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1. Reconstructing paleoenvironments of the Late Cretaceous Western Interior Seaway, USA, using paired triple oxygen and carbonate clumped isotope measurements

   https://doi.org/10.1130/B37543.1  

   Wostbrock, Jordan AG; Witts, James D; Gao, Yang; Peshek, Catherine; Myers, Corinne E; Henkes, Gregory; Sharp, Zachary D (July 2024, Geological Society of America Bulletin)

   Fossiliferous carbonate concretions are commonly found in sediments deposited in the Late Cretaceous Western Interior Seaway. Although concretions are diagenetic features, well-preserved fossils from within them have been instrumental in reconstructing the temperature and δ18O value of Western Interior Seaway seawater, which is essential for accurate reconstruction of Late Cretaceous climate. Here, we constrain formation conditions of Late Campanian and early Maastrichtian carbonate concretions by combining triple oxygen isotope measurements with carbonate clumped isotope paleothermometry on different carbonate phases within the concretions. We measured both fossil skeletal aragonite and sparry calcite infill from cracks and within macrofossil voids to evaluate differences between “primary” and “altered” geochemical signals. Based on the two temperature-sensitive isotope systems of the primary fossil shell aragonite, the temperature of the Western Interior Seaway was between 20 °C and 40 °C and was likely thermally stratified during the Campanian. The reconstructed δ18Oseawater values of ∼−1‰ for Campanian Western Interior Seaway waters are similar to those expected for the open ocean during greenhouse climates, while the Maastrichtian Western Interior Seaway may have been more restricted, with a δ18Oseawater value of ∼2‰, which reflects more evaporative conditions. We reconstructed the diagenetic history of the sparry infill and altered fossils using a fluid-rock mixing model. Alteration temperature, alteration fluid δ18O value, and the initial formation temperature were calculated by applying the fluid-rock mixing model to a particle swarm optimization algorithm. We found a different range of initial formation temperatures between the Campanian (25−38 °C) and Maastrichtian (9−28 °C). We also found that alteration in the presence of light meteoric fluids (δ18O ≈ −10‰) is required to explain both the sparry infill and the altered fossil isotopic values. Based on our results, both lithification and alteration of the carbonates occurred soon after burial, and light meteoric fluids support prior findings that high-topographic relief existed on the western margin of the Western Interior Seaway during the Late Cretaceous. As one of the first studies to apply these techniques in concert and across multiple mineralogical phases within samples, our results provide important constraints on paleoenvironmental conditions in an enigmatic ocean system and will improve interpretations of the overall health of ecosystems leading into the end-Cretaceous mass extinction. 

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2. Northwest Greenland Aquatic Moss and Water Isotopes Modern Calibration Data, 2022

   https://doi.org/10.18739/A2QV3C564  

   Puleo, Peter; Akers, Pete; Kopec, Ben; Welker, Jeffrey; Bailey, Hannah; Osburn, Magdalena; Riis, Tenna; Axford, Yarrow (January 2024, NSF Arctic Data Center)

   This dataset contains the raw data associated with the manuscript entitled: Aquatic Moss δ18O as a Proxy for Seasonally Resolved Lake Water δ18O, Northwest Greenland (Puleo et al., 2024). Reconstructing past climate seasonality is fundamental to understanding the nature of past climate changes. This is especially true in the Arctic, where climate is intensely seasonal and proxies that can distinguish climate conditions of multiple seasons in a single year are relatively rare. We propose that submerged aquatic mosses, which are abundant subfossils in some Arctic lake sediments and have distinctive seasonal growth morphologies, can be used to estimate past lake water oxygen isotope composition (δ18Olw) across multiple seasons. Aquatic mosses are abundant, well preserved, and grow continuously in Arctic lakes whenever light is available, with some species displaying unique seasonal morphologies influenced by water temperature. Although Greenland paleorecords support that aquatic moss oxygen isotope values (δ18Oom) reflect the δ18O values of lake water, no modern calibration between δ18Oom and δ18Olw exists in Greenland, as aquatic moss samples are composed largely, but not entirely, of cellulose. We present a modern δ18Oom vs. δ18Olw calibration using multiple moss species or morphotypes from eight lakes and ponds near Pituffik (Thule), northwest Greenland. We find strong linear relationships between the δ18Oom and δ18Olw values of multiple species or morphotypes across the range of relatively low δ18Olw values at Pituffik, and our results indicate isotopic fractionations are similar to those found previously at lower latitudes. To assess the potential of mosses as archives of seasonal δ18Olw values, we analyzed δ18Oom in season-specific segments of moss strands, with seasons identified based upon growth morphology. Moss inferred lake water δ18O values (δ18Olwom) are higher in autumn than spring or summer, likely due to increasing contributions of isotopically heavier precipitation and the cumulative effects of lake water evaporation throughout the ice-free season. For moss subsampled throughout summer, δ18Olwom values generally increased through the season in parallel with observed δ18Olw values. Potential temperature dependent fractionation effects during biosynthesis, however, remain unconstrained and should be further addressed with future research. Overall, these findings suggest that aquatic mosses from lake sediments could be used to directly resolve climate seasonality of the past. Puleo, P.J.K., Akers, P.D., Kopec, B.G., Welker, J.M., Bailey, H., Osburn, M.R., Riis, T., Axford, Y., 2024. Aquatic moss δ18O as a proxy for seasonally resolved lake water δ18O, northwest Greenland. Quaternary Science Reviews 334, 1-11. 

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3. Simulation of oxygen isotopes and circulation in a late Carboniferous epicontinental sea with implications for proxy records

   https://doi.org/10.1016/j.epsl.2021.116770  

   Macarewich, Sophia I.; Poulsen, Christopher J.; Montañez, Isabel P. (April 2021, Earth and Planetary Science Letters)

   Reconstructions of ancient ocean chemistry are largely based on geochemical proxies obtained from epicontinental seas. Mounting evidence suggests that these shallow inland seas were chemically distinct from the nearby open ocean, decoupling epicontinental records from broader ocean conditions. Here we use the isotope-enabled Community Earth System Model to evaluate the extent to which the oxygen isotopic composition of the late Carboniferous epicontinental sea, the North American Midcontinent Sea (NAMS), reflects the chemistry of its open-ocean sources and connect epicontinental isotope variability in the sea to large-scale ocean-atmosphere processes. Model results support estuarine-like circulation patterns demonstrated by past empirical studies and suggest that orographic runoff produced decreases in surface seawater δ18O (δ18Ow) of up to ∼3between the NAMS and the bordering ocean. Simulated sea surface temperatures are relatively constant across the sea and broadly reproduced from proxy-based δ18O paleotemperatures for which model-based values of epicontinental δ18Oware used, indicating that offshore-onshore variability in surface proxy δ18O is primarily influenced by seawater freshening. Simulated bottom water temperatures in the NAMS are also reproduced from biogenic calcite δ18O using model-based values of epicontinental δ18Ow, suggesting that benthic marine fossil δ18O is also influenced by seawater freshening and coastal upwelling. In addition, glacial-interglacial variations in nearshore seawater freshening counteract the effects of temperature on marine biogenic δ18O values, suggesting that salinity effects should be considered in δ18O-based estimates of glacioeustatic sea level change from nearshore regions of the NAMS. Our results emphasize the importance of constraining epicontinental dynamics for interpretations of marine biogenic δ18O as proxies of paleotemperature, salinity, and glacioeustasy. 

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4. Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates

   https://doi.org/10.1016/j.gca.2023.11.017  

   Parvez, Zeeshan A.; El-Shenawy, Mohammed I.; Lucarelli, Jamie K.; Kim, Sang-Tae; Johnson, Kathleen R.; Wright, Kevin; Gebregiorgis, Daniel; Montanez, Isabel P.; Wortham, Barbara; Asrat, Asfawossen; et al (February 2024, Geochimica et Cosmochimica Acta)

   Cave carbonate minerals are an important terrestrial paleoclimate archive. A few studies have explored the potential for applying carbonate clumped isotope thermometry to speleothems as a tool for constraining past temperatures. To date, most papers utilizing this method have focused on mass-47 clumped isotope values (Δ47) at a single location and reported that cave carbonate minerals rarely achieve isotopic equilibrium, with kinetic isotope effects (KIEs) attributed to CO2 degassing. More recently, studies have shown that mass-47 and mass-48 CO2 from acid digested carbonate minerals (Δ47 and Δ48) can be used together to assess equilibrium and probe KIEs. Here, we examined 44 natural and synthetic modern cave carbonate mineral samples from 13 localities with varying environmental conditions (ventilation, water level, pCO2, temperature) for (dis)equilibrium using Δ47-Δ48 values, in concert with traditional stable carbon (δ13C) and oxygen (δ18O) isotope ratios. Data showed that 19 of 44 samples exhibited Δ47-Δ48 values indistinguishable from isotopic equilibrium, and 18 (95 %) of these samples yield Δ47-predicted temperatures within error of measured modern temperatures. Conversely, 25 samples exhibited isotopic disequilibria, 13 of which yield erroneous temperature estimates. Within some speleothemsamples, we find Δ47-Δ48 values consistent with CO2 degassing effects, however, the majority of sampleswith KIEs are consistent with other processes being dominant. We hypothesize that these values reflect isotopicbuffering effects on clumped isotopes that can be considerable and cannot be overlooked. Using a Raleigh Distillation Model, we examined carbon and oxygen isotope exchange trajectories and their relationships with dual clumped isotope disequilibria. Carbon isotope exchange is associated with depletion of both Δ47 and Δ48 relative to equilibrium, while oxygen isotope exchange is associated with enrichment of both Δ47 and Δ48 relative to equilibrium. Cave rafts collected from proximate locations in Mexico exhibit the largest averagedepartures from equilibrium (ΔΔ47 = − 0.032 ± 0.007, ΔΔ48 = − 0.104 ± 0.035, where ΔΔi is the measured value – the equilibrium value). This study shows how the Δ47-Δ48 dual carbonate clumped isotope framework can be applied to a variety of tcave carbonate mineral samples, enabling identification of isotopic equilibria and therefore quantitative application of clumped isotope thermometry for paleoclimate reconstruction, or alternatively, constraining the mechanisms of kinetic effects. 

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5. Eastern Canadian Arctic Lake water Isotope Samples, 1992-2021

   https://doi.org/10.18739/A2S756N13  

   Gorbey, Devon; Thomas, Elizabeth K (April 2025, NSF Arctic Data Center)

   Lacustrine δ2H and δ18O isotope proxies are powerful tools for reconstructing past climate and precipitation changes in the Arctic. However, robust paleoclimate record interpretations depend on site-specific lake water isotope systematics, which are poorly described in the eastern Canadian Arctic due to insufficient modern lake water isotope data. We use modern lake water isotopes (δ18O and δ2H) collected between 1994-1997 and 2017–2021 from a transect of sites spanning a Québec-to-Ellesmere Island gradient to evaluate the effects of inflow seasonality and evaporative enrichment on the δ2H and δ18O composition of lake water. Four lakes near Iqaluit, Nunavut sampled biweekly through three ice-free seasons reflect mean annual precipitation isotopes with slight evaporative enrichment. In a 23° latitudinal transect of 181 lakes, through-flowing lake water δ2H and δ18O fall along local meteoric water lines. Despite variability within each region, we observe a latitudinal pattern: southern lakes reflect mean annual precipitation isotopes, whereas northern lakes reflect summer-biased precipitation isotopes. This pattern suggests that northern lakes are more fully flushed with summer precipitation, and we hypothesize that this occurs because the ratio of runoff to precipitation increases with latitude as vegetation cover decreases. Therefore, proxy records from through-flowing lakes in this region should reflect precipitation isotopes with minimal influence of evaporation, but vegetation changes in lake catchments across a latitudinal transect and through geologic time may influence the seasonality of lake water isotopic compositions. Thus, we recommend that future lake water isotope proxy records are considered in context with temperature and ecological proxy records. 

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