Marine clay maturation induces systematic silicon isotope decrease in authigenic clays and pore fluids

Marine silicate alteration exerts a major influence on marine carbon and cation cycles, but has proven difficult to quantify. In this context, silicon isotopes of marine pore fluids became an important tracer. However, poorly constrained silicon isotope signatures of precipitates produced during silicate alteration (i.e. authigenic clays) remain a major source of uncertainty. Here we present in situ silicon isotope analyses of marine authigenic clays (intergrown iron-smectites and iron-glauconites) occurring within recent sediments from the Oregon margin, eastern North Pacific. We identify a trend to lower silicon isotopes (from −2.24‰ to −3.17‰), accompanied by decreasing aluminum/silicon ratios and increasing potassium oxide contents, which we interpret as an isotopic shift caused by progressive clay maturation via dissolution-reprecipitation reactions. Our modelling suggests that this clay maturation pathway, together with mixing of other fluid sources, may induce pore fluid silicon isotope shifts of up to −1.7‰, if sufficient newly precipitated clays are re-dissolved. This could potentially produce silicon isotopes values significantly lower than seawater and implies that conventional isotope-based approaches underestimate the prevalence of marine silicate alteration. Our findings highlight that clay maturation must be considered when interpreting silicon isotope signatures in terms of marine silicate alteration and upscaling to global element cycles.