotope effect. Significant negative correlations were found between C-AKIE and relative disappearance quantum yields (“Φ”) of ortho-dechlorinated substrates (PCB18, PCB110, and PCB138) in Hex and MeOH/H2O. However, the C-AKIE and “Φ” of PCB77 (meta/para-dechlorinated congener) obviously deviated from the above correlations. Furthermore, significantly different product-related carbon isotope enrichment factors of PCB77 in Hex were found. These results demonstrated the existence of dechlorination position-specific and masking effects in carbon isotope fractionations.</description><identifier>ISSN: 0013-936X</identifier><identifier>EISSN: 1520-5851</identifier><identifier>DOI: 10.1021/acs.est.1c00726</identifier><identifier>PMID: 34003641</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Biogeochemical Cycling ; Carbon ; Carbon 13 ; Carbon isotopes ; Chlorine ; Congeners ; Dechlorination ; Degradation ; Depletion ; Fractionation ; Hexanes ; Isotope composition ; Isotope effect ; Isotope fractionation ; Isotopes ; n-Hexane ; PCB ; Photochemicals ; Photolysis ; Polychlorinated biphenyls ; Silica ; Silica gel ; Silicon dioxide ; Substrates</subject><ispartof>Environmental science & technology, 2021-06, Vol.55 (11), p.7731-7740</ispartof><rights>2021 American Chemical Society</rights><rights>Copyright American Chemical Society Jun 1, 2021</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a361t-1dabbec0e4adacd9fc87e01db51f2a8ae31c07af419897a1ea9960d02692a2d23</citedby><cites>FETCH-LOGICAL-a361t-1dabbec0e4adacd9fc87e01db51f2a8ae31c07af419897a1ea9960d02692a2d23</cites><orcidid>0000-0001-6358-8698 ; 0000-0002-8850-2456 ; 0000-0002-2572-8108</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.est.1c00726$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.est.1c00726$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2763,27074,27922,27923,56736,56786</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/34003641$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Huang, Chenchen</creatorcontrib><creatorcontrib>Zeng, Yanhong</creatorcontrib><creatorcontrib>Cao, Ya</creatorcontrib><creatorcontrib>Zhu, Chuhong</creatorcontrib><creatorcontrib>Ren, Zihe</creatorcontrib><creatorcontrib>Liu, Yin-E</creatorcontrib><creatorcontrib>Gao, Shutao</creatorcontrib><creatorcontrib>Tian, Yankuan</creatorcontrib><creatorcontrib>Luo, Xiaojun</creatorcontrib><creatorcontrib>Mai, Bixian</creatorcontrib><title>Mechanistic Aspects Regarding the Ultraviolet Degradation of Polychlorinated Biphenyls in Different Media: Insights from Carbon and Chlorine Isotope Fractionation</title><title>Environmental science & technology</title><addtitle>Environ. Sci. Technol</addtitle><description>In this study, the carbon and chlorine isotope fractionation during ultraviolet-photolysis of polychlorinated biphenyls (PCBs, including PCB18, PCB77, PCB110, and PCB138) in n-hexane (Hex), methanol/water (MeOH/H2O), and silica gel was first investigated to explore their mechanistic processes. We observed a significant variation in ΛCl–C (εCl/εC) for the same PCBs in different photochemical systems, implying that PCB degradation processes in various photoreaction systems could differ. Although all substrates showed normal apparent carbon/chlorine kinetic isotope effects (C–/Cl–AKIE >1), the putative inverse C-AKIE of nondechlorinated pathways was suggested by 13C depletion of the average carbon isotope composition of PCB138 and corresponding dechlorinated products in MeOH/H2O, which might originate from the magnetic isotope effect. Significant negative correlations were found between C-AKIE and relative disappearance quantum yields (“Φ”) of ortho-dechlorinated substrates (PCB18, PCB110, and PCB138) in Hex and MeOH/H2O. However, the C-AKIE and “Φ” of PCB77 (meta/para-dechlorinated congener) obviously deviated from the above correlations. Furthermore, significantly different product-related carbon isotope enrichment factors of PCB77 in Hex were found. These results demonstrated the existence of dechlorination position-specific and masking effects in carbon isotope fractionations.</description><subject>Biogeochemical Cycling</subject><subject>Carbon</subject><subject>Carbon 13</subject><subject>Carbon isotopes</subject><subject>Chlorine</subject><subject>Congeners</subject><subject>Dechlorination</subject><subject>Degradation</subject><subject>Depletion</subject><subject>Fractionation</subject><subject>Hexanes</subject><subject>Isotope composition</subject><subject>Isotope effect</subject><subject>Isotope fractionation</subject><subject>Isotopes</subject><subject>n-Hexane</subject><subject>PCB</subject><subject>Photochemicals</subject><subject>Photolysis</subject><subject>Polychlorinated biphenyls</subject><subject>Silica</subject><subject>Silica gel</subject><subject>Silicon dioxide</subject><subject>Substrates</subject><issn>0013-936X</issn><issn>1520-5851</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNp1kU1vEzEURS0EomlhzQ5ZYllN6o-ZyQy7klKI1KoVohK70Rv7OeNqYg-2Uyl_h19ah4TuWHlz7rnWu4R84GzOmeAXoOIcY5pzxdhC1K_IjFeCFVVT8ddkxhiXRSvrXyfkNMZHxpiQrHlLTmTJmKxLPiN_blEN4GxMVtHLOKFKkf7ANQRt3ZqmAenDmAI8WT9iole4DqAhWe-oN_Tejzs1jD5YBwk1_WKnAd1ujNQ6emWNwYAu0VvUFj7TlYt2PWS_CX5DlxD6bAGn6fKgQLqKPvkJ6XUAte_4W_SOvDEwRnx_fM_Iw_XXn8vvxc3dt9Xy8qYAWfNUcA19j4phmT-odGtUs0DGdV9xI6ABlPlICzAlb5t2ARyhbWummahbAUILeUY-HbxT8L-3-ardo98Glys7UZWykWXVykxdHCgVfIwBTTcFu4Gw6zjr9pt0eZNunz5ukhMfj95tv0H9wv8bIQPnB2CffOn8n-4ZW7ubiA</recordid><startdate>20210601</startdate><enddate>20210601</enddate><creator>Huang, Chenchen</creator><creator>Zeng, Yanhong</creator><creator>Cao, Ya</creator><creator>Zhu, Chuhong</creator><creator>Ren, Zihe</creator><creator>Liu, Yin-E</creator><creator>Gao, Shutao</creator><creator>Tian, Yankuan</creator><creator>Luo, Xiaojun</creator><creator>Mai, Bixian</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QO</scope><scope>7ST</scope><scope>7T7</scope><scope>7U7</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>P64</scope><scope>SOI</scope><orcidid>https://orcid.org/0000-0001-6358-8698</orcidid><orcidid>https://orcid.org/0000-0002-8850-2456</orcidid><orcidid>https://orcid.org/0000-0002-2572-8108</orcidid></search><sort><creationdate>20210601</creationdate><title>Mechanistic Aspects Regarding the Ultraviolet Degradation of Polychlorinated Biphenyls in Different Media: Insights from Carbon and Chlorine Isotope Fractionation</title><author>Huang, Chenchen ; Zeng, Yanhong ; Cao, Ya ; Zhu, Chuhong ; Ren, Zihe ; Liu, Yin-E ; Gao, Shutao ; Tian, Yankuan ; Luo, Xiaojun ; Mai, Bixian</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a361t-1dabbec0e4adacd9fc87e01db51f2a8ae31c07af419897a1ea9960d02692a2d23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Biogeochemical Cycling</topic><topic>Carbon</topic><topic>Carbon 13</topic><topic>Carbon isotopes</topic><topic>Chlorine</topic><topic>Congeners</topic><topic>Dechlorination</topic><topic>Degradation</topic><topic>Depletion</topic><topic>Fractionation</topic><topic>Hexanes</topic><topic>Isotope composition</topic><topic>Isotope effect</topic><topic>Isotope fractionation</topic><topic>Isotopes</topic><topic>n-Hexane</topic><topic>PCB</topic><topic>Photochemicals</topic><topic>Photolysis</topic><topic>Polychlorinated biphenyls</topic><topic>Silica</topic><topic>Silica gel</topic><topic>Silicon dioxide</topic><topic>Substrates</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Huang, Chenchen</creatorcontrib><creatorcontrib>Zeng, Yanhong</creatorcontrib><creatorcontrib>Cao, Ya</creatorcontrib><creatorcontrib>Zhu, Chuhong</creatorcontrib><creatorcontrib>Ren, Zihe</creatorcontrib><creatorcontrib>Liu, Yin-E</creatorcontrib><creatorcontrib>Gao, Shutao</creatorcontrib><creatorcontrib>Tian, Yankuan</creatorcontrib><creatorcontrib>Luo, Xiaojun</creatorcontrib><creatorcontrib>Mai, Bixian</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Biotechnology Research Abstracts</collection><collection>Environment Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Toxicology Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Environment Abstracts</collection><jtitle>Environmental science & technology</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Huang, Chenchen</au><au>Zeng, Yanhong</au><au>Cao, Ya</au><au>Zhu, Chuhong</au><au>Ren, Zihe</au><au>Liu, Yin-E</au><au>Gao, Shutao</au><au>Tian, Yankuan</au><au>Luo, Xiaojun</au><au>Mai, Bixian</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanistic Aspects Regarding the Ultraviolet Degradation of Polychlorinated Biphenyls in Different Media: Insights from Carbon and Chlorine Isotope Fractionation</atitle><jtitle>Environmental science & technology</jtitle><addtitle>Environ. Sci. Technol</addtitle><date>2021-06-01</date><risdate>2021</risdate><volume>55</volume><issue>11</issue><spage>7731</spage><epage>7740</epage><pages>7731-7740</pages><issn>0013-936X</issn><eissn>1520-5851</eissn><abstract>In this study, the carbon and chlorine isotope fractionation during ultraviolet-photolysis of polychlorinated biphenyls (PCBs, including PCB18, PCB77, PCB110, and PCB138) in n-hexane (Hex), methanol/water (MeOH/H2O), and silica gel was first investigated to explore their mechanistic processes. We observed a significant variation in ΛCl–C (εCl/εC) for the same PCBs in different photochemical systems, implying that PCB degradation processes in various photoreaction systems could differ. Although all substrates showed normal apparent carbon/chlorine kinetic isotope effects (C–/Cl–AKIE >1), the putative inverse C-AKIE of nondechlorinated pathways was suggested by 13C depletion of the average carbon isotope composition of PCB138 and corresponding dechlorinated products in MeOH/H2O, which might originate from the magnetic isotope effect. Significant negative correlations were found between C-AKIE and relative disappearance quantum yields (“Φ”) of ortho-dechlorinated substrates (PCB18, PCB110, and PCB138) in Hex and MeOH/H2O. However, the C-AKIE and “Φ” of PCB77 (meta/para-dechlorinated congener) obviously deviated from the above correlations. Furthermore, significantly different product-related carbon isotope enrichment factors of PCB77 in Hex were found. These results demonstrated the existence of dechlorination position-specific and masking effects in carbon isotope fractionations.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>34003641</pmid><doi>10.1021/acs.est.1c00726</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0001-6358-8698</orcidid><orcidid>https://orcid.org/0000-0002-8850-2456</orcidid><orcidid>https://orcid.org/0000-0002-2572-8108</orcidid></addata></record> |
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| subjects | Biogeochemical Cycling Carbon Carbon 13 Carbon isotopes Chlorine Congeners Dechlorination Degradation Depletion Fractionation Hexanes Isotope composition Isotope effect Isotope fractionation Isotopes n-Hexane PCB Photochemicals Photolysis Polychlorinated biphenyls Silica Silica gel Silicon dioxide Substrates |
| title | Mechanistic Aspects Regarding the Ultraviolet Degradation of Polychlorinated Biphenyls in Different Media: Insights from Carbon and Chlorine Isotope Fractionation |
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