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At the redox interface, reduced sulfur might affect the fate of sorbed Cd\u00ad(II) by either reducing Mn oxides or forming strong complexes with Cd\u00ad(II). Here, we investigated the fate of Cd\u00ad(II) immobilized on \u03b4-MnO2 affected by reduced sulfur (S2\u2013 and cysteine). A low concentration of S2\u2013 led to Cd\u00ad(II) migration from vacant sites to edge sites, while a high concentration of S2\u2013 largely converted Cd\u00ad(II) adsorbed on the surface of \u03b4-MnO2 to CdS. At low pH, the cysteine addition led to the release of Cd\u00ad(II) initially adsorbed at the \u03b4-MnO2 vacant sites into the solution and caused the migration of a small portion of Cd\u00ad(II) to the \u03b4-MnO2 edge sites. At high pH, a high concentration of cysteine led to the detachment of Cd\u00ad(II) from \u03b4-MnO2, Cd\u00ad(II) readsorption by Mn\u00ad(III)-bearing minerals, and Cd\u2013cysteine formation. Changes of Cd\u00ad(II) speciation were caused by \u03b4-MnO2 dissolution induced by reduced sulfur, the competition of generated Mn\u00ad(II\/III) for the adsorption sites, and the precipitation of Cd\u00ad(II) with reduced sulfur. This study indicates that reduced sulfur is a critical factor controlling the fate of Cd\u00ad(II) immobilized on Mn oxides in the aquatic environment.<\/jats:p>","DOI":"10.1021\/acs.est.0c02936","type":"journal-article","created":{"date-parts":[[2020,11,11]],"date-time":"2020-11-11T17:02:32Z","timestamp":1605114152000},"page":"14955-14963","source":"Crossref","is-referenced-by-count":57,"title":["Role\nof Reduced Sulfur in the Transformation of Cd(II)\nImmobilized by \u03b4\u2011MnO2"],"prefix":"10.1021","volume":"54","author":[{"given":"Qian","family":"Sun","sequence":"first","affiliation":[{"name":"The Chinese Academy of Sciences , , ,","place":["Nanjing, China, 210008"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, China, 100049"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9887-2784","authenticated-orcid":true,"given":"Peixin","family":"Cui","sequence":"additional","affiliation":[{"name":"The Chinese Academy of Sciences , , ,","place":["Nanjing, China, 210008"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Song","family":"Wu","sequence":"additional","affiliation":[{"name":"Nanjing University , , ,","place":["Nanjing, China, 210008"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cun","family":"Liu","sequence":"additional","affiliation":[{"name":"The Chinese Academy of Sciences , , ,","place":["Nanjing, China, 210008"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tingting","family":"Fan","sequence":"additional","affiliation":[{"name":"Nanjing Institute of Environmental Sciences , , ,","place":["Nanjing, China, 210008"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marcelo Eduardo","family":"Alves","sequence":"additional","affiliation":[{"name":"ESALQ\/USP , , , ,","place":["Piracicaba, Sa\u0303o Paulo, Brazil, 13418-900"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hu","family":"Cheng","sequence":"additional","affiliation":[{"name":"Nanjing Forestry University , , ,","place":["Nanjing, China, 210037"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Meiying","family":"Huang","sequence":"additional","affiliation":[{"name":"The Chinese Academy of Sciences , , ,","place":["Nanjing, China, 210008"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, China, 100049"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7917-7954","authenticated-orcid":true,"given":"Dongmei","family":"Zhou","sequence":"additional","affiliation":[{"name":"The Chinese Academy of Sciences , , ,","place":["Nanjing, China, 210008"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0921-0122","authenticated-orcid":true,"given":"Yujun","family":"Wang","sequence":"additional","affiliation":[{"name":"The Chinese Academy of Sciences , , ,","place":["Nanjing, China, 210008"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, China, 100049"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2020,11,11]]},"reference":[{"key":"2026081418114039700_cit1","doi-asserted-by":"publisher","first-page":"1767","DOI":"10.1016\/j.ecoenv.2009.05.009","article-title":"Cadmium bioaccumulation\nin Proisotoma\nminuta in relation to bioavailability in soil","volume":"72","author":"Nursita","year":"2009","journal-title":"Ecotoxicol. Environ. Saf."},{"key":"2026081418114039700_cit2","doi-asserted-by":"publisher","first-page":"331","DOI":"10.1016\/s0025-3227(03)00122-1","article-title":"Uptake of elements from seawater by ferromanganese\ncrusts: solid-phase associations and seawater speciation","volume":"198","author":"Koschinsky","year":"2003","journal-title":"Mar. Geol."},{"key":"2026081418114039700_cit3","doi-asserted-by":"publisher","first-page":"4106","DOI":"10.1021\/es034070s","article-title":"Cd adsorption properties\nof components in different freshwater surface coatings: the important\nrole of ferromanganese oxides","volume":"37","author":"Dong","year":"2003","journal-title":"Environ. Sci.\nTechnol."},{"key":"2026081418114039700_cit4","doi-asserted-by":"publisher","first-page":"3359","DOI":"10.1016\/0016-7037(93)90544-7","article-title":"The rate of sulfide\noxidation by \u03b4MnO2 in seawater","volume":"57","author":"Yao","year":"1993","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit5","doi-asserted-by":"publisher","first-page":"3489","DOI":"10.1016\/j.gca.2008.04.033","article-title":"Investigating pathways of diagenetic\norganic matter sulfurization using compound-specific sulfur isotope\nanalysis","volume":"72","author":"Werne","year":"2008","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit6","doi-asserted-by":"publisher","first-page":"173","DOI":"10.1016\/j.gca.2017.07.016","article-title":"Mechanistic\ninvestigation of Fe\u00ad(III) oxide reduction\nby low molecular weight organic sulfur species","volume":"215","author":"Eitel","year":"2017","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit7","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."},{"key":"2026081418114039700_cit8","doi-asserted-by":"publisher","first-page":"2763","DOI":"10.4319\/lo.2006.51.6.2763","article-title":"Distribution of the thiols glutathione\nand 3-mercaptopropionic acid in Connecticut lakes","volume":"51","author":"Hu","year":"2006","journal-title":"Limnol. Oceanogr."},{"key":"2026081418114039700_cit9","doi-asserted-by":"publisher","first-page":"567","DOI":"10.1007\/s10498-011-9128-1","article-title":"Examination\nand refinement of the determination of aqueous hydrogen sulfide by\nthe methylene blue method","volume":"17","author":"Reese","year":"2011","journal-title":"Aquat. Geochem."},{"key":"2026081418114039700_cit10","doi-asserted-by":"publisher","first-page":"361","DOI":"10.1080\/01490458609385944","article-title":"Chemical and microbial\nstudies of sulfide-mediated\nMn reduction","volume":"4","author":"Burdige","year":"1986","journal-title":"Geomicrobiology"},{"key":"2026081418114039700_cit11","doi-asserted-by":"publisher","first-page":"2931","DOI":"10.1021\/es980307m","article-title":"Biogeochemical\ncycles of manganese and iron at the oxic-anoxic transition of a stratified\nmarine basin (Orca Basin, Gulf of Mexico)","volume":"32","author":"Van\nCappellen","year":"1998","journal-title":"Environ.\nSci. Technol."},{"key":"2026081418114039700_cit12","doi-asserted-by":"publisher","first-page":"1573","DOI":"10.1016\/s0016-7037(00)00622-0","article-title":"Anaerobic sulfide oxidation\nand stable isotope fractionation\nassociated with bacterial sulfur disproportionation in the presence\nof MnO2","volume":"65","author":"Bo\u0308ttcher","year":"2001","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit13","doi-asserted-by":"publisher","first-page":"106","DOI":"10.1016\/j.jhazmat.2015.02.018","article-title":"Oxidation\nprocess of dissolvable sulfide by synthesized todorokite\nin aqueous systems","volume":"290","author":"Gao","year":"2015","journal-title":"J. Hazard. Mater."},{"key":"2026081418114039700_cit14","doi-asserted-by":"publisher","first-page":"3338","DOI":"10.1021\/es001848q","article-title":"Mn\u00ad(III) center availability\nas a rate controlling factor\nin the oxidation of phenol and sulfide on \u03b4-MnO2","volume":"35","author":"Nico","year":"2001","journal-title":"Environ. Sci. Technol."},{"key":"2026081418114039700_cit15","doi-asserted-by":"publisher","first-page":"299","DOI":"10.1346\/ccmn.2017.064066","article-title":"Oxidation\nand catalytic oxidation of dissolved sulfide by manganite in aqueous\nsystems","volume":"65","author":"Luo","year":"2017","journal-title":"Clay Miner."},{"key":"2026081418114039700_cit16","doi-asserted-by":"publisher","first-page":"9684","DOI":"10.1021\/la034016p","article-title":"Mechanism of hydrogen sulfide oxidation\nby manganese\u00ad(IV)\noxide in aqueous solutions","volume":"19","author":"Herszage","year":"2003","journal-title":"Langmuir"},{"key":"2026081418114039700_cit17","doi-asserted-by":"publisher","first-page":"1323","DOI":"10.1007\/s11368-011-0381-0","article-title":"Oxidation\nbehavior and kinetics of sulfide by synthesized manganese oxide minerals","volume":"11","author":"Qiu","year":"2011","journal-title":"J. Soils Sediments"},{"key":"2026081418114039700_cit18","doi-asserted-by":"publisher","first-page":"13202","DOI":"10.1021\/acs.est.8b03993","article-title":"Effect of\nmanganese oxide aging and structure transformation on the kinetics\nof thiol oxidation","volume":"52","author":"Eitel","year":"2018","journal-title":"Environ. Sci. Technol."},{"key":"2026081418114039700_cit19","doi-asserted-by":"publisher","first-page":"3187","DOI":"10.1021\/acs.est.6b04347","article-title":"Impact of Mn\u00ad(II)-manganese\noxide\nreactions on Ni and Zn speciation","volume":"51","author":"Hinkle","year":"2017","journal-title":"Environ.\nSci. Technol."},{"key":"2026081418114039700_cit20","doi-asserted-by":"publisher","first-page":"3635","DOI":"10.1016\/0016-7037(93)90145-m","article-title":"Adsorption and coprecipitation\nof divalent metals with\nmackinawite (FeS)","volume":"57","author":"Morse","year":"1993","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit21","doi-asserted-by":"publisher","first-page":"604","DOI":"10.1016\/j.gca.2006.10.011","article-title":"Complexation\nof cadmium to sulfur and oxygen functional groups in an organic soil","volume":"71","author":"Karlsson","year":"2007","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit22","doi-asserted-by":"publisher","first-page":"165","DOI":"10.1016\/s0020-1693(00)84536-3","article-title":"Computer simulation\nmodels for the low-molecular-weight complex distribution of cadmium\u00ad(II)\nand nickel\u00ad(II) in human blood plasma","volume":"108","author":"Cole","year":"1985","journal-title":"Inorg.\nChim. Acta"},{"key":"2026081418114039700_cit23","doi-asserted-by":"publisher","first-page":"1844","DOI":"10.1021\/acs.est.7b04379","article-title":"Structural\ntransformation of birnessite\nby fulvic acid under anoxic conditions","volume":"52","author":"Wang","year":"2018","journal-title":"Environ.\nSci. Technol."},{"key":"2026081418114039700_cit24","doi-asserted-by":"publisher","first-page":"302","DOI":"10.1016\/j.gca.2012.02.019","article-title":"Zn sorption modifies\ndynamically the layer and interlayer\nstructure of vernadite","volume":"85","author":"Grangeon","year":"2012","journal-title":"Geochim. Cosmochim.\nActa"},{"key":"2026081418114039700_cit25","doi-asserted-by":"publisher","first-page":"2649","DOI":"10.1016\/s0016-7037(03)00217-5","article-title":"Characterization of\nthe manganese oxide produced by Pseudomonas putida strain MnB1","volume":"67","author":"Villalobos","year":"2003","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit26","volume-title":"Structure and Reactivity\nStudy of Biotic and Abiotic Poorly Crystalline Manganese Oxides","author":"Zhu","year":"2010"},{"key":"2026081418114039700_cit27","doi-asserted-by":"publisher","first-page":"3332","DOI":"10.1021\/es0340634","article-title":"Oxidation of cysteine and glutathione\nby soluble polymeric MnO2","volume":"37","author":"Herszage","year":"2003","journal-title":"Environ.\nSci. Technol."},{"key":"2026081418114039700_cit28","doi-asserted-by":"publisher","first-page":"122","DOI":"10.1016\/j.marchem.2017.06.002","article-title":"Oxidative and reductive\nprocesses contributing to manganese cycling at oxic-anoxic interfaces","volume":"195","author":"Oldham","year":"2017","journal-title":"Mar. Chem."},{"key":"2026081418114039700_cit29","doi-asserted-by":"publisher","first-page":"461","DOI":"10.1016\/j.ecss.2006.06.033","article-title":"Removal of H2S via an\niron catalytic cycle and iron sulfide precipitation in the water column\nof dead end tributaries","volume":"70","author":"Ma","year":"2006","journal-title":"Estuar. Coast Shelf\nSci."},{"key":"2026081418114039700_cit30","doi-asserted-by":"publisher","first-page":"207","DOI":"10.1016\/0003-2697(80)90139-6","article-title":"Determination\nof glutathione and glutathione disulfide using glutathione reductase\nand 2-vinylpyridine","volume":"106","author":"Griffith","year":"1980","journal-title":"Anal. Biochem."},{"key":"2026081418114039700_cit31","doi-asserted-by":"publisher","first-page":"1012","DOI":"10.1039\/c7en01109a","article-title":"Sulfidation\nMechanisms of Fe\u00ad(III)-(oxyhydr)\u00adoxide Nanoparticles: A Spectroscopic\nStudy","volume":"5","author":"Kumar","year":"2018","journal-title":"Environ. Sci.: Nano"},{"key":"2026081418114039700_cit32","doi-asserted-by":"publisher","first-page":"104932","DOI":"10.1016\/j.envint.2019.104932","article-title":"Cd\u00ad(II)\nretention and remobilization on \u03b4-MnO2 and Mn\u00ad(III)-rich\n\u03b4-MnO2 affected by Mn\u00ad(II)","volume":"130","author":"Sun","year":"2019","journal-title":"Environ. Int."},{"key":"2026081418114039700_cit33","first-page":"1427","article-title":"Oxidation\nof aspartic acid by water\nsoluble colloidal MnO2 in absence and presence of ionic\nand nonionic surfactants","volume":"46","author":"Akram","year":"2007","journal-title":"Indian J. Chem. A"},{"key":"2026081418114039700_cit34","doi-asserted-by":"publisher","first-page":"1236","DOI":"10.3866\/PKU.WHXB201602251","article-title":"Preparation,\ncharacterization and low-temperature NH3-SCR activity of\nMnOx\/SAPO-11 catalysts","volume":"32","author":"Liu","year":"2016","journal-title":"Acta Phys.-Chim.\nSin."},{"key":"2026081418114039700_cit35","first-page":"172","article-title":"Surface enhanced raman\nspectroscopic studies of the monolayer of cysteine on silver mirror","volume":"14","author":"Hao","year":"2002","journal-title":"Chin. J. Light Scatt."},{"key":"2026081418114039700_cit36","doi-asserted-by":"publisher","first-page":"149","DOI":"10.1016\/j.gca.2019.02.006","article-title":"Reductive transformations of layered manganese oxides\nby small organic acids and the fate of trace metals","volume":"250","author":"Flynn","year":"2019","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit37","doi-asserted-by":"publisher","first-page":"4465","DOI":"10.1021\/es1009955","article-title":"Cation\neffects on the layer structure of biogenic Mn-oxides","volume":"44","author":"Zhu","year":"2010","journal-title":"Environ. Sci. Technol."},{"key":"2026081418114039700_cit38","doi-asserted-by":"publisher","first-page":"191","DOI":"10.1016\/j.gca.2015.04.050","article-title":"Probing the sorption reactivity of\nthe edge surfaces in birnessite nanoparticles using nickel\u00ad(II)","volume":"164","author":"Simanova","year":"2015","journal-title":"Geochem. Cosmochim. Acta"},{"key":"2026081418114039700_cit39","doi-asserted-by":"publisher","first-page":"220","DOI":"10.1016\/j.gca.2016.07.035","article-title":"Structural response\nof phyllomanganates\nto wet aging and aqueous Mn\u00ad(II)","volume":"192","author":"Hinkle","year":"2016","journal-title":"Geochim. Cosmochim.\nActa"},{"key":"2026081418114039700_cit40","doi-asserted-by":"publisher","first-page":"1608","DOI":"10.2138\/am.2010.3516","article-title":"Structure\nof nanocrystalline phyllomanganates produced by freshwater fungi","volume":"95","author":"Grangeon","year":"2010","journal-title":"Am. Mineral."},{"key":"2026081418114039700_cit41","doi-asserted-by":"publisher","first-page":"751","DOI":"10.1016\/0016-7037(88)90335-3","article-title":"Complete oxidation\nof solid phase sulfides by manganese\nand bacteria in anoxic marine sediments","volume":"52","author":"Aller","year":"1988","journal-title":"Geochim.\nCosmochim. Acta"},{"key":"2026081418114039700_cit42","doi-asserted-by":"publisher","first-page":"564","DOI":"10.1007\/s11368-017-1774-5","article-title":"Interaction mechanism and kinetics\nof ferrous sulfide and manganese\noxides in aqueous system","volume":"18","author":"Luo","year":"2018","journal-title":"J. Soils Sediments"},{"key":"2026081418114039700_cit43","doi-asserted-by":"publisher","first-page":"4248","DOI":"10.1021\/acs.est.5b04834","article-title":"Real-time\nmanganese phase dynamics\nduring biological and abiotic manganese oxide reduction","volume":"50","author":"Johnson","year":"2016","journal-title":"Environ. Sci. Technol."},{"key":"2026081418114039700_cit44","doi-asserted-by":"publisher","first-page":"4886","DOI":"10.1021\/es506019j","article-title":"Impacts of aqueous Mn\u00ad(II) on the sorption of Zn\u00ad(II)\nby hexagonal birnessite","volume":"49","author":"Lefkowitz","year":"2015","journal-title":"Environ. Sci. Technol."},{"key":"2026081418114039700_cit45","doi-asserted-by":"publisher","first-page":"135","DOI":"10.1007\/s10895-015-1693-z","article-title":"Cd-Cysteine Nanorods as a Fluorescence Sensor for determination\nof Fe\u00ad(III) in Real Samples","volume":"26","author":"Ghiamati","year":"2016","journal-title":"J. Fluoresc."},{"key":"2026081418114039700_cit46","doi-asserted-by":"publisher","first-page":"2338","DOI":"10.1021\/es062269+","article-title":"Stability\nof metal-glutathione complexes during oxidation by hydrogen peroxide\nand Cu\u00ad(II)-catalysis","volume":"41","author":"Hsu-Kim","year":"2007","journal-title":"Environ. Sci. Technol."},{"key":"2026081418114039700_cit47","doi-asserted-by":"publisher","first-page":"109","DOI":"10.1016\/j.gca.2014.08.014","article-title":"Nucleation and growth of todorokite\nfrom birnessite: implications for trace metal cycling in marine sediments","volume":"144","author":"Atkins","year":"2014","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081418114039700_cit48","doi-asserted-by":"publisher","first-page":"205","DOI":"10.1007\/s00726-010-0635-y","article-title":"Adsorption of\ncysteine on hematite, magnetite and ferrihydrite:FT-IR,\nMo\u0308ssbauer, EPR spectroscopy and X-ray diffractometry studies","volume":"40","author":"Vieira","year":"2011","journal-title":"Amino Acids"},{"key":"2026081418114039700_cit49","doi-asserted-by":"publisher","first-page":"21","DOI":"10.1016\/j.jcis.2007.05.022","article-title":"Surface speciation\nof Cd\u00ad(II) and\nPb\u00ad(II) on kaolinite by XAFS spectroscopy","volume":"315","author":"Gra\u0308fe","year":"2007","journal-title":"J.\nColloid Interface Sci."},{"key":"2026081418114039700_cit50","doi-asserted-by":"publisher","first-page":"1108","DOI":"10.1016\/j.envpol.2011.02.019","article-title":"New insights\ninto the sorption mechanism of cadmium on red mud","volume":"159","author":"Luo","year":"2011","journal-title":"Environ. 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