Relating soil gas to weathering using rock and regolith geochemistry

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ID: 302387
2018
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Abstract
Weathering-induced fracturing (WIF) has been posited to be a mechanism that develops secondary porosity when mineral reaction fronts separate over depth intervals in regolith, and, in particular, when oxidation (which can promote porosity development through volume expansion) occurs deeper than dissolution (which grows porosity through material removal). If this is true, then the protolith9s capacity to reduce O~2~ \[for example, the Fe(II) content\] and O~2~ availability should affect WIF. This study explores the hypothesis that if the ratio of pO~2~ to pCO~2~, in soil water, *R*9~(aq)~, is greater than the ratio of the capacity of the protolith to consume O~2~ and CO~2~, *R*^0^, then WIF is more likely to occur, and regolith will become thicker. We evaluated this hypothesis by measuring the bulk geochemistry of regolith and rock and monitoring soil gas at three sites, encompassing a wide range of FeO concentrations and regolith thickness: a Pennsylvania (PA) diabase (10.15%; 3.8 m), a Virginia (VA) diabase (10.49%; 1.4 m), and a VA granite (1.45%; 20 m). We inferred soil water O~2~ concentrations from calculated equilibrium with the measured soil gas pO~2~. We observed WIF in the VA granite and PA diabase where *R*9~(aq)~ \> *R*^0^, while at the site that lacked WIF -- the VA diabase -- *R*9~(aq)~ \< *R*^0^, particularly during the wet season. In the VA diabase, the presence of swelling clays (smectite) limits the ability of the oxidant (O~2~) to diffuse deeper into the weathering profile during the wet season and microbially accelerated iron oxidation rapidly consumes O~2~, limiting O~2~ availability for WIF. Smectite has little to no observable effect on O~2~ consumption in the PA diabase because the PA diabase is more fractured. A compilation of dissolved soil gas oxidation ratios, the stoichiometric ratio of O~2~ consumed to CO~2~ produced, shows that for unsaturated conditions, the mean is −1.45 ± 0.88, which is consistent with aerobic root and microbial respiration and the oxidation of organic matter. For near-saturated conditions, the mean oxidation ratio of the compilation is −3.46 ± 1.79, which is consistent with Fe redox and microbial metabolism under reducing conditions. The consistency between the VA and PA data presented here and the compilation suggests that soil water surplus drives coupled Fe-redox reactions that may act as a negative feedback, limiting O~2~ supply and WIF under wetter soil moisture conditions. We defined *Rz*, the ratio of O~2~ consumption to CO~2~ consumption during weathering for each depth interval, *z*. For all profiles, *R*9~(aq)~ \> *Rz* near the surface but *R*9~(aq)~ approaches *Rz* in the saprolite. We suggest that *R*9~(aq)~ \> *Rz* in the soil reflects consumption of O~2~ and production of CO~2~ due to biotic processes whereas *R9~(aq)~* approaching *Rz* suggests that low fluxes at depth are at least partly dictated by rock and regolith composition, notably tortuosity of pores. In the VA diabase, we observed *R*9~(aq)~ \< *Rz* occasionally during the wet season in the lowermost soil and saprolite. Thus, at times the O~2~ availability may be less than the O~2~ consumption at that depth, consistent with Fe(II) loss and a lack of WIF. Mass-balance calculations show Fe loss in the VA diabase. The influence of rock composition on aqueous O~2~/CO~2~ concentrations in saprolite is consistent with the hypothesis that the protolith9s capacity to consume O~2~ and CO~2~ has some effect on oxidation and acid consumption deep in the weathering profile.
Reference Key
openalex_W2893256808 Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Gary E. Stinchcomb, Hyojin Kim, Elizabeth A. Hasenmueller, Pamela Sullivan, Peter B. Sak, Susan L. Brantley
Journal american journal of science
Year 2018
DOI
10.2475/07.2018.01
URL
https://doi.org/10.2475/07.2018.01
Keywords Keywords not found

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