Chemical Alteration of Riverine Particles in Seawater and Marine Sediments: Effects on Seawater Composition and Atmospheric CO2

Abstract

Numerous studies have shown that riverine particles react with seawater. Reactions include dissolution of reactive silicate minerals (e.g., feldspars) and formation of authigenic clays and carbonates. Previous studies have either focused on mineral dissolution (marine silicate weathering) or authigenic phase formation (reverse weathering). A comprehensive study that assesses all processes affecting the marine alteration of riverine particle has -to our knowledge- not yet been conducted. Our contribution aims to fill this gap. We first quantify cation exchange between seawater and riverine particles that occurs when particles enter the marine realm and show that significant global cation fluxes are induced by this process (-1.3 Tmol Na yr -1 , -0.2 Tmol K yr -1 , -0.4 Tmol Mg yr -1 , +1.2 Tmol Ca yr -1 ) where the positive sign indicates cation release into seawater while the negative sign denotes uptake on particles. We then use thermodynamic and kinetic modeling to investigate how much of the suspended particle load dissolves in contact with seawater and estimate corresponding global release rates for dissolved cations and silica assuming congruent dissolution (+0.06 Tmol Na yr -1 , +0.15 Tmol Ca yr -1 , +2.8 Tmol Si yr -1 ). Subsequently, we investigate rates of mineral dissolution and authigenic clay and carbonate formation in marine sediments applying reactive transport modeling, porewater data and mass balance calculations. Our best estimates for net fluxes across the sediment/water interface (dissolution–mineral formation) result as +1.5 Tmol Na yr -1 , -2.5 Tmol K yr -1 , -2.0 Tmol Mg yr -1 , +2.5 Tmol Ca yr -1 , and +1.9 Tmol Si yr -1 where most of the Na and Ca release is induced by plagioclase dissolution, K is taken up in authigenic clays and Mg is removed from solution by authigenic clay and carbonate formation. We conclude that the alkalinity of seawater is not significantly affected by marine silicate alteration since cation release fluxes (Na, Ca) are as high as cation uptake fluxes (K, Mg) on equivalent basis. Moreover, marine silicate weathering and reverse weathering are closely coupled since Al required for clay formation is mostly provided by feldspar dissolution while Al removal in authigenic clay promotes and maintains feldspar dissolution in marine sediments. Authigenic carbonate formation in anoxic subsurface sediments sequesters significant amounts of carbon (2.5 Tmol C yr -1 ) according to our estimates where most of the Ca and alkalinity required for carbonate formation are provided by the dissolution of Ca-bearing silicate minerals. This hidden sedimentary cycle provides a sink for dissolved inorganic carbon that may drive a slow draw-down of atmospheric CO 2 on geological timescales. Marine silicate alteration has an even stronger effect on the geochemical evolution of seawater by generating large fluxes of dissolved K, Mg, Ca and Si.