Dual carbonate clumped isotopes (Δ 47 -Δ 48 ) constrains kinetic effects and timescales in peridotite-associated springs at the Cedars, Northern California
The Cedars is an area in Northern California with a chain of highly alkaline springs resulting from CO 2 -charged meteorological water interacting with a peridotite body. Serpentinization resulting from this interaction at depth leads to the sequestration of various carbonate minerals into veins accompanied by a release of Ca 2+ and OH – enriched water to the surface, creating an environment which promotes rapid precipitation of CaCO 3 at surface springs. This environment enables us to apply the recently developed Δ 47 -Δ 48 dual clumped isotope analysis to probe kinetic isotope effects (KIEs) and timescales of CO 2 transformation in a region with the potential for geological CO 2 sequestration. Here, we analyzed CaCO 3 recovered from various localities and identified significant kinetic fractionations associated with CO 2 absorption in a majority of samples, characterized by enrichment in Δ 47 values and depletion in Δ 48 values relative to equilibrium. Surface floes exhibited the largest KIEs (ΔΔ 47 : 0.163‰, ΔΔ 48 : -0.761‰). Surface floe samples begin to precipitate out of solution within the first hour of CO 2 absorption, and the dissolved inorganic carbon (DIC) pool requires a residence time of >100 h to achieve isotopic equilibria. The Δ 48 /Δ 47 slope of samples from the Cedars (-3.223 ± 0.519) is within the range of published theoretical values designed to constrain CO 2 hydrolysis-related kinetic fractionation (-1.724 to -8.330). The Δ 47 /δ 18 O slope (-0.009 ± 0.001) and Δ 47 /δ 13 C slope (-0.009 ± 0.001) are roughly consistent with literature values reported from a peridotite in Oman of -0.006 ± 0.002 and -0.005 ± 0.002, respectively. The consistency of slopes in the multi-isotope space suggests the Δ 47 -Δ 48 dual carbonate clumped isotope framework can be applied to study CO 2 -absorption processes in applied systems, including sites of interest for geological sequestration.