Stable potassium (K) isotope characteristics at mid-ocean ridge hydrothermal vents and its implications for the global K cycle

Recent discoveries of significant variations in stable K isotope ratios (41K/39K or δ41K) among various terrestrial samples indicate that K isotopes can be a novel tracer for the global K cycle, but a key observation that seawater δ41K is ∼0.6‰ higher than the bulk silicate Earth remains unexplained. An unconstrained component critical to this puzzle is hydrothermal systems that represent both a major K source and sink in the ocean. Here we report δ41K results on mid-ocean ridge (MOR) hydrothermal fluids from the Gorda Ridge and ∼9°N East Pacific Rise (EPR), including time-series samples that recorded major perturbations in fluid chemistry induced by a local volcanic eruption. Fluid δ41K values range from -0.46‰ to -0.15‰, falling between those of fresh basalts and seawater. δ41K values of “time-zero” fluids collected shortly after the volcanic eruption are shifted towards the seawater value, followed by a return to pre-eruption values within ∼2 years. Fluid δ41K variations are largely influenced by water–rock interactions, but they cannot be solely explained by simple mixing of seawater and K leached from basalts at high temperatures. Instead, these data imply small but significant isotope fractionation that enriches heavy K isotopes in basalts, likely caused by low-temperature alteration during the recharge stage of hydrothermal circulation. Our results preclude MOR hydrothermal systems as the cause for the heavy δ41K value of seawater. Using fluid δ41K data and K isotope fractionation constrained here for hydrothermal systems, a K mass-balance model implies a critical role for a marine sedimentary sink, possibly authigenic clay formation, in the global K cycle. Also, applying the K isotope fractionation constrained here to the published δ41K data from ophiolites shows the possibility for significantly lower seawater δ41K during the Ordovician, which can be explained by enhanced reverse weathering in response to distinct climate and tectonics at that time.