Kinetic calcium isotope effects can be used as growth-rate proxies for volcanic and subvolcanic minerals. Here, we analyze Ca isotopic compositions in experimental and natural samples and confirm that large kinetic effects (>2‰) can occur during magmatic plagioclase crystallization. Experiments confirm theoretical predictions that disequilibrium isotope effects depend mainly on the rates for crystal growth relative to liquid phase Ca diffusivity (R/D). Plagioclase phenocrysts from the 1915 Mount Lassen rhyodacite eruption, the ∼650-y-old Deadman Creek Dome eruption, and several mafic subvolcanic orbicules and plagioclase comb layers from Northern California have disequilibrium Ca isotopic compositions that suggest rapid crystal growth rates (>1 cm/y to 15 cm/y). The Ca isotope results, combined with complementary crystal-size distribution analyses, suggest that magmatic rejuvenation (and eruption) events, as reflected in crystal growth times, can be as short as ∼10^-3 y. Although mafic systems are predicted to have shorter magmatic rejuvenation periods, we find similarly short timescales in both mafic and silicic systems. These results are consistent with a growing body of evidence suggesting that dominantly crystalline volcanic magma reservoirs can be rapidly reactivated by the injection of fresh magma prior to eruption. By focusing on a common mineral such as plagioclase, this approach can be applied across all major magmatic compositions, suggesting that Ca isotopes can be used as a tool for investigating the dynamics and timing of volcanic eruptions.

Abstract: Foraminifera are unicellular organisms that inhabit the oceans. They play an important role in the global carbon cycle and record valuable paleoclimate information through the uptake of trace elements such as strontium into their calcitic shells. Understanding how foraminifera control their internal fluid composition to make calcite is important for predicting their response to ocean acidification and for reliably interpreting the chemical and isotopic compositions of their shells. Here, we model foraminiferal calcification and strontium partitioning in the benthic foraminifera Cibicides wuellerstorfi and Cibicidoides mundulus based on insights from inorganic calcite experiments. The numerical model reconciles inter-ocean and taxonomic differences in benthic foraminifer strontium partitioning relationships and enables us to reconstruct the composition of the calcifying fluid. We find that strontium partitioning and mineral growth rates of foraminiferal calcite are not strongly affected by changes in external seawater pH (within 7.8–8.1) and dissolved inorganic carbon (DIC, within 2100–2300 μmol/kg) due to a regulated calcite saturation state at the site of shell formation.

The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO2 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 CaCO3 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 CO2 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 CO2-fed solution that tracks the isotopic composition of each dissolved inorganic carbon (DIC) species and CaCO3. The box model includes four sources or sinks of DIC (atmospheric CO2, high pH spring water, fresh creek water, and CaCO3 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 CO2 and the kinetic isotope fractionation factor (KFF (‰) = (α − 1) × 1000) accompanying CO2 hydroxylation, estimated here to be −17.1 ± 0.8‰ (vs. CO2(aq)) for carbon and −7.1 ± 1.1‰ (vs. ‘CO2(aq) + H2O’) for oxygen at 17.4 ± 1.0 °C. Combining our results with revised CO2 hydroxylation KFF values based on previous work suggests consistent KFF values of −17.0 ± 0.3‰ (vs. CO2(aq)) for carbon and −6.8 ± 0.8‰ for oxygen (vs. ‘CO2(aq) + H2O’) 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 HCO3-, 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.

The authors regret that in the original article, the kinetic fractionation factors (KFFs) related to the CO2 hydroxylation reaction (CO2(aq) + OH– → HCO3–) were calculated using atmospheric δ18OCO2 values of 0.0 ± 0.5 ‰ (VPDB) while the correct values are 10.25 ± 0.5 ‰ (VPDB). We erroneously employed the atmospheric δ18OCO2 values from the NOAA CO2 global network (Trolier et al., 1996) by not converting atmospheric δ18OCO2 from the VPDB-CO2 scale to the VPDB scale through the following expression (e.g. Srivastava and Verkouteren, 2018): [Formula presented] This correction affects the reported oxygen isotope KFFs for CO2 hydroxylation to form HCO3– prior to CaCO3 precipitation. We have corrected Table 7 and Fig. 13 accordingly (see below). The composition of atmospheric CO2 was also incorrectly plotted on the VPDB scale in Figs. 1, 8 and 15 of our original manuscript based on previous works (Fig. 8 in Clark and Fontes, 1990; Fig. 2 in Clark et al., 1992). Importantly, the modelling outputs and main conclusions of the original article are not affected by these corrections. Nevertheless, the updated KFFs resolve an apparent discrepancy between the laboratory and field studies in our original article. Moreover, the oxygen isotope KFF for CO2 hydroxylation now displays a positive temperature dependence over the 4–28 °C range, which was not statistically significant in the original article (Fig. 13c, r2 = 0.86, n = 10, p-value <0.01): [Formula presented]where T is in °C, the uncertainty represents one standard error, and KFF* is the oxygen isotope kinetic fractionation factor between the HCO3– product and ‘CO2(aq) + H2O’ expressed as the per mil deviation from unity: [Formula presented] Here and in the original article, the KFF is expressed relative to the weighted sum ‘CO2(aq) + H2O’ rather than ‘CO2(aq) + OH–’ (i.e. the reactants) to avoid the uncertainty on the OH––H2O fractionation factor (Zeebe, 2020; Bajnai and Herwartz, 2021). δ18O and oxygen KFF values in bold have been corrected by converting atmospheric δ18OCO2 values from the VPDB-CO2 scale to the VPDB scale using Eq. (1). The authors apologize for any inconvenience caused.

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 Δ47-Δ48 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 h to achieve isotopic equilibria. The Δ48/Δ47 slope of samples from the Cedars (−3.223 ± 0.519) is within the range of published theoretical values designed to constrain CO2 hydrolysis-related kinetic fractionation (−1.724 to −8.330). The Δ47/δ18O slope (−0.009 ± 0.001) and Δ47/δ13C 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 Δ47-Δ48 dual carbonate clumped isotope framework can be applied to study CO2-absorption processes in applied systems, including sites of interest for geological sequestration.