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Abstract: Subaqueous carbonates from the Devils Hole caves (southwestern USA) provide a continuous Holocene to Pleistocene North American paleoclimate record. The accuracy of this record relies on two assumptions: That carbonates precipitated close to isotope equilibrium and that groundwater temperature did not change significantly in the last 570 thousand years. Here, we investigate these assumptions using dual clumped isotope thermometry. This method relies on simultaneous analyses of carbonate ∆47 and ∆48 values and provides information on the existence and extent of kinetic isotope fractionation. Our results confirm the hypothesis that calcite precipitation occurred close to oxygen and clumped isotope equilibrium during the last half million years in Devils Hole. In addition, we provide evidence that aquifer temperatures varied by less than ±1°C during this interval. Thus, the Devils Hole calcite δ18O time series exclusively represents changes in groundwater δ18O values. Plain Language Summary: The oxygen isotope composition of cave carbonates records changes in Earth's climate. However, the reliability of such records depends on how stable the carbonate precipitation environment was. Here, we use a novel method called dual clumped isotope thermometry that can provide simultaneous information on a carbonate's growth temperature and whether any additional fractionation processes affected its oxygen and clumped isotope signatures. Specifically, we investigated the Devils Hole caves, which provide a reference oxygen isotope time series for North America. We find that groundwater temperature did not change significantly in the last half-million years. Variations in the oxygen isotope composition of the deposited carbonates solely reflect variations in the oxygen isotope composition of the groundwater.
Triple oxygen isotope measurements are an emerging tool in paleoclimate reconstructions. In this contribution we develop the application of triple oxygen isotope measurements to lacustrine sediments to reconstruct past elevations. We focus on a well-constrained sample set from the Eocene North American Cordillera (Cherty Limestone Formation, Elko Basin, NV, United States, 42–43.5 Ma) on the east side of the elevated Nevadaplano. We present triple oxygen isotope measurements on freshwater lacustrine chert samples from the Cherty Limestone Formation. Across an evaporation trend spanning 6.5‰ in δ18O values we observe a negative correlation with Δ′17O ranging from −0.066 to −0.111‰ (λRL = 0.528), with an empirical slope (λchert, δ′17O vs. δ′18O) of 0.5236. Additionally, we present new carbonate clumped isotope (Δ47) temperature results on the overlying fluvial-lacustrine Elko Formation, which indicate an error-weighted mean temperature of 32.5 ± 3.8°C (1σ), and evaporatively enriched lake water spanning δ18O values of −3.7 to +3.5‰ (VSMOW). Paired chert and carbonate δ18O values demonstrate that co-equilbrium among the carbonate and chert phases is unlikely. Thus, as also previously suggested, it is most likely that Elko Basin chert formed during early diagenesis in equilbirium with pore waters that reflect evaporatively 18O-enriched lake water. Using this scenario we apply a model for back-calculating unevaporated water composition to derive a source water of δ′18O = −16.1‰ (VSMOW), similar to modern local meteoric waters but lower than previous work on paired δ18O- δD measurements from the same chert samples. Further, this back-calculated unevaporated source water is higher than those derived using δD measurements of Late Eocene hydrated volcanic glass from the Elko Basin (average δ′18O equivalent of approximately −18.4‰, VSMOW). This suggests, assuming Eocene meteoric water Δ′17O values similar to today (∼0.032‰), either that: (1) the hypsometric mean elevation recorded by the lacustrine Cherty Limestone was lower than that derived from the average of the volcanic glass δD measurements alone; or (2) there was hydrogen exchange in volcanic glass with later low δD meteoric fluids. Nonetheless, our new findings support a relatively high (∼2.5–3 km) plateau recorded in the Elko Basin during the mid-Eocene.
Reconstructing Oligocene-Miocene paleoelevation contributes to our understanding of the evolutionary history of the European Alps and sheds light on geodynamic and Earth’s surface processes involved in the development of Alpine topography. Despite being one of the most intensively explored mountain ranges worldwide, constraints on the elevation history of the European Alps, however, remain scarce. Here we present stable and clumped isotope geochemistry 15 measurements to provide a new paleoelevation estimate for the mid-Miocene (~14.5 Ma) European Central Alps. We apply stable isotope δ-δ paleoaltimetry on near sea level pedogenic carbonate oxygen isotope (δ18O) records from the Northern Alpine Foreland Basin (Swiss Molasse Basin) and high-Alpine phyllosilicate hydrogen isotope (δD) records from the Simplon Fault Zone (Swiss Alps). We further explore Miocene paleoclimate and paleoenvironmental conditions in the Swiss Molasse Basin through carbonate stable (δ18O, δ13C) and clumped (Δ47) isotope data from three foreland basin sections in different 20 alluvial megafan settings (proximal, mid-fan, and distal). Combined pedogenic carbonate δ18O values and Δ47 temperatures (30 ± 5°C) yield a near sea level precipitation δ18Ow value of -5.8 ± 0.2‰ and in conjunction with the high-Alpine phyllosilicate δD record suggest that the region surrounding the SFZ attained surface elevations of >4000 m no later than the mid-Miocene. Our near sea level δ18Ow estimate is supported by paleoclimate (iGCM Echam5-wiso) modeled δ18O values, which vary between -4.2 and -7.6‰ for the Northern Alpine Foreland Basin.
Reconstructing Oligocene–Miocene paleoelevation contributes to our understanding of the evolutionary history of the European Alps and sheds light on geodynamic and Earth surface processes involved in the development of Alpine topography. Despite being one of the most intensively explored mountain ranges worldwide, constraints on the elevation history of the European Alps remain scarce. Here we present stable and clumped isotope measurements to provide a new paleoelevation estimate for the mid-Miocene (∼14.5 Ma) European Central Alps. We apply stable isotope δ–δ paleoaltimetry to near-sea-level pedogenic carbonate oxygen isotope (δ18O) records from the Northern Alpine Foreland Basin (Swiss Molasse Basin) and high-Alpine phyllosilicate hydrogen isotope (δD) records from the Simplon Fault Zone (Swiss Alps). We further explore Miocene paleoclimate and paleoenvironmental conditions in the Swiss Molasse Basin through carbonate stable (δ18O, δ13C) and clumped (Δ47) isotope data from three foreland basin sections in different alluvial megafan settings (proximal, mid-fan, and distal). Combined pedogenic carbonate δ18O values and Δ47 temperatures (30±5 ∘C) yield a near-sea-level precipitation δ18Ow value of ‰ and, in conjunction with the high-Alpine phyllosilicate δD value of ‰, suggest that the region surrounding the Simplon Fault Zone attained surface elevations of >4000 m no later than the mid-Miocene. Our near-sea-level δ18Ow estimate is supported by paleoclimate (iGCM ECHAM5-wiso) modeled δ18O values, which vary between −4.2 ‰ and −7.6 ‰ for the Northern Alpine Foreland Basin.