{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T17:28:07Z","timestamp":1787074087024,"version":"build-2736575974"},"reference-count":59,"publisher":"American Chemical Society (ACS)","issue":"32","license":[{"start":{"date-parts":[[2026,8,7]],"date-time":"2026-08-07T00:00:00Z","timestamp":1786060800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100019109","name":"Environmental Molecular Sciences Laboratory","doi-asserted-by":"publisher","award":["60963"],"award-info":[{"award-number":["60963"]}],"id":[{"id":"10.13039\/100019109","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,18]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The reductive transformation of ferrihydrite (Fh) is a key process controlling iron mineral evolution and mineral-associated organic matter (MAOM) cycling in soils and sediments, yet the regulating role of coprecipitated silica remains poorly constrained. Here, we investigated the influence of coprecipitated silica on cysteine-induced Fh transformation under anoxic conditions using Fh and Si-Fh coprecipitates with Si\/Fe molar ratios of 0.05 and 0.1. Mineral evolution and Fe speciation were monitored using X-ray diffraction (XRD), Mo\u0308ssbauer spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy coupled with energy-dispersive X-ray analysis (TEM-EDX), and selective chemical extractions. In silica-free Fh, cysteine induced rapid transformation into lepidocrocite through reductive dissolution and recrystallization pathways that largely excluded silica and MAOM from the newly formed mineral phase. In contrast, coprecipitated silica altered the extent, rate, and pathway of mineral evolution. At a Si\/Fe ratio of 0.05, crystalline phase formation was delayed and redirected toward a porous-like goethite phase that retained substantial silica and organic associations. At a Si\/Fe ratio of 0.1, formation of crystalline secondary phases was strongly suppressed, coinciding with accumulation of labile surface-associated Fe(III). These findings demonstrate that coprecipitated silica can decouple reductive electron transfer from mineral recrystallization and alter the fate of MAOM during Fh transformation under anoxic conditions.<\/jats:p>","DOI":"10.1021\/acs.est.6c02208","type":"journal-article","created":{"date-parts":[[2026,8,7]],"date-time":"2026-08-07T16:02:09Z","timestamp":1786118529000},"page":"22466-22476","source":"Crossref","is-referenced-by-count":0,"title":["Coprecipitated\nSilica\nControls the Divergent Pathways\nof Cysteine-Induced Ferrihydrite Transformation"],"prefix":"10.1021","volume":"60","author":[{"given":"Yinyin","family":"Zheng","sequence":"first","affiliation":[{"name":"The Hebrew University of Jerusalem , , ,","place":["Rehovot, Israel, 7610001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Libor","family":"Kovarik","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99354"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ravi K.","family":"Kukkadapu","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99354"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4489-3691","authenticated-orcid":true,"given":"Qian","family":"Zhao","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99354"]},{"name":"The University of Texas at Dallas , , , ,","place":["Richardson, Texas, United States, 75080"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0100-9037","authenticated-orcid":true,"given":"Maya","family":"Engel","sequence":"additional","affiliation":[{"name":"The Hebrew University of Jerusalem , , ,","place":["Rehovot, Israel, 7610001"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,7]]},"reference":[{"issue":"4","key":"2026081810421467700_cit1","doi-asserted-by":"publisher","first-page":"1682","DOI":"10.1039\/D3EN00828B","article-title":"Influence\nof Time and Ageing Conditions on the Properties of Ferrihydrite","volume":"11","author":"Sassi","year":"2024","journal-title":"Environ. 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Technol."},{"key":"2026081810421467700_cit4","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2023.168376","article-title":"Cooperative Roles of\nPhosphate and Dissolved Organic Matter in Inhibiting Ferrihydrite\nTransformation and Their Distinct Fates","volume":"908","author":"Chi","year":"2024","journal-title":"Sci.\nTotal Environ."},{"issue":"24","key":"2026081810421467700_cit5","doi-asserted-by":"publisher","first-page":"10601","DOI":"10.1021\/acs.est.4c01519","article-title":"Iron Oxyhydroxide\nTransformation in a Flooded Rice Paddy Field and the Effect of Adsorbed\nPhosphate","volume":"58","author":"Schulz","year":"2024","journal-title":"Environ. Sci. Technol."},{"issue":"21","key":"2026081810421467700_cit6","doi-asserted-by":"publisher","first-page":"12316","DOI":"10.1021\/acs.est.8b03206","article-title":"Impact of\nOrganic Matter on Iron(II)-Catalyzed Mineral Transformations in Ferrihydrite\u2013Organic\nMatter Coprecipitates","volume":"52","author":"ThomasArrigo","year":"2018","journal-title":"Environ. Sci. Technol."},{"issue":"9","key":"2026081810421467700_cit7","doi-asserted-by":"publisher","first-page":"5929","DOI":"10.1021\/acs.est.1c08789","article-title":"Stabilization\nof Ferrihydrite and Lepidocrocite by Silicate during Fe(II)-Catalyzed\nMineral Transformation: Impact on Particle Morphology and Silicate\nDistribution","volume":"56","author":"Schulz","year":"2022","journal-title":"Environ. Sci. 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Technol."},{"key":"2026081810421467700_cit28","doi-asserted-by":"publisher","DOI":"10.1016\/j.cocis.2024.101888","article-title":"The Underestimated\nand Important Role of Thiol Moieties\nin Predicting the Fate of Toxic Metals in the Environment","volume":"75","author":"Catrouillet","year":"2025","journal-title":"Curr. Opin. Colloid Interface Sci."},{"key":"2026081810421467700_cit29","doi-asserted-by":"publisher","DOI":"10.3389\/fmicb.2022.1085214","article-title":"Metabolic Turnover of Cysteine-Related\nThiol Compounds\nat Environmentally Relevant Concentrations by Geobacter Sulfurreducens","volume":"13","author":"Gutensohn","year":"2023","journal-title":"Front. Microbiol."},{"key":"2026081810421467700_cit30","volume-title":"Iron Oxides\nin the Laboratory: Preparation and Characterization","author":"Schwertmann","year":"2008"},{"key":"2026081810421467700_cit31","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2024.136406","article-title":"Silicate Impedes\nArsenic Release and Oxidation from Ferrihydrite","volume":"480","author":"Huang","year":"2024","journal-title":"J. Hazard. Mater."},{"key":"2026081810421467700_cit32","doi-asserted-by":"publisher","first-page":"37","DOI":"10.1016\/j.chemgeo.2015.09.009","article-title":"Formation\nand Secondary Mineralization of Ferrihydrite in the Presence of Silicate\nand Mn(II)","volume":"415","author":"Wang","year":"2015","journal-title":"Chem. Geol."},{"issue":"4","key":"2026081810421467700_cit33","doi-asserted-by":"publisher","first-page":"503","DOI":"10.1021\/acsearthspacechem.8b00179","article-title":"One-Step Route Synthesis\nof Siliceous Six-Line Ferrihydrite: Implication\nfor the Formation of Natural Ferrihydrite","volume":"3","author":"Lee","year":"2019","journal-title":"ACS\nEarth Space Chem."},{"issue":"6","key":"2026081810421467700_cit34","doi-asserted-by":"publisher","first-page":"2276","DOI":"10.4319\/lo.2004.49.6.2276","article-title":"Thiols in Wetland Interstitial\nWaters and Their Role in Mercury and Methylmercury Speciation","volume":"49","author":"Zhang","year":"2004","journal-title":"Limnol. Oceanogr."},{"issue":"7","key":"2026081810421467700_cit35","doi-asserted-by":"publisher","first-page":"779","DOI":"10.1021\/ac60289a016","article-title":"Ferrozine-a\nNew Spectrophotometric Reagent for Iron","volume":"42","author":"Stookey","year":"1970","journal-title":"Anal.\nChem."},{"key":"2026081810421467700_cit36","doi-asserted-by":"crossref","unstructured":"Aasodi, R.; Murugan, V.; Kumari, P.; Shree, V.\n          Development of Analytical Method\nfor Separation and Quantification of Cysteine Hydrochloride Monohydrate,\nFollowed by Validation with Total Error Concept by Using Ultra Performance\nLiquid Chromatography with Pre-Column Derivatization\n          J. Chromatogr. Sep. Technol.\n          2018;\nVol. 09(04), 10.4172\/2157-7064.1000406.","DOI":"10.4172\/2157-7064.1000406"},{"issue":"10","key":"2026081810421467700_cit37","doi-asserted-by":"publisher","first-page":"2953","DOI":"10.1039\/D0EN00730G","article-title":"Nanoscale Observations of Fe(ii)-Induced Ferrihydrite\nTransformation","volume":"7","author":"Qafoku","year":"2020","journal-title":"Environ. Sci. 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Technol."},{"key":"2026081810421467700_cit40","doi-asserted-by":"publisher","first-page":"48","DOI":"10.1016\/j.gca.2012.05.041","article-title":"Pertechnetate\n(TcO4\u2212) Reduction\nby Reactive Ferrous Iron Forms in Naturally Anoxic, Redox Transition\nZone Sediments from the Hanford Site, USA","volume":"92","author":"Peretyazhko","year":"2012","journal-title":"Geochim.\nCosmochim. Acta"},{"issue":"6","key":"2026081810421467700_cit41","doi-asserted-by":"publisher","first-page":"3801","DOI":"10.1021\/acs.est.1c08044","article-title":"Understanding the Importance of Labile\nFe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron\nOxyhydroxides","volume":"56","author":"Liu","year":"2022","journal-title":"Environ. Sci. Technol."},{"issue":"10","key":"2026081810421467700_cit42","doi-asserted-by":"publisher","first-page":"5477","DOI":"10.1021\/es4043275","article-title":"Effect\nof Solution and Solid-Phase Conditions on the Fe(II)-Accelerated Transformation\nof Ferrihydrite to Lepidocrocite and Goethite","volume":"48","author":"Boland","year":"2014","journal-title":"Environ. Sci. Technol."},{"issue":"10","key":"2026081810421467700_cit43","doi-asserted-by":"publisher","first-page":"4938","DOI":"10.1039\/D0NA00643B","article-title":"Further Insights\ninto the Fe(ii) Reduction of 2-Line Ferrihydrite: A Semi in Situ and in Situ TEM Study","volume":"2","author":"Gomez","year":"2020","journal-title":"Nanoscale Adv."},{"issue":"21","key":"2026081810421467700_cit44","doi-asserted-by":"publisher","first-page":"11663","DOI":"10.1021\/acs.est.6b03015","article-title":"Influence\nof Dissolved Silicate on Rates of Fe(II) Oxidation","volume":"50","author":"Kinsela","year":"2016","journal-title":"Environ. Sci. Technol."},{"key":"2026081810421467700_cit45","unstructured":"Hem, J. D.; Cropper, W. H.\n          Survey of Ferrous-Ferric\nChemical Equilibria and Redox Potentials. No. 1459-A, USGPO1959."},{"key":"2026081810421467700_cit46","volume-title":"Aquatic Chemistry:\nChemical Equilibria and Rates in Natural Waters","author":"Stumm","year":"1996","edition":"3"},{"key":"2026081810421467700_cit47","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.gca.2019.11.009","article-title":"Interaction of FeII and Si under Anoxic and Reducing\nConditions: Structural Characteristics of Ferrous Silicate Co-Precipitates","volume":"270","author":"Francisco","year":"2020","journal-title":"Geochim. Cosmochim. 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Solid State Chem."},{"key":"2026081810421467700_cit49","doi-asserted-by":"crossref","DOI":"10.1007\/978-1-4419-9040-2","volume-title":"Mo\u0308ssbauer\nSpectroscopy\nof Environmental Materials and Their Industrial Utilization","author":"Murad","year":"2004"},{"issue":"2","key":"2026081810421467700_cit50","doi-asserted-by":"publisher","first-page":"161","DOI":"10.1180\/claymin.1988.023.2.04","article-title":"The Influence of\nCrystallinity on Magnetic Ordering in Natural Ferrihydrites","volume":"23","author":"Murad","year":"1988","journal-title":"Clay Miner."},{"issue":"3","key":"2026081810421467700_cit51","doi-asserted-by":"publisher","first-page":"301","DOI":"10.1180\/claymin.1983.018.3.07","article-title":"The Influence of Aluminium Substitution\nand Crystallinity\non the Mo\u0308ssbauer Spectra of Goethite","volume":"18","author":"Murad","year":"1983","journal-title":"Clay Miner."},{"issue":"19","key":"2026081810421467700_cit52","doi-asserted-by":"publisher","first-page":"3559","DOI":"10.1016\/S0016-7037(03)00160-1","article-title":"Iron (III)-Silica\nInteractions in Aqueous Solution: Insights from X-Ray Absorption Fine\nStructure Spectroscopy","volume":"67","author":"Pokrovski","year":"2003","journal-title":"Geochim. Cosmochim.\nActa"},{"issue":"21","key":"2026081810421467700_cit53","doi-asserted-by":"publisher","first-page":"7891","DOI":"10.1021\/es800881w","article-title":"Characterization\nof Ferrihydrite-Soil Organic Matter Coprecipitates by X-Ray Diffraction\nand Mo\u0308ssbauer Spectroscopy","volume":"42","author":"Eusterhues","year":"2008","journal-title":"Environ.\nSci. Technol."},{"issue":"12","key":"2026081810421467700_cit54","doi-asserted-by":"publisher","first-page":"7309","DOI":"10.1021\/acs.est.0c00996","article-title":"Citrate Controls\nFe(II)-Catalyzed Transformation of Ferrihydrite by Complexation of\nthe Labile Fe(III) Intermediate","volume":"54","author":"Sheng","year":"2020","journal-title":"Environ. 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