Buffering of potassium in seawater by alteration of basalt in low-temperature, off-axis, hydrothermal systems

It is generally accepted that the composition of seawater has varied through the Phanerzoic and that the variation is linked to changes in the same global fluxes that control the long-term carbon cycle. However, K is observed to be stable at a value of 10 mmol/L despite variable river and hydrothermal fluxes [1]. Secondary K-bearing phases are widely observed in altered upper oceanic crust, suggesting that reactions between seawater and basalt in low-temperature, off-axis, oceanic hydrothermal systems could buffer the K concentration of seawater [2]. As K-feldspar is a common secondary K-bearing mineral in Cretaceous and rare in Cenozoic oceanic crust, the formation of K-feldspar by breakdown of plagioclase reacting with a model Cretaceous seawater was modeled at 15 °C using the PhreeqC code (version 3.2) and the associated llnl.dat database. A fluid with a K-content of 11 mmol/L in equilibrium with K-feldspar and calcite was generated, consistent with K-feldspar acting as a buffer for the K-content in Cretaceous seawater and the production of alkalinity stabilizing atmospheric CO2 levels on the long-term timescales. A compilation of the K2O content of lavas from DSDP and ODP drill cores (from: http://www.earthchem.org/petdb) shows that the average K-content of altered crust was higher in the Cretaceous than the Cenozoic. This data is inconsistent with the model for the composition of seawater presented in [2], but is consistent with an updated and modified version of this model, that uses more realistic fluxes [3]. We conclude that oceanic off-axis hydrothermal systems probably do buffer the K-content of seawater. [1] Timofeeff et al. (2006), Geochim. Cosmochim. Acta. 70, 1977-1994; [2] Demicco et al. (2005), Geology 33, 877-880. [3] Coogan & Dosso (2012), Earth Planet. Sci. Lett. 323-324, 92-101.