Natural variations of δ30Si ratios during progressive basalt weathering, Hawaiian Islands

Silicon stable isotopes can be used to trace the biogeochemical pathways of Si as it moves from its continental sources to its sink in ocean sediments. Along the way, Si is incorporated into clay minerals, taken up by plants where it forms plant opal, and leached into rivers, the major land-to-ocean conduit. Compared to igneous rocks, the waters that drain continents are enriched in heavy Si isotopes, but the mechanisms that control fractionation have not been elucidated. We studied Si isotope fractionation along a 4 million yr basaltic soil chronosequence on the Hawaiian Islands. Using the natural context of these samples in combination with laboratory experiments, we demonstrate that the isotopic composition of dissolved Si in weathering systems is determined by the combined effects of rock disintegration, clay mineral neosynthesis, and Si biocycling. Weathering preferentially releases Si-28 into solution, whereas secondary mineral formation preferentially removes Si-28 from solution. In humid environments, leached soils have lost large amounts of this soluble Si, thus creating a net loss of Si-30 from the entire soil system. As soils develop and greater fractions of Si reside in neoformed clay minerals, delta(30)Si(bulk) (soil) values change progressively toward more negative values; basalt delta(30)Si values are about -0.5 parts per thousand, but older soils have delta(30)Si values up to -2.5 parts per thousand. The difference between the solid and solution delta(30)Si values remains more or less constant with progressive weathering, and therefore, soil water from older soils has a more negative delta(30)Si composition. In the upper horizons of the Hawaiian soils, this weathering-driven delta(30)Si shift is modified by the addition of unweathered primary minerals via dust, carrying delta(30)Si values of about -0.5 parts per thousand, and by biocycling of Si via plants, producing negative delta(30)Si values in phytoliths and positive delta(30)Si values in soil solutions derived from upper horizons. Due to the high concentrations of dissolved Si in these near-surface layers, rivers have more positive delta(30)Si values than predicted based on the weathering status of the lower horizons. When combined with published delta(30)Si values from large rivers worldwide, we find that the results from Hawaii point to weathering control of Si isotopes delivered to the oceans, and thus, to an important continent-ocean linkage that warrants further investigation. Copyright (c) 2005 Elsevier Ltd.