Abstract The Δ47 clumped isotope thermometer has been applied to multiple studies aimed at reconstructing the paleoelevation and paleoclimate of sedimentary basins and paleosol sequences. Ideally, this technique directly preserves the temperature of carbonate formation, avoiding any speculation on the composition of surface water from which the carbonate precipitated. Recently, however, concerns about post-depositional alteration of the Δ47 isotope signature from the effects of burial and/or diagenetic alteration have arisen, potentially complicating the application of the Δ47 clumped isotope thermometer for determining paleo-surface temperatures. Here we investigate the effect of burial history on mass-47 clumped isotope. To this purpose we collected samples, from the surface and from drill cores, in two different areas of the Greater Green River basin: the Washakie Basin near Rock Springs, Wyoming and the Green River Basin near Pinedale, Wyoming. Both basins are filled with a thick sequence of Eocene lacustrine strata and the thermal histories of both basins are well documented from petroleum prospecting studies. Clumped isotope Δ47 compositions were measured from lacustrine micritic limestones with a range of peak burial depths from 1 to 6.5 km. For samples from the Washakie Basin that did not experience burial depths exceeding ∼2000 meters, the measured Δ47 values vary from 0.623‰ to 0.684‰, yielding carbonate formation temperatures consistent with previously hypothesized Paleocene-Eocene surface temperatures. In contrast, samples from the Green River Basin, collected from greater burial depths, demonstrate significantly lower Δ47 values (higher temperatures). The consistency of δ18O values and lack of CL evidence for recrystallization suggest closed-system resetting of the clumped isotope thermometer by either partial solid-state re-ordering or carbonate reprecipitation during burial. The Δ47 values of the deeply buried samples have been compared to values derived from recrystallization and temperature history reordering models (THRMs). Both recrystallization and reordering models are successful at predicting Δ47 reordering at burial temperatures >100 °C. These observations, from samples collected from a basin with a remarkably well-constrained thermal history and geothermal gradient, highlight the challenges in elucidating burial histories or diagenetic processes solely from clumped isotopic compositions.
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