{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,10]],"date-time":"2026-10-10T14:05:51Z","timestamp":1791641151515,"version":"4.3.4"},"reference-count":68,"publisher":"American Chemical Society (ACS)","issue":"21","license":[{"start":{"date-parts":[[2017,10,18]],"date-time":"2017-10-18T00:00:00Z","timestamp":1508284800000},"content-version":"vor","delay-in-days":12,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_termsofuse.html"}],"funder":[{"DOI":"10.13039\/100000146","name":"Division of Chemical, Bioengineering, Environmental, and Transport Systems","doi-asserted-by":"publisher","award":["CBET-1333476"],"award-info":[{"award-number":["CBET-1333476"]}],"id":[{"id":"10.13039\/100000146","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["51308312"],"award-info":[{"award-number":["51308312"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004731","name":"Natural Science Foundation of Zhejiang Province","doi-asserted-by":"publisher","award":["LR16E080003"],"award-info":[{"award-number":["LR16E080003"]}],"id":[{"id":"10.13039\/501100004731","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2017,11,7]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>In water treatment processes that involve contaminant reduction by zerovalent iron (ZVI), reduction of water to dihydrogen is a competing reaction that must be minimized to maximize the efficiency of electron utilization from the ZVI. Sulfidation has recently been shown to decrease H2 formation significantly, such that the overall electron efficiency of (or selectivity for) contaminant reduction can be greatly increased. To date, this work has focused on nanoscale ZVI (nZVI) and solution-phase sulfidation agents (e.g., bisulfide, dithionite or thiosulfate), both of which pose challenges for up-scaling the production of sulfidated ZVI for field applications. To overcome these challenges, we developed a process for sulfidation of microscale ZVI by ball milling ZVI with elemental sulfur. The resulting material (S-mZVIbm) exhibits reduced aggregation, relatively homogeneous distribution of Fe and S throughout the particle (not core\u2013shell structure), enhanced reactivity with trichloroethylene (TCE), less H2 formation, and therefore greatly improved electron efficiency of TCE dechlorination (\u03b5e). Under ZVI-limited conditions (initial Fe0\/TCE = 1.6 mol\/mol), S-mZVIbm gave surface-area normalized reduction rate constants (k\u2032SA) and \u03b5e that were \u223c2- and 10-fold greater than the unsulfidated ball-milled control (mZVIbm). Under TCE-limited conditions (initial Fe0\/TCE = 2000 mol\/mol), sulfidation increased kSA and \u03b5e \u2248 5- and 50-fold, respectively. The major products from TCE degradation by S-mZVIbm were acetylene, ethene, and ethane, which is consistent with dechlorination by \u03b2-elimination, as is typical of ZVI, iron oxides, and\/or sulfides. However, electrochemical characterization shows that the sulfidated material has redox properties intermediate between ZVI and Fe3O4, mostly likely significant coverage of the surface with FeS.<\/jats:p>","DOI":"10.1021\/acs.est.7b03604","type":"journal-article","created":{"date-parts":[[2017,10,6]],"date-time":"2017-10-06T10:45:16Z","timestamp":1507286716000},"page":"12653-12662","source":"Crossref","is-referenced-by-count":398,"title":["Mechanochemically\nSulfidated Microscale Zero Valent\nIron: Pathways, Kinetics, Mechanism, and Efficiency of Trichloroethylene\nDechlorination"],"prefix":"10.1021","volume":"51","author":[{"given":"Yawei","family":"Gu","sequence":"first","affiliation":[{"name":"Zhejiang University of Technology , , ,","place":["Hangzhou, China, 310014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Binbin","family":"Wang","sequence":"additional","affiliation":[{"name":"Zhejiang University of Technology , , ,","place":["Hangzhou, China, 310014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7056-8510","authenticated-orcid":true,"given":"Feng","family":"He","sequence":"additional","affiliation":[{"name":"Zhejiang University of Technology , , ,","place":["Hangzhou, China, 310014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miranda J.","family":"Bradley","sequence":"additional","affiliation":[{"name":"Oregon Health & Science University , 3181 SW Sam Jackson Park Road , , ,","place":["Portland, Oregon, United States, 97239"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8818-6417","authenticated-orcid":true,"given":"Paul G.","family":"Tratnyek","sequence":"additional","affiliation":[{"name":"Oregon Health & Science University , 3181 SW Sam Jackson Park Road , , ,","place":["Portland, Oregon, United States, 97239"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2017,10,6]]},"reference":[{"issue":"6","key":"2026090204212800600_cit1","doi-asserted-by":"publisher","first-page":"958","DOI":"10.1111\/j.1745-6584.1994.tb00935.x","article-title":"Enhanced\nDegradation of Halogenated Aliphatics by Zero-Valent\nIron","volume":"32","author":"Gillham","year":"1994","journal-title":"Groundwater"},{"issue":"12","key":"2026090204212800600_cit2","doi-asserted-by":"publisher","first-page":"2045","DOI":"10.1021\/es00061a012","article-title":"Reductive Dehalogenation\nof Chlorinated Methanes by\nIron Metal","volume":"28","author":"Matheson","year":"1994","journal-title":"Environ. 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Water Resour."},{"issue":"3\u20134","key":"2026090204212800600_cit6","doi-asserted-by":"publisher","first-page":"533","DOI":"10.1016\/j.apcatb.2008.05.008","article-title":"Hydrodechlorination\nof trichloroethene using stabilized\nFe-Pd nanoparticles: Reaction mechanism and effects of stabilizers,\ncatalysts and reaction conditions","volume":"84","author":"He","year":"2008","journal-title":"Appl. Catal.,\nB"},{"issue":"21","key":"2026090204212800600_cit7","doi-asserted-by":"publisher","first-page":"6837","DOI":"10.1021\/es060921v","article-title":"Exploring the influence of granular iron additives\non 1,1,1-trichloroethane reduction","volume":"40","author":"Cwiertny","year":"2006","journal-title":"Environ.\nSci. 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Technol."},{"issue":"12","key":"2026090204212800600_cit12","doi-asserted-by":"publisher","first-page":"2489","DOI":"10.1021\/nl0518268","article-title":"Adsorbed\ntriblock copolymers deliver reactive iron nanoparticles to the oil\/water\ninterface","volume":"5","author":"Saleh","year":"2005","journal-title":"Nano Lett."},{"issue":"13","key":"2026090204212800600_cit13","doi-asserted-by":"publisher","first-page":"5079","DOI":"10.1021\/es900171v","article-title":"Particle Size Distribution,\nConcentration,\nand Magnetic Attraction Affect Transport of Polymer-Modified Fe-0\nNanoparticles in Sand Columns","volume":"43","author":"Phenrat","year":"2009","journal-title":"Environ. 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Technol."},{"issue":"7","key":"2026090204212800600_cit17","doi-asserted-by":"publisher","first-page":"2360","DOI":"10.1016\/j.watres.2009.12.041","article-title":"Field assessment\nof carboxymethyl\ncellulose stabilized iron nanoparticles for in situ destruction of\nchlorinated solvents in source zones","volume":"44","author":"He","year":"2010","journal-title":"Water\nRes."},{"issue":"3","key":"2026090204212800600_cit18","doi-asserted-by":"publisher","first-page":"1573","DOI":"10.1021\/es304564q","article-title":"Field-Scale\nTransport and Transformation of Carboxymethylcellulose-Stabilized\nNano Zero-Valent Iron","volume":"47","author":"Johnson","year":"2013","journal-title":"Environ. Sci. Technol."},{"issue":"5","key":"2026090204212800600_cit19","doi-asserted-by":"publisher","first-page":"2862","DOI":"10.1021\/es4044209","article-title":"Characterization of nZVI Mobility\nin a Field Scale Test","volume":"48","author":"Kocur","year":"2014","journal-title":"Environ. Sci. 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Technol."},{"issue":"22","key":"2026090204212800600_cit22","doi-asserted-by":"publisher","first-page":"8616","DOI":"10.1021\/es901968g","article-title":"Multifunctional\ncolloidal particles for in situ remediation of chlorinated hydrocarbons","volume":"43","author":"Zhan","year":"2009","journal-title":"Environ. Sci. Technol."},{"key":"2026090204212800600_cit23","doi-asserted-by":"publisher","first-page":"443","DOI":"10.1016\/j.jhazmat.2015.07.038","article-title":"Degradation\nof Trichloroethene with a Novel Ball Milled Fe-C Nanocomposite","volume":"300","author":"Gao","year":"2015","journal-title":"J. Hazard. 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J."},{"issue":"2","key":"2026090204212800600_cit27","doi-asserted-by":"publisher","first-page":"886","DOI":"10.1016\/j.watres.2010.09.025","article-title":"Removal of Chromium\n(VI) from wastewater\nusing bentonite-supported nanoscale zero-valent iron","volume":"45","author":"Shi","year":"2011","journal-title":"Water Res."},{"key":"2026090204212800600_cit28","doi-asserted-by":"publisher","first-page":"224","DOI":"10.1016\/j.watres.2015.02.034","article-title":"The limitations\nof applying zero-valent\niron technology in contaminants sequestration and the corresponding\ncountermeasures: The development in zero-valent iron technology in\nthe last two decades (1994\u20132014)","volume":"75","author":"Guan","year":"2015","journal-title":"Water\nRes."},{"key":"2026090204212800600_cit29","doi-asserted-by":"publisher","first-page":"32","DOI":"10.1016\/j.jhazmat.2016.04.014","article-title":"Rapid and\nhighly selective removal of lead from water using graphene oxide-hydrated\nmanganese oxide nanocomposites","volume":"314","author":"Wan","year":"2016","journal-title":"J. Hazard. Mater."},{"issue":"9","key":"2026090204212800600_cit30","doi-asserted-by":"publisher","first-page":"5090","DOI":"10.1021\/acs.est.6b04832","article-title":"Coupled Effect of\nFerrous Ion and Oxygen on the Electron\nSelectivity of Zerovalent Iron for Selenate Sequestration","volume":"51","author":"Qin","year":"2017","journal-title":"Environ. Sci. Technol."},{"issue":"4","key":"2026090204212800600_cit31","doi-asserted-by":"publisher","first-page":"27","DOI":"10.1002\/rem.21481","article-title":"Selectivity of Nano Zerovalent Iron\nin In Situ Chemical Reduction: Challenges and Improvements","volume":"26","author":"Fan","year":"2016","journal-title":"Remediation Journal"},{"issue":"5","key":"2026090204212800600_cit32","doi-asserted-by":"publisher","first-page":"1338","DOI":"10.1021\/es049195r","article-title":"TCE dechlorination\nrates, pathways, and efficiency of nanoscale iron particles with different\nproperties","volume":"39","author":"Liu","year":"2005","journal-title":"Environ. Sci. Technol."},{"issue":"17","key":"2026090204212800600_cit33","doi-asserted-by":"publisher","first-page":"9558","DOI":"10.1021\/acs.est.6b02170","article-title":"Sulfidation of Nano\nZerovalent Iron (nZVI) for Improved Selectivity During In-Situ Chemical\nReduction (ISCR)","volume":"50","author":"Fan","year":"2016","journal-title":"Environ. Sci. Technol."},{"key":"2026090204212800600_cit34","doi-asserted-by":"publisher","first-page":"277","DOI":"10.1016\/j.watres.2016.05.031","article-title":"The influences of\niron characteristics, operating conditions and solution chemistry\non contaminants removal by zero-valent iron: A review","volume":"100","author":"Sun","year":"2016","journal-title":"Water Res."},{"key":"2026090204212800600_cit35","doi-asserted-by":"publisher","first-page":"69","DOI":"10.1016\/j.scitotenv.2015.05.033","article-title":"Electron\nefficiency of nZVI does\nnot change with variation of environmental parameters","volume":"535","author":"Schoftner","year":"2015","journal-title":"Sci. Total Environ."},{"issue":"5","key":"2026090204212800600_cit36","doi-asserted-by":"publisher","first-page":"1457","DOI":"10.1021\/am200016v","article-title":"Facile Synthesis\nand Characterization of Fe\/FeS Nanoparticles for Environmental Applications","volume":"3","author":"Kim","year":"2011","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"2026090204212800600_cit37","doi-asserted-by":"publisher","first-page":"144","DOI":"10.1016\/j.watres.2015.04.009","article-title":"Enhanced reductive\ndechlorination of trichloroethylene\nby sulfidated nanoscale zerovalent iron","volume":"78","author":"Rajajayavel","year":"2015","journal-title":"Water\nRes."},{"issue":"27","key":"2026090204212800600_cit38","doi-asserted-by":"publisher","first-page":"9343","DOI":"10.1021\/ie400165a","article-title":"Remediation\nof Trichloroethylene by FeS-Coated Iron Nanoparticles in Simulated\nand Real Groundwater: Effects of Water Chemistry","volume":"52","author":"Kim","year":"2013","journal-title":"Ind. Eng. Chem. Res."},{"issue":"10","key":"2026090204212800600_cit39","doi-asserted-by":"publisher","first-page":"5243","DOI":"10.1021\/acs.est.6b00734","article-title":"Enhanced\nDechlorination of 1,2-Dichloroethane\nby Coupled Nano Iron-Dithionite Treatment","volume":"50","author":"Garcia","year":"2016","journal-title":"Environ.\nSci. Technol."},{"issue":"23","key":"2026090204212800600_cit40","doi-asserted-by":"publisher","first-page":"12992","DOI":"10.1021\/acs.est.6b03997","article-title":"Reductive Dechlorination of Trichloroethene by Zero-valent\nIron Nanoparticles: Reactivity Enhancement through Sulfidation Treatment","volume":"50","author":"Han","year":"2016","journal-title":"Environ. Sci. 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