Isotopic fractionation accompanying CO2 hydroxylation and carbonate precipitation from high pH waters at The Cedars, California, USA.

The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO 2 and at times via mixing with surface water. These processes lead to distinct carbonate morphologies with "floes" forming at the atmosphere-water interface, "snow" of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO 3 precipitation occurring in waters with low Mg/Ca (<0.01). Precipitation of aragonite is likely promoted by the high pH (11.5–12.0) of pool waters, in agreement with published experiments illustrating the effect of pH on calcium carbonate polymorph selection. The calcium carbonates exhibit an extreme range and approximately 1:1 covariation in δ13C (−9 to −28‰ VPDB) and δ18O (0 to −20‰ VPDB) that is characteristic of travertine formed in high pH waters. The large isotopic fractionations have previously been attributed to kinetic isotope effects accompanying CO 2 hydroxylation but the controls on the δ13C-δ18O endmembers and slope have not been fully resolved, limiting the use of travertine as a paleoenvironmental archive. The limited areal extent of the springs (∼0.5 km2) and the limited range of water sources and temperatures, combined with our sampling strategy, allow us to place tight constraints on the processes involved in generating the systematic C and O isotope variations. We develop an isotopic reaction–diffusion model and an isotopic box model for a CO 2 -fed solution that tracks the isotopic composition of each dissolved inorganic carbon (DIC) species and CaCO 3. The box model includes four sources or sinks of DIC (atmospheric CO 2 , high pH spring water, fresh creek water, and CaCO 3 precipitation). Model parameters are informed by new floe Δ44Ca data (−0.75 ± 0.07‰), direct mineral growth rate measurements (4.8 to 8 × 10−7 mol/m2/s) and by previously published elemental and isotopic data of local water and DIC sources. Model results suggest two processes control the extremes of the array: (1) the isotopically light end member is controlled by the isotopic composition of atmospheric CO 2 and the kinetic isotope fractionation factor (KFF (‰) = (α − 1) × 1000) accompanying CO 2 hydroxylation, estimated here to be −17.1 ± 0.8‰ (vs. CO 2(aq)) for carbon and −7.1 ± 1.1‰ (vs. 'CO 2(aq) + H 2 O') for oxygen at 17.4 ± 1.0 °C. Combining our results with revised CO 2 hydroxylation KFF values based on previous work suggests consistent KFF values of −17.0 ± 0.3‰ (vs. CO 2(aq)) for carbon and −6.8 ± 0.8‰ for oxygen (vs. 'CO 2(aq) + H 2 O') over the 17–28 °C temperature range. (2) The isotopically heavy endmember of calcium carbonates at The Cedars reflects the composition of isotopically equilibrated DIC from creek or surface water (mostly HC O 3 - , pH = 7.8–8.7) that occasionally mixes with the high-pH spring water. The bulk carbonate δ13C and δ18O values of modern and ancient travertines therefore reflect the proportion of calcium carbonate formed by processes (1) and (2), with process (2) dominating the carbonate precipitation budget at The Cedars. These results show that recent advances in understanding kinetic isotope effects allow us to model complicated but common natural processes, and suggest ancient travertine may be used to retrieve past meteoric water δ18O and atmospheric δ13C values. There is evidence that older travertine at The Cedars recorded atmospheric δ13C that predates large-scale combustion of fossil fuels. [ABSTRACT FROM AUTHOR]