Chemical composition, coordination, and stability of Ca–organic associations in the presence of dissolving calcite

Qafoku, Odeta; Battu, Anil Krishna; Varga, Tamas; Marcus, Matthew A.; O'Callahan, Brian T.; Zhao, Qian; Mergelsberg, Sebastian T.; Kew, William R.; Loring, John S.; Qafoku, Nikolla P.; Leichty, Sarah I.

doi:10.1039/d2en01143c

Title: Chemical composition, coordination, and stability of Ca–organic associations in the presence of dissolving calcite

Journal Article · 02 May 2023 · Environmental Science: Nano

DOI: https://doi.org/10.1039/d2en01143c · OSTI ID:1984028

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)

Environmental biotic and abiotic factors and soil physical, mineralogical, and chemical properties control the chemical composition of soil organic matter (SOM). Particularly, soil mineralogy and the presence of multivalent cations affect SOM labile fraction composition, stability, and environmental persistence. The persistence of SOM in aridic or limestone deposit derived soils, i.e., calcareous soils, has been partially attributed to SOM stabilization through adsorption or inclusion into the calcite mineral structure. Recently, however, it was shown that Ca(aq) released during calcite dissolution formed aqueous Ca–organic associations with OM components, which were unbound to mineral surface sites. This study investigates the structure, composition, and coordination of these associations by characterizing lyophilized Ca–organic containing solutions with spectromicroscopy [Scanning Transmission X-ray Microscopy (STXM)] and with a nanoimaging chemical probe [Infrared scattering-Scanning Nearfield Optical Microscopy (IR s-SNOM)]. Chemical stability of Ca–organic associations is furthermore determined with pyrolysis mass spectrometry analysis. The results demonstrate that Ca–organic associations are formed in the presence of dissolving calcite and OM components relevant to soil chemistry, i.e., lignin and amino acids. This study further reveals a spatial homogeneity of solution-derived (bi) carbonate in Ca–organic associations indicating for the first time that an inorganic anion, such as (bi)carbonate, may be part of these associations. Most likely, Ca ions are bound to both the (bi)carbonate and the organic components. These Ca (bi)carbonate–organic associations seem to have greater chemical stability than the pristine organic mixtures and, possibly, a higher environmental stability and reduced mineralization rate.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Award DOI(s):: https://doi.org/10.46936/intm.proj.2020.51672/60000251
Awarding Organization: USDOE

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231

OSTI ID:: 1984028

Report Number(s):: PNNL-SA-181173

Journal Information:: Environmental Science: Nano, Vol. 10, Issue 5; ISSN 2051-8153

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Chemical composition, coordination, and stability of Ca–organic associations in the presence of dissolving calcite

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