Cited by 126Paleontology and Stratigraphy of FossilsGeochemistry and Elemental AnalysisGeological formations and processes

The Weathering of Sedimentary Organic Matter as a Control on Atmospheric O2: II. Theoretical Modeling

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Bolton, E. W., Berner, R. A., Petsch, S. T.·2006·American Journal of Science

Abstract

To investigate the weathering of sedimentary organic matter and its role in regulating atmospheric oxygen, a theoretical modeling study is presented that addresses the fundamental controls on atmospheric oxygen uptake: erosion rate, organic matter content, and reaction rate. We compare model results with the previous part of this study that analyzed a drill core of black shale from the New Albany formation (Upper Devonian, Clay City, KY) for total and organic carbon, pyrite sulfur, porosity, permeability and specific surface area. As was observed in the field study, the model predicts that the loss of organic matter by oxidative weathering takes place across a reaction "front" where organic carbon content decreases sharply toward the land surface along with pyrite loss. The model is based on kinetic control of reaction of organic matter and pyrite with O~2~ dissolved in soil water. The downward diffusion of gaseous O~2~ partitions with dissolved O~2~ in water films on sediment grains via Henry's law. Once a weathering profile is developed, the downward migrating O~2~ reacts with shale organic matter and pyrite. Pyrite reacts faster with O~2~ than does organic matter (for a given local concentration of oxygen) making the pyrite front generally deeper than the organic matter front. We explore the influence of differing erosion rates, atmospheric O~2~ concentrations, organic matter contents, porosities, tortuosities, and rates of reaction (that could include possible acceleration due to microbes) on the oxygen consumption. We conclude, based on our modeling, that the erosion rate and the concentration of buried reduced matter, as opposed to the level of atmospheric O~2~, normally limits the rate of drawdown of atmospheric oxygen. For the vast majority of erosion rates and Phanerozoic oxygen levels, essentially all ancient reduced material is oxidized before reaching the surface. Only in regions of unusually rapid erosion or during very low atmospheric oxygen levels can rates of diffusion of O~2~ in soils and rates of reaction control O~2~ drawdown, leading to weathering that is O~2~-dependent. In this case erosion and rapid reburial of unoxidized organic matter would occur.

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  • Near modern pO2 (∼1 PAL), uplifted organic carbon is completely oxidized in slowly eroding soil environments, meaning oxidative weathering is transport-controlled by the supply of reduced material, rather than kinetically controlled by the pO2 level.

    “This is because near modern pO2 (∼1 PAL), uplifted organic carbon is completely oxidized in slowly eroding soil environments32, meaning oxidative weathering is transport-controlled by the supply of reduced material, rather than kinetically controlled by the pO2 level.”
  • In the modern oxygenated environment, much of the sedimentary organic carbon that is uplifted is oxidized, with the remainder returning to the sediments as 'detrital' organic carbon.

    “In the modern oxygenated environment (Fig. 1d), much of the sedimentary organic carbon that is uplifted is oxidized32, with the remainder returning to the sediments as ‘detrital' organic carbon37”
  • At pO2∼1 PAL organic carbon is completely oxidized for uplift rates <10 cm kyr−1 and even conservative (low porosity; n*=2) shale parameters.

    “As demonstrated by Bolton et al.32, at pO2∼1 PAL organic carbon is completely oxidized for uplift rates <10 cm kyr−1 and even conservative (low porosity; n*=2) shale parameters.”
  • The oxidative weathering model has been calibrated against laboratory measurements constraining local kerogen and pyrite oxidation kinetics, and a field study constraining oxygen transport through porous shale.

    “The model has been calibrated against laboratory measurements constraining local kerogen45 and pyrite3263 oxidation kinetics, and a field study constraining oxygen transport through porous shale43.”
  • Model parameters are taken from the default parameter set of Bolton et al., which generate a reaction front at depth ∼10 m for oxidative weathering of organic carbon at global-mean values for TOC (1 wt%) and erosion rate (5 cm kyr−1).

    “Model parameters (summarized in Table 2) are taken from the default parameter set of Bolton et al.32 (their Table 1 and Figs 3–5), which generate a reaction front at depth ∼10 m for oxidative weathering of organic carbon at global-mean values for TOC (1 wt%) and erosion rate (5 cm kyr−1) (Fig. 6).”

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Research works printed but not linked: 8

  1. ------2004, The Phanerozoic Carbon Cycle : CO 2 and O 2 : New York, Oxford University Press, 150 p.
  2. Chang, S., ms, 1997, Coal weathering and the geochemical carbon cycle: New Haven, Connecticut, Ph.D. Dissertation, Yale University, 102 p.
  3. Garrels, R. M., and Perry, E. A., 1974, Cycling of carbon, sulfur and oxygen through geologic time, in Goldberd, E. D., editor, The Sea-Ideas and Observations on Progress in the Study of the Seas: New York, Wiley, Marine Chemistry, v. 5, p. 303-16.
  4. Gevantman, L. H., 2006, Solubility of Selected Gases in Water, in Lide, D. R., editor, CRC Handbook of Chemistry and Physics, 86 th edition, Internet Version 2006, http://www.hbcpnetbase.com: Boca Raton, Florida, Taylor and Francis, online data.
  5. ------1984, The Chemistry of the Atmosphere and Oceans: New York, Wiley, 582 p.
  6. Hu, Q., and Feng, S., 2003, A daily soil temperature dataset and soil temperature climatology of the contiguous United States: Journal of Applied Meteorology, v. 42, p. 1139 -1156.
  7. Petsch, S. T., ms, 2000, A study on the weathering of organic matter in black shales and implications for the geochemical cycles of carbon and oxygen: New Haven, Connecticut, Ph.D. dissertation, Yale University, 273 p.
  8. Washburn, E. W., editor, 2003, International Critical Tables of Numerical Data, Physics, Chemistry and Technology: First Electronic Edition: prepared under the auspices of the International Research Council and the National Academy of Sciences by the National Research Council of the United States of America: Norwich, New York, Knovel online book.

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Authors
Bolton, E. W., Berner, R. A., & Petsch, S. T.
Affiliations
University of Massachusetts Amherst (US)
Venue
American Journal of Science
Published
2006-10-01
Volume
306
Issue
8
Pages
575-615
ISSN
0002-9599 (ISSN-L)
OpenAlex
W2024710393
Cited by
126
References
74
Citations by year
2026: 3 · 2025: 6 · 2024: 10 · 2023: 10 · 2022: 20 · 2021: 8 · 2020: 13 · 2019: 10 · 2018: 6 · 2017: 8 · 2016: 5 · 2015: 3 · 2014: 2 · 2013: 7 · 2012: 2
FWCI
1.68
Type
journal article
Language
en
Open access
Locations
American Journal of Science (publishedVersion)
Funders
  • National Science Foundation (0104797)
  • U.S. Department of Energy (DE‐FG02‐, FG02-01ER15173, FG0201ER15216)
  • National Aeronautics and Space Administration (NNG05GQ97G)
  • Yale University
  • NASA Astrobiology Institute
  • Office of Science
  • Basic Energy Sciences (DE-FG02)
Topics
  • Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
  • Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
  • Physical Sciences › Earth and Planetary Sciences › Earth-Surface Processes › Geological formations and processes
Keywords
atmospheric oxygen, oxidative weathering, sediment organic matter, pyrite oxidation, black shales, New Albany Shale, erosion rate, oxygen diffusion, Henry's law, reaction front, organic carbon, porosity and permeability, microbial oxidation

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