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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. 

Abstract Estimates of the permafrost-climate feedback vary in magnitude and sign, partly because permafrost carbon stability in warmer-than-present conditions is not well constrained. Here we use a Plio-Pleistocene lacustrine reconstruction of mean annual air temperature (MAAT) from the Tibetan Plateau, the largest alpine permafrost region on the Earth, to constrain past and future changes in permafrost carbon storage. Clumped isotope-temperatures (Δ 47 -T) indicate warmer MAAT (~1.2 °C) prior to 2.7 Ma, and support a permafrost-free environment on the northern Tibetan Plateau in a warmer-than-present climate. Δ 47 -T indicate ~8.1 °C cooling from 2.7 Ma, coincident with Northern Hemisphere glacial intensification. Combined with climate models and global permafrost distribution, these results indicate, under conditions similar to mid-Pliocene Warm period (3.3–3.0 Ma), ~60% of alpine permafrost containing ~85 petagrams of carbon may be vulnerable to thawing compared to ~20% of circumarctic permafrost. This estimate highlights ~25% of permafrost carbon and the permafrost-climate feedback could originate in alpine areas. 

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 CO₂beyond 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 CO₂record 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 CO₂thresholds in biological and cryosphere evolution.

 

Estimates of global mean near‐surface air temperature (global SAT) for the Cenozoic era rely largely on paleo‐proxy data of deep‐sea temperature (DST), with the assumption that changes in global SAT covary with changes in the global mean deep‐sea temperature (global DST) and global mean sea‐surface temperature (global SST). We tested the validity of this assumption by analyzing the relationship between global SST, SAT, and DST using 25 different model simulations from the Deep‐Time Model Intercomparison Project simulating the early Eocene Climatic Optimum (EECO) with varying CO₂levels. Similar to the modern situation, we find limited spatial variability in DST, indicating that local DST estimates can be regarded as a first order representative of global DST. In line with previously assumed relationships, linear regression analysis indicates that both global DST and SAT respond stronger to changes in atmospheric CO₂than global SST by a similar factor. Consequently, this model‐based analysis validates the assumption that changes in global DST can be used to estimate changes in global SAT during the early Cenozoic. Paleo‐proxy estimates of global DST, SST, and SAT during EECO show the best fit with model simulations with a 1,680 ppm atmospheric CO₂level. This matches paleo‐proxies of EECO atmospheric CO₂, indicating a good fit between models and proxy‐data.

 

Since the last glacial period, North America has experienced dramatic changes in regional climate, including the collapse of ice sheets and changes in precipitation. We use clumped isotope (∆₄₇) thermometry and carbonate δ¹⁸O measurements of glacial and deglacial pedogenic carbonates from the Palouse Loess to provide constraints on hydroclimate changes in the Pacific Northwest. We also employ analysis of climate model simulations to help us further provide constraints on the hydroclimate changes in the Pacific Northwest. The coldest clumped isotope soil temperaturesT(₄₇) (13.5 ± 1.9°C to 17.1 ± 1.7°C) occurred ∼34,000–23,000 years ago. Using a soil‐to‐air temperature transfer function, we estimate Last Glacial Maximum (LGM) mean annual air temperatures of ∼−5.5°C and warmest average monthly temperatures (i.e., mean summer air temperatures) of ∼4.4°C. These data indicate a regional warming of 16.4 ± 2.6°C from the LGM to the modern temperatures of 10.9°C, which was about 2.5–3 times the global average. Proxy data provide locality constraints on the boundary of the cooler anticyclone induced by LGM ice sheets, and the warmer cyclone in the Eastern Pacific Ocean. Climate model analysis suggests regional amplification of temperature anomalies is due to the proximal location of the study area to the Laurentide Ice Sheet margin and the impact of the glacial anticyclone on the region, as well as local albedo. Isotope‐enabled model experiments indicate variations in water δ¹⁸O largely reflect atmospheric circulation changes and enhanced rainout upstream that brings more depleted vapor to the region during the LGM.