Stable isotopes in pedogenic calcite: Can the positive linear covariant trends be used to quantify paleo-evaporation rates?

Paleoclimatological models suggest enhanced evaporation rates in subtropical regions during greenhouse- world conditions. Laboratory evaporation experiments show that calcites precipitated from variably saturated solutions yield a positive linear covariant trend (PLCT) in δ18O vs δ13C values. This investigation experimentally quantifies calcite PLCT so that δ13C of subtropical paleosol calcretes may be used as a regional proxy of paleo-evaporation rates. A series of powdered CaCO3 samples with δ18O and δ13C values of -19.6‰ and -37.2‰ VPDB respectively were dissolved in deionized water in a pressure sealed container; it also contained separate vials of calcite reacted with HCl to generate a range of pCO2 environments, thus simulating a soil atmosphere. The variable pCO2 conditions simulate expected soil atmosphere pCO2 conditions in a calcrete horizon during alternative phases of calcite dissolution and precipitation. After 24 hrs, the solutions were placed in an open beaker in an incubator at 36°C and allowed to evaporate. Aliquots of 100 μL were removed at 24 hr intervals and the time of calcite crystal nucleation was also noted. Water analyses yielded δ18O enrichments ranging from an initial value of -4.8‰ VSMOW to a range of +10.0‰ to +14.8‰ VSMOW after an evaporation period of 75 hrs. The most enriched water values were attained from the solutions formed under lower pCO2 conditions (more enriched calcite δ18O, δ13C). The array of calcite δ18O vs δ13C values fall upon a PLCT that projects from a theoretical meteoric calcite line (MCL) calculated from the incubation temperature and deionized water δ18O and δ13C values. The precipitated calcite δ18O values range from the MCL value of -8.8‰ VPDB to +0.5‰ VPDB. The higher pCO2 waters precipitated calcite very early during evaporation, and thus the δ18O and δ13C calcite values are slightly enriched relative to the theoretical MCL. The lower pCO2 conditions precipitated calcite late in the evaporation of the fluids, and thus yield more enriched calcite δ18O and δ13C values. Ongoing experiments under warmer and cooler evaporation temperatures will aid in the development of a quantitative model for paleo-evaporation rates from paleosol calcretes.