Evaluation of meteoric calcite cements as a proxy material for mass-47 clumped isotope thermometry

Meteoric diagenetic cements are ubiquitous throughout geologic history, affecting most carbonate exposures worldwide. They can often be difficult to interpret, as it is usually difficult to separate the influences of water δ18O and temperature on isotopic signals contained within the carbonate rock body. Despite this difficulty in interpretation, meteoric phreatic cements can potentially be a useful proxy material, as they form slowly in equilibrium at mean annual temperature and are not affected by any biogenic effects that can bias other proxy materials.We applied the mass-47 clumped isotope paleothermometer to Pleistocene and Holocene carbonates from Bermuda and Barbados in order to investigate the effects of meteoric diagenesis on Δ47 signals, and to determine their suitability as a paleotemperature proxy. Phreatic calcite cements are found to record the same temperatures as unaltered carbonate sediments, while any sample exhibiting vadose characteristics is biased towards unreasonably hot apparent formation temperatures. Burial heating and re-equilibration are not geologically viable explanations for the anomalously hot temperatures recorded in vadose cements, as neither Bermuda or Barbados has any burial history. Instead, it is likely that precipitation in the vadose zone occurs on timescales quicker than isotopic equilibrium can be achieved, driven by a combination of CO2 degassing and evaporation, which have been previously shown to cause problems in speleothems and pedogenic carbonates.We conclude by suggesting that meteoric phreatic calcites may be an ideal phase for paleotemperature reconstruction, as they accurately record mean annual temperatures and form under equilibrium conditions, while also being resistant to further mineral driven diagenesis. Vadose cements, and any sample likely affected by processes similar to vadose diagenesis, should be avoided for climate reconstructions using the mass-47 clumped isotope thermometer.