{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T14:00:14Z","timestamp":1791295214809,"version":"4.1.0"},"reference-count":51,"publisher":"American Chemical Society (ACS)","issue":"39","license":[{"start":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T00:00:00Z","timestamp":1790121600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T00:00:00Z","timestamp":1790121600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T00:00:00Z","timestamp":1790121600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"name":"National Key Technology Research and Development Program of China","award":["2023YFC3706505"],"award-info":[{"award-number":["2023YFC3706505"]}]},{"name":"National Nature Science Foundation of China","award":["42025703"],"award-info":[{"award-number":["42025703"]}]},{"name":"National Nature Science Foundation of China","award":["42102040"],"award-info":[{"award-number":["42102040"]}]},{"name":"National Nature Science Foundation of China","award":["42477081"],"award-info":[{"award-number":["42477081"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Fe(II)-bearing clay minerals are widespread reductants of hexavalent chromium (Cr(VI)) in subsurface environments. However, the influences of coexisting Fe (hydr)oxides on Cr(VI) reduction by Fe(II)-bearing clay minerals remain elusive. Here, Cr(VI) reduction was investigated in premixed systems of reduced nontronite NAu-2 (rNAu-2) and various Fe (hydr)oxides. Results showed that coexisting ferrihydrite significantly facilitated Cr(VI) reduction during the quick stage (0\u20132.5 min) across pH 5.5\u20139.0. During the subsequent slow stage (2.5\u2013205 min), ferrihydrite inhibited Cr(VI) reduction at pH 5.5\u20137.0 but enhanced it at pH 9.0. In contrast, coexisting goethite had negligible effects. Without Fe (hydr)oxides, direct reduction by rNAu-2 dominated for Cr(VI) removal. In the presence of Fe (hydr)oxides, competitive adsorption was found to inhibit direct Cr(VI) reduction, yet Fe (hydr)oxide-mediated electron transfer effectively offset this inhibitory effect. Both competitive adsorption and mediated electron transfer were influenced by the type and dosage of Fe (hydr)oxides, as well as solution pH. Kinetic modeling revealed that ferrihydrite-mediated electron transfer contributed 1.8\u201371.5% of the total Cr(VI) reduction, with greater contributions observed at higher solution pH and ferrihydrite dosage. Our findings provide new insights into mineral\u2013mineral electron transfer and its role in regulating Cr(VI) fate in subsurface environments.<\/jats:p>","DOI":"10.1021\/acs.est.5c13507","type":"journal-article","created":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T15:02:47Z","timestamp":1790175767000},"page":"27990-28000","source":"Crossref","is-referenced-by-count":0,"title":["Mechanisms\nof Hexavalent Chromium Reduction in Fe(II)-Bearing\nClay Mineral and Fe (hydr)oxide Binary Systems: Competitive Adsorption\nversus Mediated Electron Transfer"],"prefix":"10.1021","volume":"60","author":[{"given":"Ao","family":"Qian","sequence":"first","affiliation":[{"name":"China University of Geosciences , , ,","place":["Wuhan, P. R. China, 430078"]},{"name":"Jianghan University , , ,","place":["Wuhan, P. R. China, 430056"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-7498-5067","authenticated-orcid":true,"given":"Yunsong","family":"Zheng","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Wuhan, P. R. China, 430078"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2664-9601","authenticated-orcid":true,"given":"Peng","family":"Zhang","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Wuhan, P. R. China, 430078"]},{"name":"China University of Geosciences , , ,","place":["Wuhan, P. R. China, 430078"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuxi","family":"Lu","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Wuhan, P. R. China, 430078"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chenglong","family":"Yu","sequence":"additional","affiliation":[{"name":"Chengdu University of Technology , , ,","place":["Chengdu, P. R. China, 610059"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7256-177X","authenticated-orcid":true,"given":"Wenjuan","family":"Liao","sequence":"additional","affiliation":[{"name":"Hunan Agricultural University , , ,","place":["Changsha, P. R. China, 410128"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6119-1646","authenticated-orcid":true,"given":"Songhu","family":"Yuan","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Wuhan, P. R. China, 430078"]},{"name":"China University of Geosciences , , ,","place":["Wuhan, P. R. China, 430078"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,23]]},"reference":[{"key":"2026100609065843600_cit1","doi-asserted-by":"publisher","first-page":"466","DOI":"10.1346\/CCMN.2006.0540407","article-title":"Redox properties\nof structural Fe\nin ferruginous smectite. A discussion of the standard potential and\nits environmental implications","volume":"54","author":"Favre","year":"2006","journal-title":"Clays Clay Miner."},{"key":"2026100609065843600_cit2","doi-asserted-by":"publisher","first-page":"1505","DOI":"10.2138\/am.2009.3246","article-title":"Microbe-clay mineral\ninteractions","volume":"94","author":"Dong","year":"2009","journal-title":"Am. Mineral."},{"key":"2026100609065843600_cit3","doi-asserted-by":"publisher","first-page":"8661","DOI":"10.1021\/acs.est.6b02019","article-title":"Iron isotope\nfractionations reveal a finite bioavailable Fe pool for structural\nFe(III) reduction in nontronite","volume":"50","author":"Shi","year":"2016","journal-title":"Environ. Sci.\nTechnol."},{"key":"2026100609065843600_cit4","doi-asserted-by":"publisher","first-page":"235","DOI":"10.1021\/es0515147","article-title":"Reduction of nitroaromatic compounds\nby Fe(II) species associated with iron-rich smectites","volume":"40","author":"Hofstetter","year":"2006","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit5","doi-asserted-by":"publisher","first-page":"13139","DOI":"10.1021\/acs.est.5b03463","article-title":"Redox interactions\nof Tc(VII), U(VI), and Np(V) with microbially reduced biotite and\nchlorite","volume":"49","author":"Brookshaw","year":"2015","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit6","doi-asserted-by":"publisher","first-page":"4082","DOI":"10.1021\/es9001967","article-title":"Reduction\nof polychlorinated ethanes and carbon tetrachloride by structural\nFe(II) in smectites","volume":"43","author":"Neumann","year":"2009","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit7","doi-asserted-by":"publisher","first-page":"9042","DOI":"10.1021\/acs.est.7b02191","article-title":"Tc(VII)\nand Cr(VI) interaction with naturally\nreduced ferruginous smectite from a redox transition zone","volume":"51","author":"Qafoku","year":"2017","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit8","doi-asserted-by":"publisher","first-page":"422","DOI":"10.1016\/j.gca.2017.12.025","article-title":"Mechanisms\nof electron transfer from structural Fe (II) in reduced\nnontronite to oxygen for production of hydroxyl radicals","volume":"223","author":"Yuan","year":"2018","journal-title":"Geochim. Cosmochim. 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Sci.\nTechnol."},{"key":"2026100609065843600_cit12","doi-asserted-by":"publisher","first-page":"7903","DOI":"10.1021\/acs.est.7b00700","article-title":"Solid-phase Fe speciation\nalong the vertical redox gradients in floodplains using XAS and Mossbauer\nspectroscopies","volume":"51","author":"Chen","year":"2017","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit13","doi-asserted-by":"publisher","first-page":"89","DOI":"10.1016\/j.gca.2018.05.019","article-title":"Contrasting evolution\nof iron phase composition in soils exposed\nto redox fluctuations","volume":"235","author":"Winkler","year":"2018","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026100609065843600_cit14","doi-asserted-by":"publisher","first-page":"104","DOI":"10.1016\/j.gca.2017.01.035","article-title":"Redox controls on arsenic enrichment\nand release from aquifer sediments in central Yangtze River Basin","volume":"204","author":"Schaefer","year":"2017","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026100609065843600_cit15","doi-asserted-by":"publisher","first-page":"141","DOI":"10.1021\/acs.est.6b03484","article-title":"Quantifying Cr(VI)\nproduction and export from serpentine soil of the California coast\nrange","volume":"51","author":"McClain","year":"2017","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit16","doi-asserted-by":"publisher","first-page":"12416","DOI":"10.1021\/acs.est.7b04097","article-title":"Rates of\nCr(VI) generation from CrxFe1\u2013x(OH)3 solids upon reaction with manganese oxide","volume":"51","author":"Pan","year":"2017","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit17","doi-asserted-by":"publisher","first-page":"1921","DOI":"10.1021\/es0621997","article-title":"Hydrogarnet: A host\nphase for Cr(VI) in chromite ore processing residue (COPR) and other\nhigh pH wastes","volume":"41","author":"Hillier","year":"2007","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit18","doi-asserted-by":"publisher","first-page":"464A","DOI":"10.1021\/es022466i","article-title":"Peer Reviewed:\nIn situ treatment of chromium-contaminated groundwater","volume":"36","author":"Fruchter","year":"2002","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit19","doi-asserted-by":"publisher","first-page":"1261","DOI":"10.1007\/s10953-007-9179-5","article-title":"Chromium(III) hydroxide solubility in the aqueous K+-H+-OH\u2013-CO2-HCO3\u2013-CO32--H2O system: A thermodynamic model","volume":"36","author":"Rai","year":"2007","journal-title":"J.\nSolution Chem."},{"key":"2026100609065843600_cit20","doi-asserted-by":"publisher","first-page":"88","DOI":"10.1016\/j.gca.2019.02.039","article-title":"Reactivity\nof redox cycled Fe-bearing subsurface sediments towards hexavalent\nchromium reduction","volume":"252","author":"Bishop","year":"2019","journal-title":"Geochim. Cosmochim. 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Hazard. Mater."},{"key":"2026100609065843600_cit24","doi-asserted-by":"publisher","first-page":"9817","DOI":"10.1021\/acs.est.7b02934","article-title":"Kinetics and\nproducts of chromium(VI)\nreduction by iron(II\/III)-bearing clay minerals","volume":"51","author":"Joe-Wong","year":"2017","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit25","doi-asserted-by":"publisher","first-page":"13767","DOI":"10.1021\/acs.est.9b05208","article-title":"Effect of coexisting Fe(III) (oxyhydr)oxides\non Cr(VI) reduction by Fe(II)-bearing clay minerals","volume":"53","author":"Liao","year":"2019","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit26","doi-asserted-by":"publisher","first-page":"84","DOI":"10.2175\/106143005X84558","article-title":"Chromate removal by an iron sorbent: Mechanism and\nmodeling","volume":"78","author":"Smith","year":"2006","journal-title":"Water Environ. 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J."},{"key":"2026100609065843600_cit29","first-page":"525","article-title":"The Iron Oxides:\nStructure, Properties, Reactions, Occurences and Uses","volume-title":"Synthesis","author":"Cornell","year":"2003","edition":"2"},{"key":"2026100609065843600_cit30","doi-asserted-by":"publisher","first-page":"191","DOI":"10.1346\/CCMN.1984.0320306","article-title":"Preparation and handling\nof dithionite-reduced smectite suspensions","volume":"32","author":"Stucki","year":"1984","journal-title":"Clays Clay Miner."},{"key":"2026100609065843600_cit31","doi-asserted-by":"publisher","first-page":"213","DOI":"10.1097\/00010694-197704000-00001","article-title":"Retention\nof phenolic acids by noncrystalline hydroxyaluminum and -iron compounds\nand clay minerals of soils","volume":"123","author":"Huang","year":"1977","journal-title":"Soil Sci."},{"key":"2026100609065843600_cit32","doi-asserted-by":"publisher","first-page":"11337","DOI":"10.1021\/es5031849","article-title":"Redox\ninteractions between Cr(VI) and Fe(II) in bioreduced biotite and chlorite","volume":"48","author":"Brookshaw","year":"2014","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit33","doi-asserted-by":"publisher","first-page":"779","DOI":"10.1021\/ac60289a016","article-title":"Ferrozine:\nA new spectrophotometric reagent for iron","volume":"42","author":"Stookey","year":"1970","journal-title":"Anal.\nChem."},{"key":"2026100609065843600_cit34","doi-asserted-by":"publisher","first-page":"537","DOI":"10.1107\/S0909049505012719","article-title":"ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray\nabsorption spectroscopy using IFEFFIT","volume":"12","author":"Ravel","year":"2005","journal-title":"J. Synchrotron\nRadiat."},{"key":"2026100609065843600_cit35","doi-asserted-by":"publisher","first-page":"322","DOI":"10.1107\/S0909049500016964","article-title":"IFEFFIT: interactive\nXAFS analysis and FEFF fitting","volume":"8","author":"Newville","year":"2001","journal-title":"J. Synchrotron\nRadiat."},{"key":"2026100609065843600_cit36","unstructured":"Ianni, J. C.\n          \n          Kintecus-enzyme\n& combustion chemical kinetics and equilibrium Software\n          2018\n          https:\/\/kintecus.com\/ (accessed Nov 26, 2024)."},{"key":"2026100609065843600_cit37","doi-asserted-by":"publisher","first-page":"394","DOI":"10.1016\/j.gca.2018.07.018","article-title":"Mechanisms\nof hydroxyl radicals production from pyrite oxidation by hydrogen\nperoxide: surface versus aqueous reactions","volume":"238","author":"Zhang","year":"2018","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026100609065843600_cit38","doi-asserted-by":"publisher","first-page":"117","DOI":"10.1016\/j.gca.2015.03.026","article-title":"Ferrous iron oxidation\nby molecular\noxygen under acidic conditions: the effect of citrate, EDTA and fulvic\nacid","volume":"160","author":"Jones","year":"2015","journal-title":"Geochim. Cosmochim. 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Acta"},{"key":"2026100609065843600_cit41","doi-asserted-by":"publisher","first-page":"966","DOI":"10.2138\/am.2007.2318","article-title":"XANES study\nof the oxidation state of Cr in lower mantle phases: periclase and\nmagnesium silicate perovskite","volume":"92","author":"Eeckhout","year":"2007","journal-title":"Am. Mineral."},{"key":"2026100609065843600_cit42","doi-asserted-by":"publisher","first-page":"1202","DOI":"10.2138\/am.2010.3274","article-title":"The Cr X-ray\nabsorption K-edge structure of poorly crystalline Fe(III)\u2013Cr(III)-oxyhydroxides","volume":"95","author":"Frommer","year":"2010","journal-title":"Am. Mineral."},{"key":"2026100609065843600_cit43","doi-asserted-by":"publisher","first-page":"169","DOI":"10.1016\/j.chemosphere.2014.03.059","article-title":"A XAFS study of plain and composite\niron(III) and chromium(III) hydroxides","volume":"111","author":"Papassiopi","year":"2014","journal-title":"Chemosphere"},{"key":"2026100609065843600_cit44","doi-asserted-by":"publisher","first-page":"75","DOI":"10.1016\/j.clay.2004.01.001","article-title":"Colloidal behavior\nof aqueous montmorillonite suspensions:\nthe specific role of pH in the presence of indifferent electrolytes","volume":"27","author":"Tomba\u0301cz","year":"2004","journal-title":"Appl. Clay Sci."},{"key":"2026100609065843600_cit45","doi-asserted-by":"publisher","first-page":"13502","DOI":"10.1021\/acs.est.6b03637","article-title":"Dynamics of chromium(VI)\nremoval from drinking water by iron electrocoagulation","volume":"50","author":"Pan","year":"2016","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit46","doi-asserted-by":"publisher","first-page":"13732","DOI":"10.1021\/acs.est.9b04769","article-title":"Synergistic\neffects of reduced nontronite and organic ligands on Cr(VI) reduction","volume":"53","author":"Liu","year":"2019","journal-title":"Environ. Sci. Technol."},{"key":"2026100609065843600_cit47","doi-asserted-by":"publisher","first-page":"4436","DOI":"10.1016\/j.gca.2006.06.1557","article-title":"Effect of pH and organic ligands\non the kinetics of smectite dissolution at 25\u00b0C","volume":"70","author":"Golubev","year":"2006","journal-title":"Geochim. Cosmochim. Acta"},{"issue":"1\u20132","key":"2026100609065843600_cit48","doi-asserted-by":"publisher","first-page":"81","DOI":"10.1016\/0304-4203(92)90049-G","article-title":"Seasonal iron cycling in the salt-marsh\nsedimentary environment:\nthe importance of ligand complexes with Fe(II) and Fe(III) in the\ndissolution of Fe(III) minerals and pyrite, respectively","volume":"40","author":"Luther","year":"1992","journal-title":"Mar. Chem."},{"key":"2026100609065843600_cit49","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2020.140061","article-title":"Contribution\nof clay-aquitard to aquifer iron concentrations\nand water quality","volume":"741","author":"Liu","year":"2020","journal-title":"Sci. Total Environ."},{"key":"2026100609065843600_cit50","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-50974-x","article-title":"Directional long-distance\nelectron transfer from reduced\nto oxidized zones in the subsurface","volume":"15","author":"Zhang","year":"2024","journal-title":"Nat. Commun."},{"key":"2026100609065843600_cit51","doi-asserted-by":"publisher","first-page":"2228","DOI":"10.1021\/ic00261a013","article-title":"Solubility of amorphous\nchromium(III)-iron(III) hydroxide solid solutions","volume":"26","author":"Sass","year":"1987","journal-title":"Inorg. Chem."}],"container-title":["Environmental Science &amp;\nTechnology"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.est.5c13507","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/esthag\/article-pdf\/60\/39\/27990\/68621141\/acs.est.5c13507.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/esthag\/article-pdf\/60\/39\/27990\/68621141\/acs.est.5c13507.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T13:29:20Z","timestamp":1791293360000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/esthag\/article\/60\/39\/27990\/5436603\/Mechanisms-of-Hexavalent-Chromium-Reduction-in-Fe"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,23]]},"references-count":51,"journal-issue":{"issue":"39","published-online":{"date-parts":[[2026,9,23]]},"published-print":{"date-parts":[[2026,10,6]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.est.5c13507","relation":{},"ISSN":["0013-936X","1520-5851"],"issn-type":[{"value":"0013-936X","type":"print"},{"value":"1520-5851","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,23]]}}}