Reverse weathering in marine sediments and the geochemical cycle of potassium in seawater: Insights from the K isotopic composition (⁴¹K/³⁹K) of deep-sea pore-fluids

In situ Al-silicate formation, also known as “reverse weathering,” is an important sink of many of the major and minor cations in seawater (e.g. Mg, K, and Li). However, the importance of this sink in global geochemical cycles and isotopic budgets of these elements remains poorly constrained. Here, we report on the potassium isotopic composition (41K/39K) of deep-sea sediment pore-fluids from four (Integrated) Ocean Drilling Program sites (1052, U1378, U1395 and U1403) to characterize potassium isotopic fractionation associated with the formation of authigenic Al-silicate minerals in marine sediments and its role in elevating the 41K/39K of seawater relative to bulk silicate Earth. Isotopic ratios are obtained by high-resolution multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in cold plasma conditions with a long-term external reproducibility of ca. 0.17‰. We find that, although all sites are characterized by pore-fluid K concentrations that decline with increasing depth, their K isotopic profiles vary systematically from site-to-site; at sites characterized by rapid sedimentation rates, pore-fluid profiles of 41K/39K are relatively invariant whereas at sites characterized by slow sedimentation rates, 41K/39K declines with depth by up to 1.8‰. Results from 1-D diffusion-advection-reaction models suggest that these differences may result from a complex interplay between sedimentation rate and fractionation of K isotopes during diffusion, Al-silicate authigenesis, and ion exchange. Model simulations suggest fractionation factors between 0.9980 and 1.0000 for reverse weathering reactions in deep-sea sediments. Although deep-sea sites do not constitute major sinks of K in seawater, some of the processes responsible for K isotopic fractionation at these sites (diffusion and Al-silicate authigenesis) likely play a role in determining the 41K/39K of seawater.