Isotopes in Speleothems: Methods and Application

Abstract

Speleothems (cave carbonate deposits) have been recognized as a multi-proxy paleoclimate archive. Variations in carbon and oxygen isotopes in speleothems can record past climate changes (e.g., temperature, rainfall and vegetation) under isotopic equilibrium conditions. However, non-climatic noises caused by in-cave processes may affect these stable isotope records under non-equilibrium isotopic conditions. The identification of equilibrium and non-equilibrium isotopic conditions in speleothems is still disputed in the speleothem research community; however, this is a prerequisite for the interpretation of carbon and oxygen isotope records in speleothems as paleoclimate proxies. In this Ph.D. thesis, a series of laboratory experiments under cave-analogue conditions were performed to simulate the formation of speleothems in natural caves. The results of these experiments demonstrate that stable isotope equilibrium in speleothems is achieved under slow carbonate precipitation in pool-like settings (pool carbonates). On the basis of these pool carbonates, equilibrium carbon and oxygen isotope fractionation factors between calcite and water (or DIC for carbon) were determined. Our experiments show larger carbon and oxygen isotope non-equilibrium fractionations between calcite and water (or DIC for carbon) in stalagmite-like settings (fast carbonate precipitate) than those determined in pool-like settings. The flow rate of drip water above the surface of stalagmite appears to control the magnitude of these non-equilibrium isotope effects which increase with decreasing the flow rate. Furthermore, a natural speleothem sample was examined as a paleoclimate archive in this thesis. The growth of a double stalagmite (WS-5d) in Wadi Sannur Cave from the Northeastern Sahara was used to infer the greening of the Sahara (intensive rainfall and vegetation). The U/Th dating in the WS-5d stalagmite suggests that greening conditions extended widely in the Sahara during the interglacial Marine Isotope Stages MIS 5.5, MIS 7.3, and the early MIS 9. Based upon oxygen isotope compositions from the WS-5d, we attributed the source of these greening periods to long-traveling rains from the Atlantic Ocean that were delivered via the West African monsoon system. Our study suggests that the two youngest greening periods were concurrent with the arrival of Homo sapiens in the Levant and an earlier possible change in human population at 244 ka, indicating a key role of the Sahara route in early human dispersal out of Africa. Finally, clumped isotope measurements (Δ47) on carbonate-derived CO2 have been shown to reflect the formation temperature of the carbonate minerals. The absolute Δ47 values of these isotopic measurements seem to be sensitive to the standardization methods (heated CO2 gases and water-equilibrated CO2 gases) that are used to normalize the raw Δ47 measurements. Neither the hypothetical base for the heated CO2 gas standardization method nor the theoretical base for the water-equilibrated CO2 gas standardization method has been experimentally tested. A series of CO2 gases were heated in pre-dehumidified quartz tubes to obtain equilibrium Δ47 values of these CO2 gases at temperature range of 50 – 1100 °C. Consequently, the first experimentally derived Δ47 – T calibration in a CO2 gas phase was proposed. This experimental calibration provides a validated base for the standardization of the raw Δ47 data. Moreover, heating CO2 in a pre-humidified quartz tube enables us to easily prepare a CO2 standard gas of a similar Δ47 value to the CO2 sample (i.e., similar Δ47 correction matrix). This will lead to an improvement in the correction scheme of the carbonate clumped isotope thermometry and reliably adjust the absolute Δ47 scale.