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V. Oldham, Shannon Owings, M. Jones, B. Tebo, G. Luther (2015)
Evidence for the presence of strong Mn(III)-binding ligands in the water column of the Chesapeake BayMarine Chemistry, 171
M. Jones, G. Luther, A. Mucci, B. Tebo (2019)
Concentrations of reactive Mn(III)-L and MnO2 in estuarine and marine waters determined using spectrophotometry and the leuco base, leucoberbelin blue.Talanta, 200
KL Casciotti (2016)
10.1098/20150295Philosl Trans A, 374
X. Zhu-Barker, A. Cavazos, N. Ostrom, W. Horwath, J. Glass (2015)
The importance of abiotic reactions for nitrous oxide productionBiogeochemistry, 126
C. Buchwald, K. Casciotti (2013)
Isotopic ratios of nitrite as tracers of the sources and age of oceanic nitriteNature Geoscience, 6
Martin Hoener, A. Bodi, P. Hemberger, T. Endres, T. Kasper (2020)
Threshold photoionization shows no sign of nitryl hydride in methane oxidation with nitric oxide.Physical chemistry chemical physics : PCCP
Robert Trouwborst, B. Clement, B. Tebo, B. Glazer, G. Luther (2006)
Soluble Mn(III) in Suboxic ZonesScience, 313
Julián and, M. Afonso (2003)
Mechanism of hydrogen sulfide oxidation by manganese(IV) oxide in aqueous solutionsLangmuir, 19
V. Oldham, M. Jones, B. Tebo, G. Luther (2017)
Oxidative and reductive processes contributing to manganese cycling at oxic-anoxic interfacesMarine Chemistry, 195
G. Luther, Bjørn Sundby, B. Lewis, P. Brendel, N. Silverberg (1997)
Interactions of manganese with the nitrogen cycle: Alternative pathways to dinitrogenGeochimica et Cosmochimica Acta, 61
E. Yakushev, F. Pollehne, G. Jost, I. Kuznetsov, B. Schneider, L. Umlauf (2007)
Analysis of the water column oxic/anoxic interface in the Black and Baltic seas with a numerical modelMarine Chemistry, 107
(2013)
Abundant Mn(III) in porewaters
J. Klewicki, J. Morgan (1998)
Kinetic Behavior of Mn(III) Complexes of Pyrophosphate, EDTA, and CitrateEnvironmental Science & Technology, 32
G. Luther, A. Chanvalon, V. Oldham, E. Estes, B. Tebo, A. Madison (2018)
Reduction of Manganese Oxides: Thermodynamic, Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer StepsAquatic Geochemistry, 24
(2017)
Oxidative and reductive processes contributing
C. Matocha, D. Sparks, J. Amonette, R. Kukkadapu (2001)
Kinetics and Mechanism of Birnessite Reduction by CatecholSoil Science Society of America Journal, 65
G. Luther, J. Popp (2002)
Kinetics of the Abiotic Reduction of Polymeric Manganese Dioxide by Nitrite: An Anaerobic Nitrification ReactionAquatic Geochemistry, 8
A. Stone, J. Morgan (1984)
Reduction and dissolution of manganese(III) and manganese(IV) oxides by organics: 2. Survey of the reactivity of organics.Environmental science & technology, 18 8
Hui Lin, M. Taillefert (2014)
Key geochemical factors regulating Mn(IV)-catalyzed anaerobic nitrification in coastal marine sedimentsGeochimica et Cosmochimica Acta, 133
W. Yao, Frank Millero (1995)
Oxidation of Hydrogen Sulfide by Mn(IV) and Fe(III) (Hydr)Oxides in Seawater
O. Dellwig, B. Schnetger, H. Brumsack, H. Grossart, L. Umlauf (2012)
Dissolved reactive manganese at pelagic redoxclines (part II): Hydrodynamic conditions for accumulationJournal of Marine Systems, 90
Shannon Owings, G. Luther, M. Taillefert (2019)
Development of a rate law for arsenite oxidation by manganese oxidesGeochimica et Cosmochimica Acta
G. Luther (2005)
Manganese(II) Oxidation and Mn(IV) Reduction in the Environment—Two One-Electron Transfer Steps Versus a Single Two-Electron StepGeomicrobiology Journal, 22
V. Oldham, Megan Miller, L. Jensen, G. Luther (2017)
Revisiting Mn and Fe removal in humic rich estuariesGeochimica et Cosmochimica Acta, 209
J. Watters, I. Kolthoff (1948)
Potentiometric Investigation of Tripyrophosphatomanganic (III) AcidJournal of the American Chemical Society, 70
Xiaofen Zhang, F. Bordwell (1993)
Homolytic Bond Dissociation Energies of the Benzylic C-H Bonds in Radical Anions and Radical Cations Derived from Fluorenes, Triphenylmethanes, and Related CompoundsChemInform, 24
G. Luther (2010)
The Role of One- and Two-Electron Transfer Reactions in Forming Thermodynamically Unstable Intermediates as Barriers in Multi-Electron Redox ReactionsAquatic Geochemistry, 16
J. Kostka, G. Luther, K. Nealson (1995)
CHEMICAL AND BIOLOGICAL REDUCTION OF MN (III)-PYROPHOSPHATE COMPLEXES : POTENTIAL IMPORTANCE OF DISSOLVED MN (III) AS AN ENVIRONMENTAL OXIDANTGeochimica et Cosmochimica Acta, 59
W. Yao, F. Millero (1993)
The rate of sulfide oxidation by δMnO2 in seawaterGeochimica et Cosmochimica Acta, 57
Xian‐Man Zhang, F. Bordwell (1992)
Homolytic bond dissociation energies of the benzylic carbon-hydrogen bonds in radical anions and radical cations derived from fluorenes, triphenylmethanes, and related compoundsJournal of the American Chemical Society, 114
A. Stone, J. Morgan (1984)
Reduction and dissolution of manganese(III) and manganese(IV) oxides by organics. 1. Reaction with hydroquinone.Environmental science & technology, 18 6
G. Luther (2004)
Kinetics of the Reactions of Water, Hydroxide Ion and Sulfide Species with CO2, OCS and CS2: Frontier Molecular Orbital ConsiderationsAquatic Geochemistry, 10
(2013)
Abundant Mn ( III ) in porewaters is a major component of the sedimentary redox system
(2017)
Soluble Mn(III)-L complexes are ubiquitous in oxygenated waters and stabilized by humic ligands
V. Oldham, A. Mucci, B. Tebo, G. Luther (2017)
Soluble Mn(III)–L complexes are abundant in oxygenated waters and stabilized by humic ligandsGeochimica et Cosmochimica Acta, 199
P. Anschutz, Bjørn Sundby, Lucie Lefrançois, G. Luther, A. Mucci (2000)
Interactions between metal oxides and species of nitrogen and iodine in bioturbated marine sedimentsGeochimica et Cosmochimica Acta, 64
R. Bach, A. Ayala, H. Schlegel (1996)
A REASSESSMENT OF THE BOND DISSOCIATION ENERGIES OF PEROXIDES. AN AB INITIO STUDYJournal of the American Chemical Society, 118
O. Dellwig, T. Leipe, C. März, M. Glockzin, F. Pollehne, B. Schnetger, E. Yakushev, M. Böttcher, H. Brumsack (2010)
A new particulate Mn–Fe–P-shuttle at the redoxcline of anoxic basinsGeochimica et Cosmochimica Acta, 74
(1984)
Reduction and dissolution of manganese (III) and manganese(IV) oxides byorganics
A. Cavazos, M. Taillefert, Yuanzhi Tang, J. Glass (2018)
Kinetics of nitrous oxide production from hydroxylamine oxidation by birnessite in seawaterMarine Chemistry, 202
Reduction and dissolution of manganese ( III ) and manganese ( IV ) oxides byorganics . 1
K. Casciotti (2016)
Nitrite isotopes as tracers of marine N cycle processesPhilosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 374
A. Madison, B. Tebo, A. Mucci, B. Sundby, G. Luther (2013)
Abundant Porewater Mn(III) Is a Major Component of the Sedimentary Redox SystemScience, 341
J. Karolewski, Kevin Sutherland, C. Hansel, S. Wankel (2021)
An isotopic study of abiotic nitrite oxidation by ligand-bound manganese (III)Geochimica et Cosmochimica Acta
G. Luther (2016)
Inorganic Chemistry for Geochemistry and Environmental Sciences: Fundamentals and Applications
K. Casciotti (2009)
Inverse kinetic isotope fractionation during bacterial nitrite oxidation.Geochimica et Cosmochimica Acta, 73
Ao Qian, W. Zhang, Chengming Shi, C. Pan, D. Giammar, S. Yuan, Hongliang Zhang, Zimeng Wang (2019)
Geochemical Stability of Dissolved Mn(III) in the Presence of Pyrophosphate as a Model Ligand: Complexation and Disproportionation.Environmental science & technology, 53 10
Jannis Heil, Shurong Liu, H. Vereecken, N. Brüggemann (2015)
Abiotic nitrous oxide production from hydroxylamine in soils and their dependence on soil propertiesSoil Biology & Biochemistry, 84
Shurong Liu, A. Berns, H. Vereecken, Di Wu, N. Brüggemann (2017)
Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixturesScientific Reports, 7
Matthew Siebecker, A. Madison, G. Luther (2015)
Reduction Kinetics of Polymeric (Soluble) Manganese (IV) Oxide (MnO2) by Ferrous Iron (Fe2+)Aquatic Geochemistry, 21
Given their environmental abundances, it has been long hypothesized that geochemical interactions between reactive forms of manganese and nitrogen may play important roles in the cycling of these elements. Indeed, recent studies have begun shedding light on the possible role of soluble, ligand-bound Mn(III) in promoting abiotic transformations under environmentally relevant conditions. Here, using the kinetic data of Karolewski et al. (Geochim Cosmochim Acta 293:365–378, 2021), we provide the chemical mechanism for the abiotic oxidation of nitrite (NO2−) by Mn(III)-pyrophosphate, MnIIIPP, to form nitrate (NO3−). Nitrous acid (HNO2), not NO2−, is the reductant in the reaction, based on thermodynamic and kinetic considerations. As soluble Mn(III) complexes react in a one-electron transfer reaction, two one-electron transfer steps must occur. In step one, HNO2 is first oxidized to nitrogen dioxide, ·NO2, a free radical via a hydrogen atom transfer (HAT) reaction. We show that this inner sphere reaction process is the rate-limiting step in the reaction sequence. In step two, ·NO2 reacts with a second MnIIIPP complex to form the nitronium ion (NO2+), which is isoelectronic with CO2. Unlike the poor electron-accepting capability of CO2, NO2+ is an excellent electron acceptor for both OH− and H2O, so NO2+ reacts quickly with water to form the end-product NO3− (step 3 in the reaction sequence). Thus, water provides the O atom in this nitrification reaction in accordance with the O-isotope data. This work provides mechanistic perspective on a potentially important interaction between Mn and nitrogen species, thereby offering a framework in which to interpret kinetic and isotopic data and to further investigate the relevance of this reaction under environmental conditions.
Aquatic Geochemistry – Springer Journals
Published: May 31, 2021
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