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

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

Journal Article · Tue May 02 04:00:00 EDT 2023 · Environmental Science: Nano

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

^[1]; ^[1]; ^[1]; Marcus, Matthew A. ^[2]; O'Callahan, Brian T. ^[1]; ^[1]; ^[3]; ^[1]; ^[3]; ^[4]; Leichty, Sarah I. ^[1]

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.

View Accepted Manuscript (DOE)

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); USDOE

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

OSTI ID:: 1984028

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

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

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (61)

Synchrotron-Based Near-Edge X-Ray Spectroscopy of Natural Organic Matter in Soils and Sediments Lehmann, J.; Solomon, D.; Brandes, J. Biophysico‐Chemical Processes Involving Natural Nonliving Organic Matter in Environmental Systems https://doi.org/10.1002/9780470494950.ch17	book	July 2009
The retention of organic matter in soils Oades, J. M. Biogeochemistry, Vol. 5, Issue 1 https://doi.org/10.1007/BF02180317	journal	February 1988
Calcium-mediated stabilisation of soil organic carbon Rowley, Mike C.; Grand, Stéphanie; Verrecchia, Éric P. Biogeochemistry, Vol. 137, Issue 1-2 https://doi.org/10.1007/s10533-017-0410-1	journal	December 2017
Dynamics of organic matter in soils of temperate regions: Its action on pedogenesis Duchaufour, P. Geoderma, Vol. 15, Issue 1 https://doi.org/10.1016/0016-7061(76)90068-9	journal	January 1976
Residual effects of additions of calcium compounds on soil structure and strength Grant, C. Soil and Tillage Research, Vol. 22, Issue 3-4 https://doi.org/10.1016/0167-1987(92)90044-C	journal	January 1992
Role of the soil matrix and minerals in protecting natural organic materials against biological attack Baldock, J. A.; Skjemstad, J. O. Organic Geochemistry, Vol. 31, Issue 7-8 https://doi.org/10.1016/S0146-6380(00)00049-8	journal	July 2000
Characterization of Ca-phosphate biological materials by scanning transmission X-ray microscopy (STXM) at the Ca L2,3-, P L2,3- and C K-edges Cosmidis, Julie; Benzerara, Karim; Nassif, Nadine Acta Biomaterialia, Vol. 12 https://doi.org/10.1016/j.actbio.2014.10.003	journal	January 2015
Spontaneous aggregation of humic acid observed with AFM at different pH Colombo, Claudio; Palumbo, Giuseppe; Angelico, Ruggero Chemosphere, Vol. 138 https://doi.org/10.1016/j.chemosphere.2015.08.010	journal	November 2015
Near edge X-ray absorption fine structure (NEXAFS) of model compounds for the humic acid/actinide ion interaction Plaschke, Markus; Rothe, Jörg; Altmaier, Marcus Journal of Electron Spectroscopy and Related Phenomena, Vol. 148, Issue 3 https://doi.org/10.1016/j.elspec.2005.05.001	journal	September 2005
Optimization of analysis of soft X-ray spectromicroscopy at the Ca 2p edge Hanhan, S.; Smith, A. M.; Obst, M. Journal of Electron Spectroscopy and Related Phenomena, Vol. 173, Issue 1 https://doi.org/10.1016/j.elspec.2009.04.010	journal	June 2009
Data analysis in spectroscopic STXM Marcus, Matthew A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 264 https://doi.org/10.1016/j.elspec.2023.147310	journal	April 2023
Molecular simulation of humic substance–Ca-montmorillonite complexes Sutton, Rebecca; Sposito, Garrison Geochimica et Cosmochimica Acta, Vol. 70, Issue 14 https://doi.org/10.1016/j.gca.2006.04.032	journal	July 2006
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
Initial soil aggregate formation and stabilisation in soils developed from calcareous loess Pihlap, Evelin; Steffens, Markus; Kögel-Knabner, Ingrid Geoderma, Vol. 385 https://doi.org/10.1016/j.geoderma.2020.114854	journal	March 2021
Interaction between humic acid and montmorillonite in the presence of calcium ions II. Colloidal interactions: Charge state, dispersing and/or aggregation of particles in suspension Majzik, Andrea; Tombácz, Etelka Organic Geochemistry, Vol. 38, Issue 8 https://doi.org/10.1016/j.orggeochem.2007.04.002	journal	August 2007
Synchrotron infrared nano-spectroscopy and -imaging Bechtel, Hans A.; Johnson, Samuel C.; Khatib, Omar Surface Science Reports, Vol. 75, Issue 3 https://doi.org/10.1016/j.surfrep.2020.100493	journal	August 2020
Natural organic matter-cations complexation and its impact on water treatment: A critical review Adusei-Gyamfi, Junias; Ouddane, Baghdad; Rietveld, Luuk Water Research, Vol. 160 https://doi.org/10.1016/j.watres.2019.05.064	journal	September 2019
Automated Chemical Analysis of Internally Mixed Aerosol Particles Using X-ray Spectromicroscopy at the Carbon K-Edge ^† Moffet, Ryan C.; Henn, Tobias; Laskin, Alexander Analytical Chemistry, Vol. 82, Issue 19 https://doi.org/10.1021/ac1012909	journal	October 2010
Moving beyond the van Krevelen Diagram: A New Stoichiometric Approach for Compound Classification in Organisms Rivas-Ubach, Albert; Liu, Yina; Bianchi, Thomas S. Analytical Chemistry, Vol. 90, Issue 10 https://doi.org/10.1021/acs.analchem.8b00529	journal	April 2018
Crystal Structure, Polymorphism, and Anisotropic Thermal Expansion of α-Ca(CH₃COO)₂ Bette, Sebastian; Eggert, Gerhard; Emmerling, Sebastian Crystal Growth & Design, Vol. 20, Issue 8 https://doi.org/10.1021/acs.cgd.0c00563	journal	June 2020
Ab Initio Molecular Dynamics Simulations of Amorphous Calcium Carbonate: Interpretation of Pair Distribution Function and X-ray Absorption Spectroscopy Data Prange, Micah P.; Mergelsberg, Sebastian T.; Kerisit, Sebastien N. Crystal Growth & Design, Vol. 21, Issue 4 https://doi.org/10.1021/acs.cgd.0c01655	journal	March 2021
Nanometer-Resolved Spectroscopic Study Reveals the Conversion Mechanism of CaO·Al ₂ O ₃ ·10H ₂ O to 2CaO·Al ₂ O ₃ ·8H ₂ O and 3CaO·Al ₂ O ₃ ·6H ₂ O at an Elevated Temperature Geng, Guoqing; Li, Jiaqi; Yu, Young-Sang Crystal Growth & Design, Vol. 17, Issue 8 https://doi.org/10.1021/acs.cgd.7b00553	journal	June 2017
Molecular Dynamics Simulation of the Structures, Dynamics, and Aggregation of Dissolved Organic Matter Devarajan, Deepa; Liang, Liyuan; Gu, Baohua Environmental Science & Technology, Vol. 54, Issue 21 https://doi.org/10.1021/acs.est.0c01176	journal	September 2020
Spatial Associations and Chemical Composition of Organic Carbon Sequestered in Fe, Ca, and Organic Carbon Ternary Systems Sowers, Tyler D.; Adhikari, Dinesh; Wang, Jian Environmental Science & Technology, Vol. 52, Issue 12 https://doi.org/10.1021/acs.est.8b01158	journal	May 2018
Direct Observations of the Occlusion of Soil Organic Matter within Calcite Chi, Jialin; Zhang, Wenjun; Wang, Lijun Environmental Science & Technology, Vol. 53, Issue 14 https://doi.org/10.1021/acs.est.8b06807	journal	June 2019
Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F. Environmental Science & Technology Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acs.estlett.6b00460	journal	December 2016
A Mechanistic Exploration of Natural Organic Matter Aggregation and Surface Complexation in Smectite Mesopores Loganathan, Narasimhan; Ferguson, Brennan O.; Arey, Bruce The Journal of Physical Chemistry A, Vol. 124, Issue 47 https://doi.org/10.1021/acs.jpca.0c08244	journal	November 2020
Structural Role and Spatial Distribution of Carbonate Ions in Amorphous Calcium Phosphate Yasar, Ozlen F.; Liao, Wei-Chih; Stevensson, Baltzar The Journal of Physical Chemistry C, Vol. 125, Issue 8 https://doi.org/10.1021/acs.jpcc.0c10355	journal	February 2021
Integrated Molecular and Microscopic Scale Insight into Morphology and Ion Dynamics in Ca ²⁺ -Mediated Natural Organic Matter Floccs Bowers, Geoffrey M.; Argersinger, Haley E.; Reddy, U. Venkataswara The Journal of Physical Chemistry C, Vol. 119, Issue 31 https://doi.org/10.1021/acs.jpcc.5b05509	journal	July 2015
Imaging Nanoscale Heterogeneity in Ultrathin Biomimetic and Biological Crystals O’Callahan, Brian T.; Crampton, Kevin T.; Novikova, Irina V. The Journal of Physical Chemistry C, Vol. 122, Issue 43 https://doi.org/10.1021/acs.jpcc.8b06681	journal	September 2018
Attenuated Total Reflection-Fourier Transform Infrared and Atomic Force Microscopy-Infrared Spectroscopic Investigation of Suwannee River Fulvic Acid and Its Interactions with α-FeOOH Kim, Deborah; Grassian, Vicki H. ACS Earth and Space Chemistry, Vol. 6, Issue 1 https://doi.org/10.1021/acsearthspacechem.1c00288	journal	December 2021
Selective Interactions of Soil Organic Matter Compounds with Calcite and the Role of Aqueous Ca Qafoku, Odeta; Andersen, Amity; Kew, William R. ACS Earth and Space Chemistry, Vol. 6, Issue 7 https://doi.org/10.1021/acsearthspacechem.2c00016	journal	June 2022
Unraveling the Structural Components of Soil Humin by Use of Solution-State Nuclear Magnetic Resonance Spectroscopy Simpson, Andre J.; Song, Guixue; Smith, Emma Environmental Science & Technology, Vol. 41, Issue 3 https://doi.org/10.1021/es061576c	journal	December 2006
Soft X-ray Spectromicroscopy Study of Mineral-Organic Matter Associations in Pasture Soil Clay Fractions Chen, Chunmei; Dynes, James J.; Wang, Jian Environmental Science & Technology, Vol. 48, Issue 12 https://doi.org/10.1021/es405485a	journal	May 2014
Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand Inorganic Chemistry, Vol. 54, Issue 4 https://doi.org/10.1021/ic501991e	journal	December 2014
Nanoscale Transforming Mineral Phases in Fresh Nacre DeVol, Ross T.; Sun, Chang-Yu; Marcus, Matthew A. Journal of the American Chemical Society, Vol. 137, Issue 41 https://doi.org/10.1021/jacs.5b07931	journal	October 2015
X-ray Linear Dichroism in Apatite Stifler, Cayla A.; Wittig, Nina Kølln; Sassi, Michel Journal of the American Chemical Society, Vol. 140, Issue 37 https://doi.org/10.1021/jacs.8b05547	journal	September 2018
Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals DeVol, Ross T.; Metzler, Rebecca A.; Kabalah-Amitai, Lee The Journal of Physical Chemistry B, Vol. 118, Issue 28 https://doi.org/10.1021/jp503700g	journal	May 2014
Metal Cation Complexation with Natural Organic Matter in Aqueous Solutions: Molecular Dynamics Simulations and Potentials of Mean Force Iskrenova-Tchoukova, Eugenia; Kalinichev, Andrey G.; Kirkpatrick, R. James Langmuir, Vol. 26, Issue 20 https://doi.org/10.1021/la102535n	journal	October 2010
Persistence of soil organic matter as an ecosystem property Schmidt, Michael W. I.; Torn, Margaret S.; Abiven, Samuel Nature, Vol. 478, Issue 7367 https://doi.org/10.1038/nature10386	journal	October 2011
Dynamic interactions at the mineral–organic matter interface Kleber, Markus; Bourg, Ian C.; Coward, Elizabeth K. Nature Reviews Earth & Environment, Vol. 2, Issue 6 https://doi.org/10.1038/s43017-021-00162-y	journal	May 2021
Non-negative matrix analysis for effective feature extraction in X-ray spectromicroscopy Mak, Rachel; Lerotic, Mirna; Fleckenstein, Holger Faraday Discuss., Vol. 171 https://doi.org/10.1039/C4FD00023D	journal	January 2014
Probing calcium solvation by XAS, MD and DFT calculations Yang, Feipeng; Liu, Yi-Sheng; Feng, Xuefei RSC Advances, Vol. 10, Issue 46 https://doi.org/10.1039/D0RA05905F	journal	January 2020
The role of Ca-organic interactions in soil aggregate stability .I. Laboratory studies with glucose 14C, CaCO3 and CaSO4.2.H2O Muneer, M.; Oades, Jm Soil Research, Vol. 27, Issue 2 https://doi.org/10.1071/SR9890389	journal	January 1989
The role of Ca-organic interactions in soil aggregate stability .II. Field studies with 14C-labeled straw, CaCO3 and CaSO4.2.H2O Muneer, M.; Oades, Jm Soil Research, Vol. 27, Issue 2 https://doi.org/10.1071/SR9890401	journal	January 1989
Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule Politi, Y.; Metzler, R. A.; Abrecht, M. Proceedings of the National Academy of Sciences, Vol. 105, Issue 45 https://doi.org/10.1073/pnas.0806604105	journal	November 2008
Calcium L -edge XANES study of some calcium compounds Naftel, S. J.; Sham, T. K.; Yiu, Y. M. Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500019555	journal	March 2001
A new bend-magnet beamline for scanning transmission X-ray microscopy at the Advanced Light Source Warwick, Tony; Ade, Harald; Kilcoyne, David Journal of Synchrotron Radiation, Vol. 9, Issue 4 https://doi.org/10.1107/S0909049502005502	journal	June 2002
Interferometer-controlled scanning transmission X-ray microscopes at the Advanced Light Source Kilcoyne, A. L. D.; Tyliszczak, T.; Steele, W. F. Journal of Synchrotron Radiation, Vol. 10, Issue 2 https://doi.org/10.1107/S0909049502017739	journal	February 2003
Humic acid metal cation interaction studied by spectromicroscopy techniques in combination with quantum chemical calculations Plaschke, M.; Rothe, J.; Armbruster, M. K. Journal of Synchrotron Radiation, Vol. 17, Issue 2 https://doi.org/10.1107/S0909049509048742	journal	February 2010
Carbon K -edge spectra of carbonate minerals Brandes, Jay A.; Wirick, Sue; Jacobsen, Chris Journal of Synchrotron Radiation, Vol. 17, Issue 5 https://doi.org/10.1107/S0909049510020029	journal	July 2010
Molecular dynamics simulation of cationic complexation with natural organic matter Kalinichev, A. G.; Kirkpatrick, R. J. European Journal of Soil Science, Vol. 58, Issue 4 https://doi.org/10.1111/j.1365-2389.2007.00929.x	journal	August 2007
Scanning transmission X-ray microscopy study of microbial calcification Benzerara, K.; Yoon, T. H.; Tyliszczak, T. Geobiology, Vol. 2, Issue 4 https://doi.org/10.1111/j.1472-4677.2004.00039.x	journal	October 2004
Quantitative organic and light-element analysis of comet 81P/Wild 2 particles using C-, N-, and O-μ-XANES Cody, George D.; Ade, Harald; Alexander, M. O'D. Meteoritics & Planetary Science, Vol. 43, Issue 1-2 https://doi.org/10.1111/j.1945-5100.2008.tb00627.x	journal	February 2008
Infrared vibrational nanocrystallography and nanoimaging Muller, Eric A.; Pollard, Benjamin; Bechtel, Hans A. Science Advances, Vol. 2, Issue 10 https://doi.org/10.1126/sciadv.1601006	journal	October 2016
Imaging of Humic Substance Macromolecular Structures in Water and Soils Myneni, S. C. Science, Vol. 286, Issue 5443 https://doi.org/10.1126/science.286.5443.1335	journal	November 1999
The synergistic effect of calcium on organic carbon sequestration to ferrihydrite Sowers, Tyler D.; Stuckey, Jason W.; Sparks, Donald L. Geochemical Transactions, Vol. 19, Issue 1 https://doi.org/10.1186/s12932-018-0049-4	journal	February 2018
Analytical model for quantitative prediction of material contrasts in scattering-type near-field optical microscopy Cvitkovic, A.; Ocelic, N.; Hillenbrand, R. Optics Express, Vol. 15, Issue 14 https://doi.org/10.1364/OE.15.008550	journal	January 2007
Ca L _2,3 -edge near edge X-ray absorption fine structure of tricalcium aluminate, gypsum, and calcium (sulfo)aluminate hydrates Geng, Guoqing; Myers, Rupert J.; Kilcoyne, Arthur L. D. American Mineralogist, Vol. 102, Issue 4 https://doi.org/10.2138/am-2017-5670	journal	April 2017
Calcium L2,3-edge XANES of carbonates, carbonate apatite, and oldhamite (CaS) Fleet, M. E.; Liu, X. American Mineralogist, Vol. 94, Issue 8-9 https://doi.org/10.2138/am.2009.3228	journal	August 2009
Spectromicroscopy at the organic-inorganic interface in biominerals De Stasio, G. American Journal of Science, Vol. 305, Issue 6-8 https://doi.org/10.2475/ajs.305.6-8.673	journal	June 2005

Similar Records

The role of Ca-bridged organic matter in an alkaline soil, as revealed by multimodal chemical imaging

Journal Article · Tue Apr 01 00:00:00 EDT 2025 · Geoderma · OSTI ID:2555850

Strong mineralogic control of soil organic matter composition in response to nutrient addition across diverse grassland sites

Journal Article · Tue Sep 01 00:00:00 EDT 2020 · Science of Total Environment · OSTI ID:1637580

Related Subjects

54 ENVIRONMENTAL SCIENCES
soil organic matter (SOM)

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

Citation Formats

References (61)

Similar Records

Related Subjects