Potassium isotopic compositions measured by MC-ICP-MS in cold-plasma, high-resolution mode indicate terrestrial variability in 41K/39K ratios.

Carbon capture and geological storage represents a potential means of managing atmospheric carbon dioxide levels. Understanding the role of faults, as either barriers or conduits to the flow of carbon dioxide, is crucial for predicting the long-term integrity of geological storage sites. Of particular concern is the influence of geochemical reactions on the sealing behaviour of faults and the impact of seismicity and stress regime on fault stability. Here, we examine a 135,000-year palaeorecord of carbon dioxide leakage from a faulted, natural carbon dioxide reservoir in Utah. We assess the isotope and trace-element composition of U-Th-dated carbonate veins, deposited by carbon-dioxide-rich fluids. Temporal changes in vein geochemistry reveal pulses of carbon dioxide injection into the reservoir from deeper formations. Surface leakage rates increase by several orders of magnitude following these pulses. We show that each pulse occurs around 100-2,000 years after the onset of significant local climatic warming, at glacial to interglacial transitions. We suggest that carbon dioxide leakage rates increase as a result of fracture opening, potentially caused by changes in groundwater hydrology, the intermittent presence of a buoyant gas cap and postglacial crustal unloading of regions surrounding the fault

The iron isotope composition of sedimentary pyrite has been proposed as a potential proxy to trace microbial metabolism and the redox evolution of the oceans. We demonstrate that Fe isotope fractionation accompanies abiotic pyrite formation in the absence of Fe(II) redox change. Combined fractionation factors between Fe(II)(aq), mackinawite, and pyrite permit the generation of pyrite with Fe isotope signatures that nearly encapsulate the full range of sedimentary δ(56)Fe(pyrite) recorded in Archean to modern sediments. We propose that Archean negative Fe isotope excursions reflect partial Fe(II)(aq) utilization during abiotic pyrite formation rather than microbial dissimilatory Fe(III) reduction. Late Proterozoic to modern sediments may reflect greater Fe(II)(aq) utilization and variations in source composition.

To evaluate sites for long-term geological storage of CO 2 and optimize techniques for monitoring the fate of injected CO 2 , it is crucial to investigate potential CO 2 migration pathways out of a reservoir and surface leakage magnitudes. For the fi rst time, we calculate CO 2 leakage rates and volumes from ancient fault-related travertines and from an abandoned borehole. U-Th-dated travertine along two faults near Green River, Utah (western United States), shows that leakage has occurred in this area for over 400 k.y. and has switched location repeatedly over kilometer-scale distances. One individual travertine was active for at least 11 k.y. Modern leakage is predominantly through the active Crystal Geyser, which erupts from an abandoned exploration well. Using age data and travertine volume, we calculate magnitudes and rates of CO 2 emission. Fault-focused leakage volume is twice as great as diffuse leakage through unconfi ned aquifers. The leakage rate from a poorly completed borehole is 13 times greater than the long-term time-averaged fault-focused leakage. Although magnitudes and rates of any leakage from future storage sites will be highly dependent on local geology and pressure regime, our results highlight that leakage from abandoned wells is likely to be more signifi cant than through faults.

The feedbacks of climate variability on CO2 consumption fluxes and carbon dynamics are thought to play an important role in moderating the global carbon cycle. High‐frequency sampling campaigns and analyses were conducted in this study to investigate temporal variations of river water chemistry and the impacts of climate variability on CO2 consumption fluxes and carbon dynamics for the Xijiang River, Southwest China. Physical processes modify biogeochemical processes, so major ions display different responses to changing discharge. The annual CO2 consumption rate is (6.8 ± 0.2) × 106 ton/year by carbonate weathering and (2.4 ± 0.3) × 106 ton/year by silicate weathering. The annual CO2 consumption flux is much higher than most world rivers, and strong CO2 consumption capacities are observed in catchments in Southwest China. Lower negative δ13CDIC values are found in the high‐flow season which corresponds with high temperatures compared to those in the low‐flow season. High discharge will accelerate material transport, and high temperatures will increase primary production in the catchment, both of which can be responsible for the shift of δ13CDIC values in the high‐flow season. Increased mineral weathering and biological carbon influx in the catchment are the main factors controlling carbon dynamics. Overall, these findings highlight the sensitivity of CO2 consumption fluxes and carbon dynamics in response to climate variability in the riverine systems.