Manganese Oxidation States in Volcanic Soils across Annual Rainfall Gradients

Wen, Ke; Chadwick, Oliver A.; Vitousek, Peter M.; Paulus, Elizabeth L.; Landrot, Gautier; Tappero, Ryan V.; Kaszuba, John P.; Luther, George W.; Wang, Zimeng; Reinhart, Benjamin J.; Zhu, Mengqiang

doi:10.1021/acs.est.2c02658

Manganese Oxidation States in Volcanic Soils across Annual Rainfall Gradients

Journal Article · Mon Dec 19 23:00:00 EST 2022 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.2c02658· OSTI ID:1961775

^[1]; Chadwick, Oliver A. ^[2]; Vitousek, Peter M. ^[3]; Paulus, Elizabeth L. ^[3]; ^[4]; Tappero, Ryan V. ^[5]; ^[1]; Luther, George W. ^[6]; ^[7]; ^[8]; ^[1]

University of Wyoming, Laramie, WY (United States)
University of California, Santa Barbara, CA (United States)
Stanford University, CA (United States)
Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin (France)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
University of Delaware, Newark, DE (United States)
Fudan University, Shanghai (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Manganese (Mn) exists as Mn(II), Mn(III), or Mn(IV) in soils, and the Mn oxidation state controls the roles of Mn in numerous environmental processes. However, the variations of Mn oxidation states with climate remain unknown. Here we determined the Mn oxidation states in highly weathered bulk volcanic soils (primary minerals free) across two rainfall gradients covering mean annual precipitation (MAP) of 0.25–5 m in the Hawaiian Islands. With increasing MAP, the soil redox conditions generally shifted from oxic to suboxic and to anoxic despite fluctuating at each site; concurrently, the proportions of Mn(IV) and Mn(II) decreased and increased, respectively. Mn(III) was low at both low and high MAP, but accumulated substantially, up to 80% of total Mn, in soils with prevalent suboxic conditions at intermediate MAP. Mn(III) was likely hosted in Mn(III,IV) and iron(III) oxides or complexed with organic matter, and its distribution among these hosts varied with soil redox potentials and soil pH. Soil redox conditions and rainfall-driven leaching jointly controlled exchangeable Mn(II) in soils, with its concentration peaking at intermediate MAP. The Mn redox chemistry was at disequilibrium, with the oxidation states correlating with long-term average soil redox potentials better than with soil pH. The soil redox conditions likely fluctuated between oxic and anoxic conditions more frequently at intermediate than at low and high MAP, creating biogeochemical hot spots where Mn, Fe, and other redox-sensitive elements may be actively cycled.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; AC02-76SF00515; AC02-06CH11357

OSTI ID:: 1961775

Report Number(s):: BNL-224116-2023-JAAM

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 1 Vol. 57; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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