Aquatic Geochemistry

, Volume 24, Issue 4, pp 257–277 | Cite as

Reduction of Manganese Oxides: Thermodynamic, Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer Steps

  • George W. LutherIIIEmail author
  • Aubin Thibault de Chanvalon
  • Véronique E. Oldham
  • Emily R. Estes
  • Bradley M. Tebo
  • Andrew S. Madison
Original Article


Manganese oxides, typically similar to δ-MnO2, form in the aquatic environment at near neutral pH via bacterially promoted oxidation of Mn(II) species by O2, as the reaction of [Mn(H2O)6]2+ with O2 alone is not thermodynamically favorable below pH of ~ 9. As manganese oxide species are reduced by the triphenylmethane compound leucoberbelein blue (LBB) to form the colored oxidized form of LBB (λmax = 623 nm), their concentration in the aquatic environment can be determined in aqueous environmental samples (e.g., across the oxic–anoxic interface of the Chesapeake Bay, the hemipelagic St. Lawrence Estuary and the Broadkill River estuary surrounded by salt marsh wetlands), and their reaction progress can be followed in kinetic studies. The LBB reaction with oxidized Mn solids can occur via a hydrogen atom transfer (HAT) reaction, which is a one-electron transfer process, but is unfavorable with oxidized Fe solids. HAT thermodynamics are also favorable for nitrite with LBB and MnO2 with ammonia (NH3). Reactions are unfavorable for NH4+ and sulfide with oxidized Fe and Mn solids, and NH3 with oxidized Fe solids. In laboratory studies and aquatic environments, the reduction of manganese oxides leads to the formation of Mn(III)-ligand complexes [Mn(III)L] at significant concentrations even when two-electron reductants react with MnO2. Key reductants are hydrogen sulfide, Fe(II) and organic ligands, including the siderophore desferioxamine-B. We present laboratory data on the reaction of colloidal MnO2 solutions (λmax ~ 370 nm) with these reductants. In marine waters, colloidal forms of Mn oxides (< 0.2 µm) have not been detected as Mn oxides are quantitatively trapped on 0.2-µm filters. Thus, the reactivity of Mn oxides with reductants depends on surface reactions and possible surface defects. In the case of MnO2, Mn(IV) is an inert cation in octahedral coordination; thus, an inner-sphere process is likely for electrons to go into the empty e g * conduction band of its orbitals. Using frontier molecular orbital theory and band theory, we discuss aspects of these surface reactions and possible surface defects that may promote MnO2 reduction using laboratory and field data for the reaction of MnO2 with hydrogen sulfide and other reductants.


Manganese oxide reduction Electron transfer Hydrogen atom transfer Mn(III) ligands Band theory 



This work was funded by grants from the Chemical Oceanography program of the National Science Foundation (OCE-1558738 to GWL; OCE-1558692 to BMT). We thank A. Mucci for constructive comments on an earlier version of this manuscript. We also thank the anonymous reviewers for their constructive comments.


  1. Altmann HJ (1972) Determination of dissolved oxygen in water with leukoberbelin-blue I. A quick Winkler method. Anal Chem 262:97–99CrossRefGoogle Scholar
  2. Audi AA, Sherwood PMA (2002) Valence-band X-ray photoelectron spectroscopic studies of manganese and its oxides interpreted by cluster and band structure calculations. Surf Interface Anal 33:274–282CrossRefGoogle Scholar
  3. Bargar JR, Tebo BM, Bergmann U, Webb SM, Glatzel P, Chiu VQ, Villalobos M (2005) Biotic and abiotic products of Mn(II) oxidation by spores of the marine Bacillus sp. Strain SG-1. Am Mineral 90:143–154CrossRefGoogle Scholar
  4. Clement BG, Luther GW, Tebo BM (2009) Rapid, oxygen-dependent microbial Mn(II) oxidation kinetics at sub-micromolar oxygen concentrations in the Black Sea suboxic zone. Geochim Cosmochim Acta 73:1878–1889. CrossRefGoogle Scholar
  5. Dénès F, Pichowicz M, Povie G, Renaud P (2014) Thiyl radicals in organic synthesis. Chem Rev 114:2587–2693CrossRefGoogle Scholar
  6. Duckworth OW, Sposito G (2005) Siderophore-manganese (III) interactions I. Manganite dissolution promoted by desferrioxamine-B. Environ Sci Technol 39:6045–6051CrossRefGoogle Scholar
  7. Duckworth OW, Sposito G (2007) Siderophore-promoted dissolution of synthetic and biogenic layer-type Mn oxides. Chem Geol 242:497–508CrossRefGoogle Scholar
  8. Estes ER, Andeer PF, Nordlund D, Wankel SD, Hansel CM (2016) Biogenic manganese oxides as reservoirs of organic carbon and proteins in terrestrial and marine environments. Geobiology 15:158–172. CrossRefGoogle Scholar
  9. Foti MC, Johnson ER, Vinqvist MR, Wright JS, Barclay LRC, Ingold KU (2002) Naphthalene diols: a new class of antioxidants intramolecular hydrogen bonding in catechols, naphthalene diols, and their aryloxyl radicals. J Org Chem 67:5190–5196CrossRefGoogle Scholar
  10. Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate: oxidations of arylalkanes in organic solvents. Inorg Chem 36:2069–2078CrossRefGoogle Scholar
  11. Herszage J, dos Santos Afonso M (2003) Mechanism of hydrogen sulfide oxidation by manganese(IV) oxide in aqueous solutions. Langmuir 19:9684–9692CrossRefGoogle Scholar
  12. Javanaud C, Michotey V, Guasco S, Garcia N, Anschutz P, Canton M, Bonin P (2011) Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level. Res Microbiol 162:848–857CrossRefGoogle Scholar
  13. Kartal B, de Almeida NM, Maalcke WJ, Op den Camp HJM, Jetten MSM, Keltjens JT (2013) How to make a living from anaerobic ammonium oxidation. FEMS Microbiol Rev 37:428–461CrossRefGoogle Scholar
  14. Konovalov S, Luther GW, Friederich GE, Nuzzio DB, Tebo BM, Murray JW, Oguz T, Glazer B, Trouwborst RE, Clement B, Murray KJ, Romanov AS (2003) Lateral injection of oxygen with the Bosporus plume: fingers of oxidizing potential in the Black Sea. Limnol Oceanogr 48:2369–2376CrossRefGoogle Scholar
  15. Learman DL, Voelker BM, Vazquez-Rodriguez AI, Hansel CM (2011a) Formation of manganese oxides by bacterially generated superoxide. Nat Geosci 4:95–98CrossRefGoogle Scholar
  16. Learman DL, Wankel SD, Webb SM, Martinez N, Madden AS, Hansel CM (2011b) Coupled biotic–abiotic Mn(II) oxidation pathway mediates the formation and structural evolution of biogenic Mn oxides. Geochim Cosmochim Acta 75:6048–6063. CrossRefGoogle Scholar
  17. Lin H, Taillefert M (2014) Key geochemical factors regulating Mn(IV)-catalyzed anaerobic nitrification in coastal marine sediments. Geochim Cosmochim Acta 133:17–33CrossRefGoogle Scholar
  18. Lucarini M, Pedrielli P, Pedulli GF (1996) Bond dissociation energies of O–H bonds in substituted phenols from equilibration studies. J Org Chem 61:9259–9263CrossRefGoogle Scholar
  19. Lucarini M, Mugnaini V, Pedulli GF (2002) Bond dissociation enthalpies of polyphenols: the importance of cooperative effects. J Org Chem 67:928–931CrossRefGoogle Scholar
  20. Luther GW (2010) The role of one and two electron transfer reactions in forming thermodynamically unstable intermediates as barriers in multi-electron redox reactions. Aquat Geochem 16:395–420CrossRefGoogle Scholar
  21. Luther GW (2016) Inorganic chemistry for geochemistry and environmental sciences: fundamentals and applications. Wiley, New YorkGoogle Scholar
  22. Luther GW, Popp JI (2002) Kinetics of the abiotic reduction of polymeric manganese dioxide by nitrite: an anaerobic nitrification reaction. Aquat Geochem 8:15–36CrossRefGoogle Scholar
  23. Luther GW, Sundby B, Lewis BL, Brendel PJ, Silverberg N (1997) Interactions of manganese with the nitrogen cycle: alternative pathways to dinitrogen. Geochim Cosmochim Acta 61:4043–4052CrossRefGoogle Scholar
  24. Madison AS, Tebo BM, Mucci A, Sundby B, Luther GW (2013) Abundant Mn(III) in porewaters is a major component of the sedimentary redox system. Science 341:875–878. CrossRefGoogle Scholar
  25. Matocha CJ, Sparks DL, Amonette JE, Kukkadapu RK (2001) Kinetics and mechanism of birnessite reduction by catechol. Soil Sci Soc Am J 65:58–66CrossRefGoogle Scholar
  26. Mayer JM (2011) Understanding hydrogen atom transfer: from bond strengths to marcus theory. Acc Chem Res 44:36–46CrossRefGoogle Scholar
  27. Morse JW, Luther GW (1999) Chemical influences on trace metal-sulfide interactions in anoxic sediments. Geochim Cosmochim Acta 63:3373–3378CrossRefGoogle Scholar
  28. Oldham VE, Owings SM, Jones M, Tebo BM, Luther GW (2015) Evidence for the presence of strong Mn(III)-binding ligands in the water column of the Chesapeake Bay. Mar Chem 171:58–66. CrossRefGoogle Scholar
  29. Oldham VE, Mucci A, Tebo BM, Luther GW (2017a) Soluble Mn(III)-L complexes are ubiquitous in oxygenated waters and stabilized by humic ligands. Geochim Cosmochim Acta 199:238–246. CrossRefGoogle Scholar
  30. Oldham VE, Jones MR, Tebo BM, Luther GW (2017b) Oxidative and reductive processes contributing to manganese cycling at oxic–anoxic interfaces. Mar Chem 195:122–128. CrossRefGoogle Scholar
  31. Oldham VE, Miller MT, Jensen LT, Luther GW (2017c) Revisiting Mn and Fe removal in humic rich estuaries. Geochim Cosmochim Acta 209:267–283. CrossRefGoogle Scholar
  32. Perez-Benito JF, Brillas E, Pouplana R (1989) Identification of a soluble form of colloidal manganese (IV). Inorg Chem 28:390–392CrossRefGoogle Scholar
  33. Rickard D, Luther GW (2007) Chemistry of iron sulfides. Chem Rev 107:514–562CrossRefGoogle Scholar
  34. Salter-Blanc AJ, Bylaska EJ, Lyon MA, Ness SC, Tratnyek PG (2016) Structure–activity relationships for rates of aromatic amine oxidation by manganese dioxide. Environ Sci Technol 50:5094–5102CrossRefGoogle Scholar
  35. Sheriff TS, Carr P, Piggott B (2003) Manganese catalysed reduction of dioxygen to hydrogen peroxide: structural studies on a manganese(III)-catecholate complex. Inorg Chim Acta 348:115–122CrossRefGoogle Scholar
  36. Siebecker MG, Madison AS, Luther GW (2015) Reduction kinetics of polymeric (soluble) manganese (IV) oxide (MnO2) by ferrous iron (Fe2+). Aquat Geochem 21:143–158. CrossRefGoogle Scholar
  37. Stone AT, Morgan JJ (1984a) Reduction and dissolution of manganese (III) and manganese(IV) oxides by organics. 1. Reaction with hydroquinone. Environ Sci Technol 18:450–456CrossRefGoogle Scholar
  38. Stone AT, Morgan JJ (1984b) Reduction and dissolution of manganese (III) and manganese(IV) oxides by organics. 2. Survey of the reactivity of organics. Environ Sci Technol 18:617–624CrossRefGoogle Scholar
  39. Taube H (1983) Electron transfer between metal complexes—retrospective. Nobel Lecture, 8 December 1983Google Scholar
  40. Tebo BM, Bargar JR, Clement B, Dick G, Murray KJ, Parker D, Verity R, Webb SM (2004) Biogenic manganese oxides: properties and mechanisms of formation. Annu Rev Earth Planet Sci 32:287–328CrossRefGoogle Scholar
  41. Wright MH, Geszvain K, Oldham VE, Luther GW, Tebo BM (2018) Oxidative formation and removal of complexed Mn(III) by pseudomonas. Front Microbiol 9:560. CrossRefGoogle Scholar
  42. Yao W, Millero FJ (1993) The rate of sulfide oxidation by δMnO2 in seawater. Geochim Cosmochim Acta 57:3359–3365CrossRefGoogle Scholar
  43. Yao W, Millero FJ (1995) Oxidation of hydrogen sulfide by Mn(IV) and Fe(III) (hydr)oxides in seawater. In: Vairavamurthy V, Schoonen MAA, Eglinton TI, Luther GW, Manowitz B (eds) Geochemical transformations of sedimentary sulfur. American chemical society symposium series, vol 612, Ch. 14. Washington, DC, pp 260–279Google Scholar
  44. Zhang X-M, Bordwell FG (1992) Homolytic bond dissociation energies of the benzylic C–H bonds in radical anions and radical cations derived from fluorenes, triphenylmethanes, and related compounds. J Am Chem Soc 114:9787–9792CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.School of Marine Science and PolicyUniversity of DelawareLewesUSA
  2. 2.Division of Environmental and Biomolecular SystemsOregon Health and Science UniversityPortlandUSA
  3. 3.Golder Associates Inc.Mt. LaurelUSA

Personalised recommendations