TY - JOUR
T1 - Molecular Nature of Mineral-Organic Associations within Redox-Active Mountainous Floodplain Sediments
AU - Anderson, Cam G.
AU - Goebel, Genevieve M.
AU - Tfaily, Malak M.
AU - Fox, Patricia M.
AU - Nico, Peter S.
AU - Fendorf, Scott
AU - Keiluweit, Marco
N1 - Publisher Copyright:
© 2023 American Chemical Society
PY - 2023/9/21
Y1 - 2023/9/21
N2 - Floodplains are critical terrestrial-aquatic interfaces that act as hotspots of organic carbon (OC) cycling, regulating ecosystem carbon storage as well as export to riverine systems. Within floodplain sediments, regular flooding and textural gradients interact to create dynamic redox conditions. While anaerobic protection of OC upon burial is a well-recognized carbon storage mechanism in redox-active floodplain sediments, the impact of protective mineral-organic associations is relatively unknown. Here we determined the quantitative importance and chemical composition of mineral-organic associations along well-defined redox gradients emerging from textural variations and depth within meander sediments of the subalpine East River watershed (Gothic, CO). We characterized mineral-organic associations using a combination of sequential extractions, physical fractionation, and high-resolution mass spectrometry. Across the meander, we found that mineral-associated OC constitutes a significant fraction of total OC, and that extractable iron (Fe) and aluminum (Al) phases as well as high-density isolates were strongly correlated with total OC content, suggesting that mineral-organic associations are quantitatively important for floodplain sediment OC protection. Our mass spectrometry results showed OC associated with increasingly ordered Fe and Al phases are relatively enriched in low-molecular weight, oxidized, aromatic compounds. Surprisingly, however, total OC content showed weak or no correlation with indicators of anaerobic protection, such as relatively bioavailable OC pools (water-extractable and particulate OC) or the molecular weight and oxidation state of OC. Overall, this work highlights that protection of OC bound to reactive mineral phases─in addition to anaerobic protection─can play a quantitatively important role in controlling soil carbon storage in redox-active floodplain sediments.
AB - Floodplains are critical terrestrial-aquatic interfaces that act as hotspots of organic carbon (OC) cycling, regulating ecosystem carbon storage as well as export to riverine systems. Within floodplain sediments, regular flooding and textural gradients interact to create dynamic redox conditions. While anaerobic protection of OC upon burial is a well-recognized carbon storage mechanism in redox-active floodplain sediments, the impact of protective mineral-organic associations is relatively unknown. Here we determined the quantitative importance and chemical composition of mineral-organic associations along well-defined redox gradients emerging from textural variations and depth within meander sediments of the subalpine East River watershed (Gothic, CO). We characterized mineral-organic associations using a combination of sequential extractions, physical fractionation, and high-resolution mass spectrometry. Across the meander, we found that mineral-associated OC constitutes a significant fraction of total OC, and that extractable iron (Fe) and aluminum (Al) phases as well as high-density isolates were strongly correlated with total OC content, suggesting that mineral-organic associations are quantitatively important for floodplain sediment OC protection. Our mass spectrometry results showed OC associated with increasingly ordered Fe and Al phases are relatively enriched in low-molecular weight, oxidized, aromatic compounds. Surprisingly, however, total OC content showed weak or no correlation with indicators of anaerobic protection, such as relatively bioavailable OC pools (water-extractable and particulate OC) or the molecular weight and oxidation state of OC. Overall, this work highlights that protection of OC bound to reactive mineral phases─in addition to anaerobic protection─can play a quantitatively important role in controlling soil carbon storage in redox-active floodplain sediments.
KW - Climate change
KW - Floodplains
KW - Mineral-organic associations
KW - Redox gradients
KW - Soil organic carbon
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U2 - 10.1021/acsearthspacechem.3c00037
DO - 10.1021/acsearthspacechem.3c00037
M3 - Article
AN - SCOPUS:85170216982
SN - 2472-3452
VL - 7
SP - 1623
EP - 1634
JO - ACS Earth and Space Chemistry
JF - ACS Earth and Space Chemistry
IS - 9
ER -