Effects of C/Mn Ratios on the Sorption and Oxidative Degradation of Small Organic Molecules on Mn-Oxides

Li, Hui; Reinhart, Benjamin; Moller, Spencer; Herndon, Elizabeth

doi:10.1021/acs.est.2c03633

Effects of C/Mn Ratios on the Sorption and Oxidative Degradation of Small Organic Molecules on Mn-Oxides

Journal Article · Mon Dec 19 04:00:00 EST 2022 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.2c03633· OSTI ID:1906561

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North Carolina State University, Raleigh, NC (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Argonne National Laboratory (ANL), Lemont, IL (United States)
University of Delaware, Newark, DE (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

We report manganese (Mn) oxides have a high surface area and redox potential that facilitate sorption and/or oxidation of organic carbon (OC), but their role in regulating soil C storage is relatively unexplored. Small OC compounds with distinct structures were reacted with Mn(III/IV)-oxides to investigate the effects of OC/Mn molar ratios on Mn–OC interaction mechanisms. Dissolved and solid-phase OC and Mn were measured to quantify the OC sorption to and/or the redox reaction with Mn-oxides. Mineral transformation was evaluated using X-ray diffraction and X-ray absorption spectroscopy. Higher OC/Mn ratios resulted in higher sorption and/or redox transformation; however, interaction mechanisms differed at low or high OC/Mn ratios for some OC. Citrate, pyruvate, ascorbate, and catechol induced Mn-oxide dissolution. The average oxidation state of Mn in the solid phase did not change during the reaction with citrate, suggesting ligand-promoted mineral dissolution, but decreased significantly during reactions with the other compounds, suggesting reductive dissolution mechanisms. Phthalate primarily sorbed on Mn-oxides with no detectable formation of redox products. Mn–OC interactions led primarily to C loss through OC oxidation into inorganic C, except phthalate, which was predominantly immobilized in the solid phase. Together, these results provided detailed fundamental insights into reactions happening at organo–mineral interfaces in soils.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Lemont, IL (United States)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; US Department of Agriculture (USDA)

Grant/Contract Number:: AC05-00OR22725; AC02-06CH11357

OSTI ID:: 1906561

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: xx Vol. xx; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

Importance of vegetation for manganese cycling in temperate forested watersheds: Biogeochemistry of Mn contaminants Herndon, Elizabeth M.; Jin, Lixin; Andrews, Danielle M. Global Biogeochemical Cycles, Vol. 29, Issue 2 https://doi.org/10.1002/2014gb004858	journal	February 2015
Determination of Plant-available Soil Manganese Reisenauer, H. M. Manganese in Soils and Plants https://doi.org/10.1007/978-94-009-2817-6_7	book	January 1988
Reduction of Manganese Oxides: Thermodynamic, Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer Steps Luther, George W.; Thibault de Chanvalon, Aubin; Oldham, Véronique E. Aquatic Geochemistry, Vol. 24, Issue 4 https://doi.org/10.1007/s10498-018-9342-1	journal	July 2018
Removal mechanism of di-n-butyl phthalate and oxytetracycline from aqueous solutions by nano-manganese dioxide modified biochar Gao, Minling; Zhang, Yue; Gong, Xiaolei Environmental Science and Pollution Research, Vol. 25, Issue 8 https://doi.org/10.1007/s11356-017-1089-5	journal	December 2017
Sorption of heavy metal ions by a hydrous manganese oxide Loganathan, P.; Burau, R. G. Geochimica et Cosmochimica Acta, Vol. 37, Issue 5 https://doi.org/10.1016/0016-7037(73)90061-6	journal	May 1973
Mineral–Organic Associations: Formation, Properties, and Relevance in Soil Environments Kleber, Markus; Eusterhues, Karin; Keiluweit, Marco https://doi.org/10.1016/bs.agron.2014.10.005	book	December 2014
Effects of Co and Ni co-doping on the structure and reactivity of hexagonal birnessite Yin, Hui; Li, Hui; Wang, Yan Chemical Geology, Vol. 381 https://doi.org/10.1016/j.chemgeo.2014.05.017	journal	August 2014
Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals Feng, Xiong Han; Zhai, Li Mei; Tan, Wen Feng Environmental Pollution, Vol. 147, Issue 2 https://doi.org/10.1016/j.envpol.2006.05.028	journal	May 2007
Reaction of MnIII,IV (hydr)oxides with oxalic acid, glyoxylic acid, phosphonoformic acid, and structurally-related organic compounds Wang, Yun; Stone, Alan T. Geochimica et Cosmochimica Acta, Vol. 70, Issue 17 https://doi.org/10.1016/j.gca.2006.06.1548	journal	September 2006
The citric acid–MnIII,IVO2(birnessite) reaction. Electron transfer, complex formation, and autocatalytic feedback Wang, Yun; Stone, Alan T. Geochimica et Cosmochimica Acta, Vol. 70, Issue 17 https://doi.org/10.1016/j.gca.2006.06.1551	journal	September 2006
Reductive transformations of layered manganese oxides by small organic acids and the fate of trace metals Flynn, Elaine D.; Catalano, Jeffrey G. Geochimica et Cosmochimica Acta, Vol. 250 https://doi.org/10.1016/j.gca.2019.02.006	journal	April 2019
Recent weathering promotes C storage inside large phyllosilicate particles in forest soil Van Der Kellen, Ingride; Derrien, Delphine; Ghanbaja, Jaafar Geochimica et Cosmochimica Acta, Vol. 318 https://doi.org/10.1016/j.gca.2021.12.009	journal	February 2022
Mapping soil organic matter concentration at different scales using a mixed geographically weighted regression method Zeng, Canying; Yang, Lin; Zhu, A-Xing Geoderma, Vol. 281 https://doi.org/10.1016/j.geoderma.2016.06.033	journal	November 2016
Kinetics of the reduction of water-soluble colloidal MnO2 by ascorbic acid Khan, Zaheer; Kumar, Parveen Journal of Colloid and Interface Science, Vol. 290, Issue 1 https://doi.org/10.1016/j.jcis.2005.04.040	journal	October 2005
The impact of particle size on the adsorption of citrate to hematite Noerpel, Matthew R.; Lenhart, John J. Journal of Colloid and Interface Science, Vol. 460 https://doi.org/10.1016/j.jcis.2015.08.028	journal	December 2015
Structure and properties of Co-doped cryptomelane and its enhanced removal of Pb 2+ and Cr 3+ from wastewater Li, Hui; Liu, Fan; Zhu, Mengqiang Journal of Environmental Sciences, Vol. 34 https://doi.org/10.1016/j.jes.2015.02.006	journal	August 2015
Abiotic oxidation of catechol by soil metal oxides Colarieti, Maria Letizia; Toscano, Giuseppe; Ardi, Maria Raffaella Journal of Hazardous Materials, Vol. 134, Issue 1-3 https://doi.org/10.1016/j.jhazmat.2005.10.054	journal	June 2006
Adsorption and removal of phthalic acid and diethyl phthalate from water with zeolitic imidazolate and metal–organic frameworks Khan, Nazmul Abedin; Jung, Beom K.; Hasan, Zubair Journal of Hazardous Materials, Vol. 282 https://doi.org/10.1016/j.jhazmat.2014.03.047	journal	January 2015
Determination of phosphate in soil extracts in the field: A green chemistry enzymatic method Campbell, Ellen R.; Warsko, Kayla; Davidson, Anna-Marie MethodsX, Vol. 2 https://doi.org/10.1016/j.mex.2015.04.003	journal	January 2015
Reaction of forest floor organic matter at goethite, birnessite and smectite surfaces Chorover, Jon; Amistadi, Mary Kay Geochimica et Cosmochimica Acta, Vol. 65, Issue 1 https://doi.org/10.1016/s0016-7037(00)00511-1	journal	January 2001
Dissolution of β-MnOOH particles by ligands: pyrophosphate, ethylenediaminetetraacetate, and citrate Klewicki, J. K.; Morgan, J. J. Geochimica et Cosmochimica Acta, Vol. 63, Issue 19-20 https://doi.org/10.1016/s0016-7037(99)00229-x	journal	October 1999
Enzymes, Manganese, or Iron? Drivers of Oxidative Organic Matter Decomposition in Soils Jones, Morris E.; LaCroix, Rachelle E.; Zeigler, Jacob Environmental Science & Technology, Vol. 54, Issue 21 https://doi.org/10.1021/acs.est.0c04212	journal	October 2020
Simple Plant and Microbial Exudates Destabilize Mineral-Associated Organic Matter via Multiple Pathways Li, Hui; Bölscher, Tobias; Winnick, Matthew Environmental Science & Technology, Vol. 55, Issue 5 https://doi.org/10.1021/acs.est.0c04592	journal	February 2021
A Critical Review on the Multiple Roles of Manganese in Stabilizing and Destabilizing Soil Organic Matter Li, Hui; Santos, Fernanda; Butler, Kristen Environmental Science & Technology, Vol. 55, Issue 18 https://doi.org/10.1021/acs.est.1c00299	journal	September 2021
Selective Reactivity and Oxidation of Dissolved Organic Matter by Manganese Oxides Trainer, Emma L.; Ginder-Vogel, Matthew; Remucal, Christina K. Environmental Science & Technology, Vol. 55, Issue 17 https://doi.org/10.1021/acs.est.1c03972	journal	August 2021
Molecular Composition and Photochemical Reactivity of Size-Fractionated Dissolved Organic Matter Maizel, Andrew C.; Remucal, Christina K. Environmental Science & Technology, Vol. 51, Issue 4 https://doi.org/10.1021/acs.est.6b05140	journal	February 2017
Structural Transformation of Birnessite by Fulvic Acid under Anoxic Conditions Wang, Qian; Yang, Peng; Zhu, Mengqiang Environmental Science & Technology, Vol. 52, Issue 4 https://doi.org/10.1021/acs.est.7b04379	journal	January 2018
The Role of Dissolved Organic Matter Composition in Determining Photochemical Reactivity at the Molecular Level Berg, Stephanie M.; Whiting, Quinn T.; Herrli, Joseph A. Environmental Science & Technology, Vol. 53, Issue 20 https://doi.org/10.1021/acs.est.9b03007	journal	September 2019
Synthesis of Birnessite in the Presence of Phosphate, Silicate, or Sulfate Wang, Qian; Liao, Xianya; Xu, Wenqian Inorganic Chemistry, Vol. 55, Issue 20 https://doi.org/10.1021/acs.inorgchem.6b01465	journal	September 2016
Degradation and Isotope Source Tracking of Glyphosate and Aminomethylphosphonic Acid Li, Hui; Joshi, Sunendra R.; Jaisi, Deb P. Journal of Agricultural and Food Chemistry, Vol. 64, Issue 3 https://doi.org/10.1021/acs.jafc.5b04838	journal	January 2016
Reduction and dissolution of manganese(III) and manganese(IV) oxides by organics. 1. Reaction with hydroquinone Stone, Alan T.; Morgan, James J. Environmental Science & Technology, Vol. 18, Issue 6 https://doi.org/10.1021/es00124a011	journal	June 1984
Reduction and dissolution of manganese(III) and manganese(IV) oxides by organics: 2. Survey of the reactivity of organics Stone, Alan T.; Morgan, James J. Environmental Science & Technology, Vol. 18, Issue 8 https://doi.org/10.1021/es00126a010	journal	August 1984
Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide. 2. Results from X-ray Absorption Spectroscopy and X-ray Diffraction Lafferty, Brandon J.; Ginder-Vogel, Matthew; Zhu, Mengqiang Environmental Science & Technology, Vol. 44, Issue 22 https://doi.org/10.1021/es102016c	journal	November 2010
Reductive Dissolution of Manganese(III/Iv) Oxides by Substituted Phenols Stone, Alan T. Environmental Science & Technology, Vol. 21, Issue 10 https://doi.org/10.1021/es50001a011	journal	October 1987
Surface Complexation of Catechol to Metal Oxides: An ATR-FTIR, Adsorption, and Dissolution Study Gulley-Stahl, Heather; Hogan, Patrick A.; Schmidt, Whitney L. Environmental Science & Technology, Vol. 44, Issue 11 https://doi.org/10.1021/es902040u	journal	April 2010
Kinetics of MnO₂-Catalyzed Acetic Acid Oxidation in Supercritical Water Yu, Jianli; Savage, Phillip E. Industrial & Engineering Chemistry Research, Vol. 39, Issue 11 https://doi.org/10.1021/ie000583l	journal	September 2000
Role of Mn(IV) oxide in abiotic formation of humic substances in the environment Shindo, H.; Huang, P. M. Nature, Vol. 298, Issue 5872 https://doi.org/10.1038/298363a0	journal	July 1982
The contentious nature of soil organic matter Lehmann, Johannes; Kleber, Markus Nature, Vol. 528, Issue 7580 https://doi.org/10.1038/nature16069	journal	November 2015
Mineral protection of soil carbon counteracted by root exudates Keiluweit, Marco; Bougoure, Jeremy J.; Nico, Peter S. Nature Climate Change, Vol. 5, Issue 6 https://doi.org/10.1038/nclimate2580	journal	March 2015
Oxalate production via oxidation of ascorbate rather than reduction of carbon dioxide Khamespanah, Fatemeh; Marx, Maximilian; Crochet, David B. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21817-w	journal	March 2021
Ascorbate oxidation by iron, copper and reactive oxygen species: review, model development, and derivation of key rate constants Shen, Jiaqi; Griffiths, Paul T.; Campbell, Steven J. Scientific Reports, Vol. 11, Issue 1 https://doi.org/10.1038/s41598-021-86477-8	journal	April 2021
Mandelic acid and phenyllactic acid “Reaction Sets” for exploring the kinetics and mechanism of oxidations by hydrous manganese oxide (HMO) Xia, Xiaomeng; Stone, Alan T. Environmental Science: Processes & Impacts, Vol. 21, Issue 6 https://doi.org/10.1039/c9em00128j	journal	January 2019
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
A NanoSIMS study on the distribution of soil organic matter, iron and manganese in a nodule from a Stagnosol: Distribution of SOM, Fe and Mn studied by NanoSIMS Rennert, T.; Händel, M.; Höschen, C. European Journal of Soil Science, Vol. 65, Issue 5 https://doi.org/10.1111/ejss.12157	journal	June 2014
Biogenic manganese oxides as reservoirs of organic carbon and proteins in terrestrial and marine environments Estes, E. R.; Andeer, P. F.; Nordlund, D. Geobiology, Vol. 15, Issue 1 https://doi.org/10.1111/gbi.12195	journal	July 2016
Stabilization of organic matter in temperate soils: mechanisms and their relevance under different soil conditions - a review Lutzow, M. v.; Kogel-Knabner, I.; Ekschmitt, K. European Journal of Soil Science, Vol. 57, Issue 4 https://doi.org/10.1111/j.1365-2389.2006.00809.x	journal	August 2006
Photooxidation and Reduction of Ascorbic Acid Studied by E.S.R. McAlpine, Robert D.; Cocivera, Michael; Chen, Holger Canadian Journal of Chemistry, Vol. 51, Issue 11 https://doi.org/10.1139/v73-252	journal	June 1973
Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter Stuckey, Jason W.; Goodwin, Christopher; Wang, Jian Geochemical Transactions, Vol. 19, Issue 1 https://doi.org/10.1186/s12932-018-0051-x	journal	February 2018
Structural controls on the catalytic polymerization of hydroquinone by birnessites Liu, Ming-Ming; Cao, Xing-Hui; Tan, Wen-Feng Clays and Clay Minerals, Vol. 59, Issue 5 https://doi.org/10.1346/CCMN.2011.0590510	journal	October 2011
Oxidation of Dihydroxybenzenes in Aerated Aqueous Suspensions of Birnessite McBride, M. B. Clays and Clay Minerals, Vol. 37, Issue 4 https://doi.org/10.1346/ccmn.1989.0370407	journal	January 1989
Oxidation of 1,2- and 1,4-Dihydroxybenzene by Birnessite in Acidic Aqueous Suspension McBride, M. B. Clays and Clay Minerals, Vol. 37, Issue 5 https://doi.org/10.1346/ccmn.1989.0370514	journal	January 1989
Synthesis of Birnessite from the Oxidation of Mn²⁺ by O₂ in Alkali Medium: Effects of Synthesis Conditions Feng, Xiong Han; Liu, Fan; Tan, Wen Feng Clays and Clay Minerals, Vol. 52, Issue 2 https://doi.org/10.1346/ccmn.2004.0520210	journal	April 2004
Evolution of CO ₂ during Birnessite-Induced Oxidation of ¹⁴ C-Labeled Catechol Majcher, Emily H.; Chorover, Jon; Bollag, Jean-Marc Soil Science Society of America Journal, Vol. 64, Issue 1 https://doi.org/10.2136/sssaj2000.641157x	journal	January 2000
Manganiferous Soils in Maryland: Regional Extent and Field-Scale Electromagnetic Induction Survey Bourgault, Rebecca R.; Rabenhorst, Martin C. Soil Science Society of America Journal, Vol. 76, Issue 6 https://doi.org/10.2136/sssaj2012.0091	journal	October 2012
An Isotope Labeling Technique to Investigate Atom Exchange during Phosphate Sorption and Desorption Li, Hui; Jaisi, Deb P. Soil Science Society of America Journal, Vol. 79, Issue 5 https://doi.org/10.2136/sssaj2015.04.0158	journal	September 2015
Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy Manceau, A.; Marcus, M. A.; Grangeon, S. American Mineralogist, Vol. 97, Issue 5-6 https://doi.org/10.2138/am.2012.3903	journal	May 2012
Root Exudation of Primary Metabolites: Mechanisms and Their Roles in Plant Responses to Environmental Stimuli Canarini, Alberto; Kaiser, Christina; Merchant, Andrew Frontiers in Plant Science, Vol. 10 https://doi.org/10.3389/fpls.2019.00157	journal	February 2019

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