Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases
•BDOC promoted the dehydrochlorination of 1,1,2,2-tetrachloroethane in basic solution.•Synergies of dipole-dipole and conjugate bases was the dominant catalysis mechanism.•The promoting effect was enhanced at a higher pH by forming more conjugate bases.•>1 kDa fraction of BDOC presented greater p...
Gespeichert in:
| Veröffentlicht in: | Water research (Oxford) 2024-08, Vol.259, p.121812, Article 121812 |
|---|---|
| Hauptverfasser: | , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | |
|---|---|
| container_issue | |
| container_start_page | 121812 |
| container_title | Water research (Oxford) |
| container_volume | 259 |
| creator | Chen, Weifeng Yu, Shuhan Zhang, Huiying Wei, Ran Ni, Jinzhi Farooq, Usman Qi, Zhichong |
| description | •BDOC promoted the dehydrochlorination of 1,1,2,2-tetrachloroethane in basic solution.•Synergies of dipole-dipole and conjugate bases was the dominant catalysis mechanism.•The promoting effect was enhanced at a higher pH by forming more conjugate bases.•>1 kDa fraction of BDOC presented greater promoting effect than 1 kDa had significantly greater ke/[DOC] values of TeCA dehydrochlorination than the fraction of 1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment.
[Display omitted] |
| doi_str_mv | 10.1016/j.watres.2024.121812 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_3062531705</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S0043135424007139</els_id><sourcerecordid>3062531705</sourcerecordid><originalsourceid>FETCH-LOGICAL-c311t-a928b3363a8f855759d156b891afcb924a6a15a216b5c81aa420ff8d60e09a143</originalsourceid><addsrcrecordid>eNp9kcGO0zAQhiMEYrsLb4CQjxya4rGd1OGABCsWkFbiAJytiT1pXSVxsZ1F5Zl4SNLNwpHTHPz9M_r9FcUL4BvgUL8-bH5ijpQ2ggu1AQEaxKNiBXrblEIp_bhYca5kCbJSF8VlSgfOuRCyeVpcSK2BS6VWxe_3Ptg9xtJR9HfkWIg7HL1lFmMbRnaMYQjZjzuW98Qc7U8uzoE-RD9i9jMROgZrWIu1KDPliPePgfIeR2I4OuZzYkPoyU49Rpb8L2LUdWRzesO-nkaKO0_pvMb544yVy7iP2jAeph1mYi0mSs-KJx32iZ4_zKvi-82Hb9efytsvHz9fv7strQTIJTZCt1LWEnWnq2pbNQ6qutUNYGfbRiisESoUULeV1YCoBO867WpOvEFQ8qp4teyd2_-YKGUz-GSp7-dKYUpG8lpUEra8mlG1oDaGlCJ15hj9gPFkgJuzJ3Mwiydz9mQWT3Ps5cOFqR3I_Qv9FTMDbxeA5p53nqJJ1tNoyfk4f51xwf__wh-L6Ki7</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>3062531705</pqid></control><display><type>article</type><title>Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases</title><source>MEDLINE</source><source>Elsevier ScienceDirect Journals Complete</source><creator>Chen, Weifeng ; Yu, Shuhan ; Zhang, Huiying ; Wei, Ran ; Ni, Jinzhi ; Farooq, Usman ; Qi, Zhichong</creator><creatorcontrib>Chen, Weifeng ; Yu, Shuhan ; Zhang, Huiying ; Wei, Ran ; Ni, Jinzhi ; Farooq, Usman ; Qi, Zhichong</creatorcontrib><description>•BDOC promoted the dehydrochlorination of 1,1,2,2-tetrachloroethane in basic solution.•Synergies of dipole-dipole and conjugate bases was the dominant catalysis mechanism.•The promoting effect was enhanced at a higher pH by forming more conjugate bases.•>1 kDa fraction of BDOC presented greater promoting effect than <1 kDa fraction.•N-containing species and aromatic protein-/polyphenol-like matters played key roles.
The environmental effects of biochar-derived organic carbon (BDOC) have attracted increasing attention. Nevertheless, it is unknown how BDOC might affect the natural attenuation of widely distributed chloroalkanes (e.g., 1,1,2,2-tetrachloroethane (TeCA)) in aqueous environments. We firstly observed that the kinetic constants (ke) of TeCA dehydrochlorination in the presence of BDOC samples or their different molecular size fractions (<1 kDa, 1∼10 kDa, and >10 kDa) ranged from 9.16×103 to 26.63×103 M−1h−1, which was significantly greater than the ke (3.53×103 M−1h−1) of TeCA dehydrochlorination in the aqueous solution at pH 8.0, indicating that BDOC samples and their different molecular size fractions all could promote TeCA dehydrochlorination. For a given BDOC sample, the kinetic constants (ke) of TeCA dehydrochlorination in the initial pH 9.0 solution was 2∼3 times greater than that in the initial pH 8.0 solution due to more formation of conjugate bases. Interestingly, their DOC concentration normalized kinetic constants (ke/[DOC]) were negatively correlated with SUVA254, and positively correlated with A220/A254 and the abundance of aromatic protein-like/polyphenol-like matters. A novel mechanism was proposed that the CH dipole of BDOC aliphatic structure first bound with the CCl dipole of TeCA to capture the TeCA molecule, then the conjugate bases (-NH-/-NH2 and deprotonated phenol-OH of BDOC) could attack the H atom attached to the β-C atom of bound TeCA, causing a CCl bond breaking and the trichloroethylene formation. Furthermore, a fraction of >1 kDa had significantly greater ke/[DOC] values of TeCA dehydrochlorination than the fraction of <1 kDa because >1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment.
[Display omitted]</description><identifier>ISSN: 0043-1354</identifier><identifier>ISSN: 1879-2448</identifier><identifier>EISSN: 1879-2448</identifier><identifier>DOI: 10.1016/j.watres.2024.121812</identifier><identifier>PMID: 38810344</identifier><language>eng</language><publisher>England: Elsevier Ltd</publisher><subject>1,1,2,2-tetrachloroethane ; Biochar-derived organic carbons ; Carbon - chemistry ; Charcoal - chemistry ; Conjugate bases ; Dehydrochlorination ; Ethane - analogs & derivatives ; Ethane - chemistry ; Halogenation ; Hydrocarbons, Chlorinated - chemistry ; Hydrogen-Ion Concentration ; Kinetics ; Molecular size ; Water Pollutants, Chemical - chemistry</subject><ispartof>Water research (Oxford), 2024-08, Vol.259, p.121812, Article 121812</ispartof><rights>2024 Elsevier Ltd</rights><rights>Copyright © 2024 Elsevier Ltd. All rights reserved.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c311t-a928b3363a8f855759d156b891afcb924a6a15a216b5c81aa420ff8d60e09a143</cites><orcidid>0000-0003-3365-2235 ; 0000-0001-7682-1786</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.watres.2024.121812$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38810344$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Chen, Weifeng</creatorcontrib><creatorcontrib>Yu, Shuhan</creatorcontrib><creatorcontrib>Zhang, Huiying</creatorcontrib><creatorcontrib>Wei, Ran</creatorcontrib><creatorcontrib>Ni, Jinzhi</creatorcontrib><creatorcontrib>Farooq, Usman</creatorcontrib><creatorcontrib>Qi, Zhichong</creatorcontrib><title>Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases</title><title>Water research (Oxford)</title><addtitle>Water Res</addtitle><description>•BDOC promoted the dehydrochlorination of 1,1,2,2-tetrachloroethane in basic solution.•Synergies of dipole-dipole and conjugate bases was the dominant catalysis mechanism.•The promoting effect was enhanced at a higher pH by forming more conjugate bases.•>1 kDa fraction of BDOC presented greater promoting effect than <1 kDa fraction.•N-containing species and aromatic protein-/polyphenol-like matters played key roles.
The environmental effects of biochar-derived organic carbon (BDOC) have attracted increasing attention. Nevertheless, it is unknown how BDOC might affect the natural attenuation of widely distributed chloroalkanes (e.g., 1,1,2,2-tetrachloroethane (TeCA)) in aqueous environments. We firstly observed that the kinetic constants (ke) of TeCA dehydrochlorination in the presence of BDOC samples or their different molecular size fractions (<1 kDa, 1∼10 kDa, and >10 kDa) ranged from 9.16×103 to 26.63×103 M−1h−1, which was significantly greater than the ke (3.53×103 M−1h−1) of TeCA dehydrochlorination in the aqueous solution at pH 8.0, indicating that BDOC samples and their different molecular size fractions all could promote TeCA dehydrochlorination. For a given BDOC sample, the kinetic constants (ke) of TeCA dehydrochlorination in the initial pH 9.0 solution was 2∼3 times greater than that in the initial pH 8.0 solution due to more formation of conjugate bases. Interestingly, their DOC concentration normalized kinetic constants (ke/[DOC]) were negatively correlated with SUVA254, and positively correlated with A220/A254 and the abundance of aromatic protein-like/polyphenol-like matters. A novel mechanism was proposed that the CH dipole of BDOC aliphatic structure first bound with the CCl dipole of TeCA to capture the TeCA molecule, then the conjugate bases (-NH-/-NH2 and deprotonated phenol-OH of BDOC) could attack the H atom attached to the β-C atom of bound TeCA, causing a CCl bond breaking and the trichloroethylene formation. Furthermore, a fraction of >1 kDa had significantly greater ke/[DOC] values of TeCA dehydrochlorination than the fraction of <1 kDa because >1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment.
[Display omitted]</description><subject>1,1,2,2-tetrachloroethane</subject><subject>Biochar-derived organic carbons</subject><subject>Carbon - chemistry</subject><subject>Charcoal - chemistry</subject><subject>Conjugate bases</subject><subject>Dehydrochlorination</subject><subject>Ethane - analogs & derivatives</subject><subject>Ethane - chemistry</subject><subject>Halogenation</subject><subject>Hydrocarbons, Chlorinated - chemistry</subject><subject>Hydrogen-Ion Concentration</subject><subject>Kinetics</subject><subject>Molecular size</subject><subject>Water Pollutants, Chemical - chemistry</subject><issn>0043-1354</issn><issn>1879-2448</issn><issn>1879-2448</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp9kcGO0zAQhiMEYrsLb4CQjxya4rGd1OGABCsWkFbiAJytiT1pXSVxsZ1F5Zl4SNLNwpHTHPz9M_r9FcUL4BvgUL8-bH5ijpQ2ggu1AQEaxKNiBXrblEIp_bhYca5kCbJSF8VlSgfOuRCyeVpcSK2BS6VWxe_3Ptg9xtJR9HfkWIg7HL1lFmMbRnaMYQjZjzuW98Qc7U8uzoE-RD9i9jMROgZrWIu1KDPliPePgfIeR2I4OuZzYkPoyU49Rpb8L2LUdWRzesO-nkaKO0_pvMb544yVy7iP2jAeph1mYi0mSs-KJx32iZ4_zKvi-82Hb9efytsvHz9fv7strQTIJTZCt1LWEnWnq2pbNQ6qutUNYGfbRiisESoUULeV1YCoBO867WpOvEFQ8qp4teyd2_-YKGUz-GSp7-dKYUpG8lpUEra8mlG1oDaGlCJ15hj9gPFkgJuzJ3Mwiydz9mQWT3Ps5cOFqR3I_Qv9FTMDbxeA5p53nqJJ1tNoyfk4f51xwf__wh-L6Ki7</recordid><startdate>20240801</startdate><enddate>20240801</enddate><creator>Chen, Weifeng</creator><creator>Yu, Shuhan</creator><creator>Zhang, Huiying</creator><creator>Wei, Ran</creator><creator>Ni, Jinzhi</creator><creator>Farooq, Usman</creator><creator>Qi, Zhichong</creator><general>Elsevier Ltd</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-3365-2235</orcidid><orcidid>https://orcid.org/0000-0001-7682-1786</orcidid></search><sort><creationdate>20240801</creationdate><title>Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases</title><author>Chen, Weifeng ; Yu, Shuhan ; Zhang, Huiying ; Wei, Ran ; Ni, Jinzhi ; Farooq, Usman ; Qi, Zhichong</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c311t-a928b3363a8f855759d156b891afcb924a6a15a216b5c81aa420ff8d60e09a143</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>1,1,2,2-tetrachloroethane</topic><topic>Biochar-derived organic carbons</topic><topic>Carbon - chemistry</topic><topic>Charcoal - chemistry</topic><topic>Conjugate bases</topic><topic>Dehydrochlorination</topic><topic>Ethane - analogs & derivatives</topic><topic>Ethane - chemistry</topic><topic>Halogenation</topic><topic>Hydrocarbons, Chlorinated - chemistry</topic><topic>Hydrogen-Ion Concentration</topic><topic>Kinetics</topic><topic>Molecular size</topic><topic>Water Pollutants, Chemical - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Chen, Weifeng</creatorcontrib><creatorcontrib>Yu, Shuhan</creatorcontrib><creatorcontrib>Zhang, Huiying</creatorcontrib><creatorcontrib>Wei, Ran</creatorcontrib><creatorcontrib>Ni, Jinzhi</creatorcontrib><creatorcontrib>Farooq, Usman</creatorcontrib><creatorcontrib>Qi, Zhichong</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Water research (Oxford)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Chen, Weifeng</au><au>Yu, Shuhan</au><au>Zhang, Huiying</au><au>Wei, Ran</au><au>Ni, Jinzhi</au><au>Farooq, Usman</au><au>Qi, Zhichong</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases</atitle><jtitle>Water research (Oxford)</jtitle><addtitle>Water Res</addtitle><date>2024-08-01</date><risdate>2024</risdate><volume>259</volume><spage>121812</spage><pages>121812-</pages><artnum>121812</artnum><issn>0043-1354</issn><issn>1879-2448</issn><eissn>1879-2448</eissn><abstract>•BDOC promoted the dehydrochlorination of 1,1,2,2-tetrachloroethane in basic solution.•Synergies of dipole-dipole and conjugate bases was the dominant catalysis mechanism.•The promoting effect was enhanced at a higher pH by forming more conjugate bases.•>1 kDa fraction of BDOC presented greater promoting effect than <1 kDa fraction.•N-containing species and aromatic protein-/polyphenol-like matters played key roles.
The environmental effects of biochar-derived organic carbon (BDOC) have attracted increasing attention. Nevertheless, it is unknown how BDOC might affect the natural attenuation of widely distributed chloroalkanes (e.g., 1,1,2,2-tetrachloroethane (TeCA)) in aqueous environments. We firstly observed that the kinetic constants (ke) of TeCA dehydrochlorination in the presence of BDOC samples or their different molecular size fractions (<1 kDa, 1∼10 kDa, and >10 kDa) ranged from 9.16×103 to 26.63×103 M−1h−1, which was significantly greater than the ke (3.53×103 M−1h−1) of TeCA dehydrochlorination in the aqueous solution at pH 8.0, indicating that BDOC samples and their different molecular size fractions all could promote TeCA dehydrochlorination. For a given BDOC sample, the kinetic constants (ke) of TeCA dehydrochlorination in the initial pH 9.0 solution was 2∼3 times greater than that in the initial pH 8.0 solution due to more formation of conjugate bases. Interestingly, their DOC concentration normalized kinetic constants (ke/[DOC]) were negatively correlated with SUVA254, and positively correlated with A220/A254 and the abundance of aromatic protein-like/polyphenol-like matters. A novel mechanism was proposed that the CH dipole of BDOC aliphatic structure first bound with the CCl dipole of TeCA to capture the TeCA molecule, then the conjugate bases (-NH-/-NH2 and deprotonated phenol-OH of BDOC) could attack the H atom attached to the β-C atom of bound TeCA, causing a CCl bond breaking and the trichloroethylene formation. Furthermore, a fraction of >1 kDa had significantly greater ke/[DOC] values of TeCA dehydrochlorination than the fraction of <1 kDa because >1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment.
[Display omitted]</abstract><cop>England</cop><pub>Elsevier Ltd</pub><pmid>38810344</pmid><doi>10.1016/j.watres.2024.121812</doi><orcidid>https://orcid.org/0000-0003-3365-2235</orcidid><orcidid>https://orcid.org/0000-0001-7682-1786</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0043-1354 |
| ispartof | Water research (Oxford), 2024-08, Vol.259, p.121812, Article 121812 |
| issn | 0043-1354 1879-2448 1879-2448 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_3062531705 |
| source | MEDLINE; Elsevier ScienceDirect Journals Complete |
| subjects | 1,1,2,2-tetrachloroethane Biochar-derived organic carbons Carbon - chemistry Charcoal - chemistry Conjugate bases Dehydrochlorination Ethane - analogs & derivatives Ethane - chemistry Halogenation Hydrocarbons, Chlorinated - chemistry Hydrogen-Ion Concentration Kinetics Molecular size Water Pollutants, Chemical - chemistry |
| title | Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-02T05%3A17%3A12IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Biochar-derived%20organic%20carbon%20promoting%20the%20dehydrochlorination%20of%201,1,2,2-tetrachloroethane%20and%20its%20molecular%20size%20effects:%20Synergies%20of%20dipole-dipole%20and%20conjugate%20bases&rft.jtitle=Water%20research%20(Oxford)&rft.au=Chen,%20Weifeng&rft.date=2024-08-01&rft.volume=259&rft.spage=121812&rft.pages=121812-&rft.artnum=121812&rft.issn=0043-1354&rft.eissn=1879-2448&rft_id=info:doi/10.1016/j.watres.2024.121812&rft_dat=%3Cproquest_cross%3E3062531705%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=3062531705&rft_id=info:pmid/38810344&rft_els_id=S0043135424007139&rfr_iscdi=true |