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Laboratory O2 clumped-isotopic composition data (as Δ36 values) for air occluded in ice core spanning gas ages of 8000-18000 ky BP. O2 clumped isotopic composition data was generated between 2017-2022 at Rice University, Houston, TX, using a Nu Perspective Isotope Ratio Mass Spectrometer (IRMS). Reported data was measured in an Antarctic ice core: West Antarctic Ice Sheet Divide Ice Core (WDC06A) . The chronology and gas ages for the core were obtained from Sigl et al., 2016 (doi:10.5194/cp-12-769-2016) and Buizert et al., 2015 (doi:10.5194/cp-11-153-2015). In addition to O2 clumped isotope data, measured δ18Ο data are also reported. Gas loss corrections to generated Δ36 data are made using previously reported raw δ18O data in Seltzer et al., 2017 (doi:10.5194/cp-13-1323-2017) and established gas loss corrections in Yeung et al., 2012 and Banerjee et al. 2022. 

Field report for Allan Hills ice core drilling and geophysics, field season 2023-2024 

This file includes the clumped-isotope composition (18O18O) molecular oxygen (O2) that is in the trapped air from the S27 ice core collected in Allan Hills Blue Ice Area. 

Abstract The history of tropospheric O₃, an important atmospheric oxidant, is poorly constrained because of uncertainties in its historical budget and a dearth of independent records. Here, we estimate the mean tropospheric O₃burden during the Last Interglacial period (LIG; 115 to 130 thousand years ago) using a record of the clumped isotopic composition of O₂(i.e., Δ₃₆values) preserved in Antarctic ice. The measured LIG Δ₃₆value is 0.03 ± 0.02‰ (95% CI) higher than the late pre‐industrial Holocene (PI; 1,590–1,850 CE) value and corresponds to a modeled 9% reduction in LIG tropospheric O₃burden (95% CI: 3%–15%), caused in part by a substantial reduction in biomass burning emissions during the LIG relative to the PI. These results are consistent with the hypothesis that late‐Pleistocene megafaunal extinctions caused woody and grassy fuels to accumulate on land, leading to enhanced biomass burning in the preindustrial Holocene. 

Abstract Ice cores and other paleotemperature proxies, together with general circulation models, have provided information on past surface temperatures and the atmosphere's composition in different climates. Little is known, however, about past temperatures at high altitudes, which play a crucial role in Earth's radiative energy budget. Paleoclimate records at high‐altitude sites are sparse, and the few that are available show poor agreement with climate model predictions. These disagreements could be due to insufficient spatial coverage, spatiotemporal biases, or model physics; new records that can mitigate or avoid these uncertainties are needed. Here, we constrain the change in upper‐tropospheric temperature at the global scale during the Last Glacial Maximum (LGM) using the clumped‐isotope composition of molecular oxygen trapped in polar ice cores. Aided by global three‐dimensional chemical transport modeling, we exploit the intrinsic temperature sensitivity of the clumped‐isotope composition of atmospheric oxygen to infer that the upper troposphere (effective mean altitude 10–11 km) was 6–9°C cooler during the LGM than during the late preindustrial Holocene. A complementary energy balance approach supports a minor or negligible steepening of atmospheric lapse rates during the LGM, which is consistent with a range of climate model simulations. Proxy‐model disagreements with other high‐altitude records may stem from inaccuracies in regional hydroclimate simulation, possibly related to land‐atmosphere feedbacks. 

Abstract Tropospheric¹⁸O¹⁸O is an emerging proxy for past tropospheric ozone and free‐tropospheric temperatures. The basis of these applications is the idea that isotope‐exchange reactions in the atmosphere drive¹⁸O¹⁸O abundances toward isotopic equilibrium. However, previous work used an offline box‐model framework to explain the¹⁸O¹⁸O budget, approximating the interplay of atmospheric chemistry and transport. This approach, while convenient, has poorly characterized uncertainties. To investigate these uncertainties, and to broaden the applicability of the¹⁸O¹⁸O proxy, we developed a scheme to simulate atmospheric¹⁸O¹⁸O abundances (quantified as ∆₃₆values) online within the GEOS‐Chem chemical transport model. These results are compared to both new and previously published atmospheric observations from the surface to 33 km. Simulations using a simplified O₂isotopic equilibration scheme within GEOS‐Chem show quantitative agreement with measurements only in the middle stratosphere; modeled ∆₃₆values are too high elsewhere. Investigations using a comprehensive model of the O‐O₂‐O₃isotopic photochemical system and proof‐of‐principle experiments suggest that the simple equilibration scheme omits an important pressure dependence to ∆₃₆values: the anomalously efficient titration of¹⁸O¹⁸O to form ozone. Incorporating these effects into the online ∆₃₆calculation scheme in GEOS‐Chem yields quantitative agreement for all available observations. While this previously unidentified bias affects the atmospheric budget of¹⁸O¹⁸O in O₂, the modeled change in the mean tropospheric ∆₃₆value since 1850 CE is only slightly altered; it is still quantitatively consistent with the ice‐core ∆₃₆record, implying that the tropospheric ozone burden increased less than 40% over the twentieth century.