The Soil Water Isotope Storage System (SWISS): An integrated soil water vapor sampling and multiport storage system for stable isotope geochemistry.

RATIONALE: Soil water stable isotopes are a powerful tool for tracking interactions among the hydrosphere, geosphere, atmosphere, and biosphere. The challenges associated with creating high-temporal-resolution soil water stable isotope datasets from a diversity of sites have limited the utility of stable isotope geochemistry in addressing a range of complex problems. A device that can enable further development of high-temporal-resolution soil water isotope datasets that are created with minimal soil profile disruption from remote sites would greatly expand the utility of soil water stable isotope analyses. METHODS: We designed a method for sampling and storing soil water vapor for stable isotope analysis that leverages recent advances in soil water sampling strategies. Here, we test the reliability of the storage system by introducing water vapor of known oxygen and hydrogen isotopic composition into the storage system, storing the water vapor for a predetermined amount of time, and then measuring the stable isotope composition of the vapor after the storage period. RESULTS: We demonstrate that water vapor stored in our flasks reliably maintains its isotope composition within overall system uncertainty (±0.5‰ for δ18 O values and ±2.4‰ for δ2 H values) for up to 30 days. CONCLUSIONS: This method has the potential to enable the collection of high-temporal-resolution soil water isotope datasets from remote sites that are not accessed daily in a time- and cost-effective manner. All the components used in the system can be easily controlled using open-source microcontrollers, which will be used in the future to automate sampling routines for remote field deployment. The system is designed to be an open-source tool for use by other researchers.

Primary to post-depositional microbial controls on the stable and clumped isotope record of shoreline sediments at Fayetteville Green Lake.

Lacustrine carbonates are a powerful archive of paleoenvironmental information but are susceptible to post-depositional alteration. Microbial metabolisms can drive such alteration by changing carbonate saturation in situ, thereby driving dissolution or precipitation. The net impact these microbial processes have on the primary δ18O, δ13C, and Δ47 values of lacustrine carbonate is not fully known. We studied the evolution of microbial community structure and the porewater and sediment geochemistry in the upper ~30 cm of sediment from two shoreline sites at Green Lake, Fayetteville, NY over 2 years of seasonal sampling. We linked seasonal and depth-based changes of porewater carbonate chemistry to microbial community composition, in situ carbon cycling (using δ13C values of carbonate, dissolved inorganic carbon (DIC), and organic matter), and dominant allochems and facies. We interpret that microbial processes are a dominant control on carbon cycling within the sediment, affecting porewater DIC, aqueous carbon chemistry, and carbonate carbon and clumped isotope geochemistry. Across all seasons and sites, microbial organic matter remineralization lowers the δ13C of the porewater DIC. Elevated carbonate saturation states in the sediment porewaters (Ω > 3) were attributed to microbes from groups capable of sulfate reduction, which were abundant in the sediment below 5 cm depth. The nearshore carbonate sediments at Green Lake are mainly composed of microbialite intraclasts/oncoids, charophytes, larger calcite crystals, and authigenic micrite-each with a different origin. Authigenic micrite is interpreted to have precipitated in situ from the supersaturated porewaters from microbial metabolism. The stable carbon isotope values (δ13Ccarb) and clumped isotope values (Δ47) of bulk carbonate sediments from the same depth horizons and site varied depending on both the sampling season and the specific location within a site, indicating localized (µm to mm) controls on carbon and clumped isotope values. Our results suggest that biological processes are a dominant control on carbon chemistry within the sedimentary subsurface of the shorelines of Green Lake, from actively forming microbialites to pore space organic matter remineralization and micrite authigenesis. A combination of biological activity, hydrologic balance, and allochem composition of the sediments set the stable carbon, oxygen, and clumped isotope signals preserved by the Green Lake carbonate sediments.

Toward a Cenozoic history of atmospheric CO2.

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.

Carbonate facies-specific stable isotope data record climate, hydrology, and microbial communities in Great Salt Lake, UT.

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ18 Owater , δ13 CDIC ), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ18 Ocarb , δ13 Ccarb , ∆47 ), as well as carbon isotopic compositions of bulk organic matter (δ13 Corg ) and dissolved inorganic carbon (DIC; δ13 CDIC ) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time-averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ∆47 isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(∆47 )), δ18 Ocarb , and calculated δ18 Owater in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation-precipitation balance, as well as identify microbially mediated carbonate formation.