ALBERT

Description: Characterizing the temporal uncertainty in palaeoclimate records is crucial for analysing past climate change, correlating climate events between records, assessing climate periodicities, identifying potential triggers and evaluating climate model simulations. The first global compilation of speleothem isotope records by the SISAL (Speleothem Isotope Synthesis and Analysis) working group showed that age model uncertainties are not systematically reported in the published literature, and these are only available for a limited number of records (ca. 15 %, n=107/691). To improve the usefulness of the SISAL database, we have (i) improved the database's spatio-temporal coverage and (ii) created new chronologies using seven different approaches for age–depth modelling. We have applied these alternative chronologies to the records from the first version of the SISAL database (SISALv1) and to new records compiled since the release of SISALv1. This paper documents the necessary changes in the structure of the SISAL database to accommodate the inclusion of the new age models and their uncertainties as well as the expansion of the database to include new records and the quality-control measures applied. This paper also documents the age–depth model approaches used to calculate the new chronologies. The updated version of the SISAL database (SISALv2) contains isotopic data from 691 speleothem records from 294 cave sites and new age–depth models, including age–depth temporal uncertainties for 512 speleothems. SISALv2 is available at https://doi.org/10.17864/1947.256 (Comas-Bru et al., 2020a).

Description: The equilibrium oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) is an important quantity in stable isotope geochemistry and allows in principle to infer temperature variations from carbonate δ18O if carbonate formation occurred in thermodynamic equilibrium. For this reason, many studies intended to determine the value of the oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) for a wide range of temperatures using modern cave calcite and the corresponding cave drip water or ancient speleothem carbonate and fluid inclusion samples. However, the picture that emerges from all of these studies indicates that speleothem calcite is not formed in thermodynamic equilibrium but under kinetic conditions, provoking a large variability of determined 18αcalcite/H2O values. Here we present a conceptual framework that can explain the variability of 18αcalcite/H2O values obtained by cave studies. Prior calcite precipitation (PCP) is calcite precipitation before cave drip water is dripping from the cave ceiling and impinges on the surface of a stalagmite or watch glass. Prior to the karst water dripping from the cave ceiling, PCP can occur in the karst above the cave as well as on the cave ceiling, the cave walls and on the surface of stalactites. We argue that PCP leads to increasing the δ18O value of the dissolved HCO3- (δ18OHCO3-), resulting in an oxygen isotope disequilibrium of the δ18OHCO3- values with respect to the δ18O value of water (δ18OH2O). The oxygen isotope disequilibrium between HCO3- and H2O is re-equilibrated by oxygen isotope exchange between H2O and HCO3. Depending on the temperature, the re-equilibration time varies from hours to days and is usually much longer than the residence time of the drip water on stalactites, but much shorter than the time required to percolate through the karst. Therefore, while the oxygen isotope equilibrium between HCO3- and H2O is very likely re-established when PCP occurred in the karst, oxygen isotope disequilibrium conditions between HCO3- and H2O still prevail when PCP occurred inside a cave, e.g., on stalactites. If the oxygen isotope disequilibrium conditions between HCO3- and H2O is not re-established, the precipitated calcite will inherit the elevated δ18O value of the HCO3- and not be in oxygen isotope equilibrium with the corresponding drip water. Consequently, if the 18αcalcite/H2O value is calculated from cave calcite samples affected by PCP, the derived value will be systematically biased.

Description: The equilibrium oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) is an important quantity in stable isotope geochemistry and allows in principle to infer temperature variations from carbonate δ18O if carbonate formation occurred in thermodynamic equilibrium. For this reason, many studies intended to determine the value of the oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) for a wide range of temperatures using modern cave calcite and the corresponding cave drip water or ancient speleothem carbonate and fluid inclusion samples. However, the picture that emerges from all of these studies indicates that speleothem calcite is not formed in thermodynamic equilibrium but under kinetic conditions, provoking a large variability of determined 18αcalcite/H2O values. Here we present a conceptual framework that can explain the variability of 18αcalcite/H2O values obtained by cave studies. Prior calcite precipitation (PCP) is calcite precipitation before cave drip water is dripping from the cave ceiling and impinges on the surface of a stalagmite or watch glass. Prior to the karst water dripping from the cave ceiling, PCP can occur in the karst above the cave as well as on the cave ceiling, the cave walls and on the surface of stalactites. We argue that PCP leads to increasing the δ18O value of the dissolved HCO3- (δ18OHCO3-), resulting in an oxygen isotope disequilibrium of the δ18OHCO3- values with respect to the δ18O value of water (δ18OH2O). The oxygen isotope disequilibrium between HCO3- and H2O is re-equilibrated by oxygen isotope exchange between H2O and HCO3. Depending on the temperature, the re-equilibration time varies from hours to days and is usually much longer than the residence time of the drip water on stalactites, but much shorter than the time required to percolate through the karst. Therefore, while the oxygen isotope equilibrium between HCO3- and H2O is very likely re-established when PCP occurred in the karst, oxygen isotope disequilibrium conditions between HCO3- and H2O still prevail when PCP occurred inside a cave, e.g., on stalactites. If the oxygen isotope disequilibrium conditions between HCO3- and H2O is not re-established, the precipitated calcite will inherit the elevated δ18O value of the HCO3- and not be in oxygen isotope equilibrium with the corresponding drip water. Consequently, if the 18αcalcite/H2O value is calculated from cave calcite samples affected by PCP, the derived value will be systematically biased.