0000000000445236
AUTHOR
Maximilian Hansen
Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model
Abstract Speleothem stable carbon isotope (δ 13 C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ 13 C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO 2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gase…
Are oxygen isotope fractionation factors between calcite and water derived from speleothems systematically biased due to prior calcite precipitation (PCP)?
Abstract 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 i…
The effects of drip rate and geometry on the isotopic composition of speleothems: Evaluation with an advection-diffusion-reaction model
Abstract The curvature and slope of speleothem surfaces have been shown to affect the reaction rates in the aqueous carbonate system by altering the thickness of the CaCO3-precipitating solution. However, the effects of speleothem geometry and drip rate on the speleothem’s carbon and oxygen isotopic composition have yet to be investigated. Over more strongly sloping surfaces, solutions are thinner and flow faster. The effects of thinner and faster-flowing solutions on the isotopic composition of carbonate minerals precipitated from these solutions are of opposite sense. Thinner solutions enhance rates of CO2 degassing and mineral formation, increasing the degree of isotopic distillation of …
Chemical evolution of dissolved inorganic carbon species flowing in thin water films and its implications for (rapid) degassing of CO2 during speleothem growth
Abstract Rapid degassing of CO2 from a thin film of drip water on the surface of stalagmites is often considered to have a large effect on both speleothem growth and stable isotope values and is offered as an explanation for higher δ13C and δ18O values than expected under conditions of stable isotope equilibrium. However, the time constant for degassing of CO2 from the solution only depends on film thickness and the coefficient of molecular diffusion for CO2. Thus, for thin films, the time for degassing of CO2 is much shorter than the time for subsequent equilibration of the dissolved carbon species and precipitation of CaCO3. In this context, degassing of CO2 is always fast. Here we presen…
Calcite Mg and Sr partition coefficients in cave environments: Implications for interpreting prior calcite precipitation in speleothems
Abstract Trace element to Ca ratios in speleothems have emerged as important proxies that reflect local environmental conditions. However, interpretations of speleothem trace element records can be challenging due to various processes. Positive correlations between speleothem Mg/Ca and Sr/Ca have often been interpreted to reflect prior calcite precipitation (PCP), a process potentially modulated by rainfall variability. For quantitative interpretation of PCP, the distribution coefficients for Mg and Sr (DMg and DSr) are required. Here, we use ten cave monitoring calcite and drip water datasets to investigate the influence of temperature and drip water and calcite Mg/Ca and Sr/Ca ratios on s…
Effects of organic matter complexation on partitioning of transition metals into calcite: Cave-analogue crystal growth experiments
We highlight the potential for first row transition metals to carry paleohydrological signals in speleothems, and argue that these metals constitute valuable proxies for climate reconstructions. Metal availability to speleothems is hypothesised to be restricted by organic complexation, which strongly limits the free ion activity of transition metals (Co2+, Ni2+ and Cu2+) in dripwater, thereby creating a kinetic overprint on metal concentrations and isotope ratios in speleothem calcite. This study presents the results of the first cave-analogue experiments of transition metal partitioning into calcite in the absence and presence of organic ligands. The Geological Microclimate (GeoMic) system…
Simulating speleothem growth in the laboratory: Determination of the stable isotope fractionation (δ13C and δ18O) between H2O, DIC and CaCO3
Abstract Here we present novel cave-analogue experiments directly investigating stable carbon and oxygen isotope fractionation between the major involved species of the carbonate system (HCO3−, CO2, CaCO3 and H2O). In these experiments, which were performed under controlled conditions inside a climate box, a thin film of solution flew down an inclined marble or glass plate. After different distances of flow and, thus, residence times on the plate, pH, electrical conductivity, supersaturation with respect to calcite, precipitation rate as well as the δ18O and δ13C values of the dissolved inorganic carbon (DIC) and the precipitated CaCO3 were obtained. Progressive precipitation of CaCO3 along…
Processes affecting the stable isotope composition of calcite during precipitation on the surface of stalagmites: Laboratory experiments investigating the isotope exchange between DIC in the solution layer on top of a speleothem and the CO2 of the cave atmosphere
Abstract We present a theoretical derivation of the exchange time, τex, needed to establish isotopic equilibrium between atmospheric CO2 in a cave and HCO3− dissolved in a thin water film covering the surface of a speleothem. The result is τ ex = τ red ex · [ HCO 3 - ] K H · p CO 2 cave , where τ red ex depends on the depth, a, of the water film and on temperature. [ HCO 3 - ] is the concentration of bicarbonate, p CO 2 cave the partial pressure of CO2, and KH is Henry’s constant. To test the theory we prepared stagnant or flowing thin films of a NaHCO3 solution and exposed them at 20 °C to an CO2 containing atmosphere of p CO 2 500, 12,500, or 25,000 ppmV and defined isotope composition. T…