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Dual carbonate clumped isotopes (Δ47-Δ48)  constrains kinetic effects and timescales in peridotite-associated springs at  The Cedars, Northern California
  • +9
  • Zeeshan Parvez,
  • Jamie K Lucarelli,
  • Irvin W Matamoros,
  • Joshua Rubi,
  • Kevin Miguel,
  • Ben Elliott,
  • Robert N Ulrich,
  • Randy Flores,
  • Robert A Eagle,
  • James M Watkins,
  • John N Christensen,
  • Aradhna Tripati
Zeeshan Parvez
University of California, Los Angeles

Corresponding Author:[email protected]

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Jamie K Lucarelli
University of California

Corresponding Author:[email protected]

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Irvin W Matamoros
University of California
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Joshua Rubi
East Los Angeles College
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Kevin Miguel
East Los Angeles College
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Ben Elliott
University of California
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Robert N Ulrich
University of California
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Randy Flores
University of California
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Robert A Eagle
University of California
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James M Watkins
University of Oregon
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John N Christensen
Lawrence Berkeley National Laboratory
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Aradhna Tripati
University of California
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Abstract

The Cedars is an area in Northern California with a chain of highly alkaline springs resulting from CO2-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 Ca2+ and OH- enriched water to the surface, creating an environment which promotes rapid precipitation of CaCO3 at surface springs. This environment enables us to apply the recently developed Δ4748 dual clumped isotope analysis to probe kinetic isotope effects (KIEs) and timescales of CO2 transformation in a region with the potential for geological CO2 sequestration. We analyzed CaCO3 recovered from various localities and identified significant kinetic fractionations associated with CO2 absorption in a majority of samples, characterized by enrichment in Δ47 values and depletion in Δ48 values relative to equilibrium. Surface floes exhibited the largest KIEs (ΔΔ­47: 0.163‰, ΔΔ­48: -0.761‰). Surface floe samples begin to precipitate out of solution within the first hour of CO2 absorption, and the dissolved inorganic carbon (DIC) pool requires a residence time of >100 hours to achieve isotopic equilibria. The Δ4847 slope of samples from the Cedars (-3.223±0.519; 1 SE) is within the range of published theoretical values designed to constrain CO2 hydrolysis-related kinetic fractionation (-1.724 to -8.330). The Δ4718O slope (-0.009±0.001) and Δ4713C 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 Δ4748 dual carbonate clumped isotope framework can be applied to study CO2-absorption processes in applied systems, including sites of interest for geological sequestration.
20 Apr 2023Submitted to ESS Open Archive
20 Apr 2023Published in ESS Open Archive