Multicomponent ionic diffusion in porewaters: Coulombic effects revisited

B.P. Boudreau, F.J.R. Meysman, J.J. Middelburg

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    The diffusion of an ion in porewaters cannot occur independently of the other ions in solution as a result of Coulombic coupling, as well as from other effects not considered here. Unfortunately, a longstanding disagreement exists about the correct form and meaning of the equations that describe Coulombic coupling in porewaters, i.e., Ben-Yaakov [Am. J. Sci. 281 (1981) 974] vs. Lasaga [Am. J. Sci. 281 (1981) 981]. This paper re-examines this controversy by reformulating the problem starting from fundamental concepts of mass and charge conservation. We show that these antagonistic formulations are both valid and, in fact, equivalent, when the different interpretations of charge balance are resolved. Most of the disagreements between Ben-Yaakov and Lasaga are then shown to result from differing methods of solution, not fundamental disparities in their models. We note, however, that the explanation for the concept of "stationary" gradients of nonreacting ions as given Ben-Yaakov is inaccurate, and such gradients do lead to diffusive fluxes that are counterbalanced by electrochemical migrational fluxes to produce no net flux (excluding advective flux). We further find that the bicarbonate diffusive flux will not balance the diffusional charge flux of sulfate during its reduction if advection is present. This latter imbalance generates compensating fluxes in the other nonreacting ions. We have applied our theory to a simplified case of sulfate reduction in a marine sediment. The results show that nonreacting ions do diffuse and that with normally expected values of porewater advection, the ratio of the bicarbonate to the sulfate flux can be far different than the ideal value of -2. [KEYWORDS: diffusion; Coulombic coupling; porewater; diagenesis]
    Originele taal-2Engels
    Pagina's (van-tot)653-666
    TijdschriftEarth and Planetary Science Letters
    Nummer van het tijdschrift2
    StatusGepubliceerd - 2004


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