Quantitative interpretation of pH distributions in aquatic sediments: A reaction-transport modeling approach

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ID: 293452
2005
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Abstract
Despite its status of master variable, there have been relatively few attempts to quantitatively predict the distributions of pH in biogeochemical reactive transport systems. Here, we propose a theoretical approach for calculating the vertical pore water profiles of pH and the rates of proton production and consumption in aquatic sediments. In this approach, the stoichiometric coefficients of species that participate in acid-base equilibrium reactions are treated as unknown variables in the biogeochemical reaction network. The mixed kinetic-equilibrium reaction system results in a set of coupled differential and algebraic equations and is solved using a new numerical solver. The diagnostic capabilities of the model are illustrated for depositional conditions representative of those encountered on the continental shelf. The early diagenetic reaction network includes the major microbial degradation pathways of organic matter and associated secondary redox reactions, mineral precipitation and dissolution processes, and homogeneous acid-base reactions. The resulting pH profile in this baseline simulation exhibits a sharp decrease below the sediment-water interface, followed by an increase with depth and again a decrease. The features of the pH profile are explained in terms of the production and consumption of protons by the various biogeochemical processes. Secondary oxygenation reactions are the principal proton producers within the oxic zone, while reduction of iron and manganese oxyhydroxides are primarily responsible for the reversal in the pH gradient in the suboxic zone. Proton production in the zone of sulfate reduction outweighs alkalinity production, maintaining the undersaturation of the pore waters with respect to calcite. Integrated over the entire depth of early diagenesis, dissolution of CaCO~3~ is the main sink for protons. Variations in the reaction rate order and rate constant for CaCO~3~ dissolution do not fundamentally alter the shape of the pH profile. An entirely different shape is obtained, however, when the pore waters are assumed to remain in thermodynamic equilibrium with calcite at all depths. Pore water (bio)irrigation decreases the amplitude of pH changes in the sediment and may modify the shape of the pH profile.
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openalex_W2074345155 Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Parisa Jourabchi
Journal american journal of science
Year 2005
DOI
10.2475/ajs.305.9.919
URL
https://ajsonline.org/article/61597.pdf
Keywords Keywords not found

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