Constraining speleothem oxygen isotope disequilibrium driven by rapid CO2 degassing and calcite precipitation: Insights from monitoring and modeling

Abstract Oxygen isotopes are the most commonly applied speleothem proxy for reconstructing Quaternary changes in precipitation and/or temperature. These interpretations are either limited to qualitative wetting and drying trends or rely on theoretical, experimental and/or empirical equilibrium isotope fractionation factors for more quantitative constraints. These various fractionation factors have similar temperature sensitivities, but their absolute values differ, and cave calcite does not appear to generally precipitate in isotopic equilibrium with its drip water. Rapid CO2 degassing paired with calcite precipitation, both occurring under disequilibrium conditions, are a set of mechanisms…

Late Quaternary Variations in the South American Monsoon System as Inferred by Speleothems – New Perspectives Using the SISAL Database

Here we present an overview of speleothem δ18O records from South America, most of which are available in the Speleothem Isotopes Synthesis and Analysis (SISAL_v1) database. South American tropical and subtropical speleothem δ18O time series are primarily interpreted to reflect changes in precipitation amount, the amount effect, and consequently history of convection intensity variability of convergence zones such as the Intertropical Convergence Zone (ITCZ) and the South America Monsoon System (SAMS). We investigate past hydroclimate scenarios in South America related to the South American Monsoon System in three different time periods: Late Pleistocene, Holocene, and the last two millenni…

Isotope disequilibrium effects: The influence of evaporation and ventilation effects on the carbon and oxygen isotope composition of speleothems – A model approach

Abstract In order to improve the understanding of variations of speleothem δ18O and δ13C values in the context of palaeoclimate research, it is important to quantify the isotope fractionation processes influencing the δ18O and δ13C values of stalagmites. Here we present an extended version of speleothem stable isotope model that accounts for evaporation and condensation effects during precipitation of calcite. The ISOLUTION-model allows to calculate the effect of evaporation on δ18Ocalcite and δ13Ccalcite values in dependence on relative humidity and wind velocity. Our results reveal that evaporation may have a significant effect on δ18Ocalcite and δ13Ccalcite due to the loss of H2O from th…

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…

North Atlantic Ice‐Rafting, Ocean and Atmospheric Circulation During the Holocene: Insights From Western Mediterranean Speleothems

In this study, we present a Holocene rainfall index based on three high-resolution speleothem records from the Western Mediterranean, a region under the influence of the westerly winds belt modulated by the North Atlantic Oscillation (NAO). On centennial to millennial timescales, we show that the North Atlantic ice-rafting events were likely associated with negative NAO-like conditions during the Early Holocene and the Late Holocene. However, our data reveal that this is not clearly the case for the mid-Holocene ice-rafting events, during which we also show evidence of positive NAO-like patterns from other paleo-oceanographic and paleo-atmospheric data. Hence, contradictory mechanisms invol…

Cryogenic cave carbonate – a new tool for estimation of the Last Glacial permafrost depth of the Central Europe

Abstract. Cryogenic cave carbonate (CCC) represents a specific type of speleothems, whose precipitation is triggered by freezing of mineralized karst water. Coarse-crystalline CCC, which formed during slow freezing of water in cave pools, is known in 20 Central European caves located in Germany, the Czech Republic, Slovakia and Poland. All these caves are situated in an area, which was glacier-free during the Weichselian. Whereas the formation of usual types of speleothems in caves of this region usually ceased during glacials, CCC precipitation was restricted to glacial periods. Since CCC represents a novel, useful paleoclimate proxy, data from Weichselian CCC occurrences in caves in Centr…

Disequilibrium carbon and oxygen isotope fractionation in recent cave calcite: Comparison of cave precipitates and model data

Abstract Speleothem proxy data provide important information in continental palaeo-climate research due to their precise chronology and wide geographic distribution. Despite a continuously growing number of field and numerical studies designed to study stable isotope fractionation effects, many aspects remain a matter of debate. Here, carbon and oxygen isotope ratios from cave drip water and calcite precipitates sampled on watch glasses in the Bunker Cave (Western Germany) are compared with the values expected for isotopic equilibrium. Furthermore, the field data are compared with the results of a numerical model simulating stalagmite growth and stable isotope ratios. Two drip sites with di…

Late Quaternary Variations in the South American Monsoon System as Inferred by Speleothems—New Perspectives using the SISAL Database

Here we present an overview of speleothem δ18O records from South America, most of which are available in the Speleothem Isotopes Synthesis and Analysis (SISAL_v1) database. South American tropical and subtropical speleothem δ18O time series are primarily interpreted to reflect changes in precipitation amount, the amount effect, and consequently history of convection intensity variability of convergence zones such as the Intertropical Convergence Zone (ITCZ) and the South America Monsoon System (SAMS). We investigate past hydroclimate scenarios in South America related to the South American Monsoon System in three different time periods: Late Pleistocene, Holocene, and the last tw…

The SISAL database: a global resource to document oxygen and carbon isotope records from speleothems

Stable isotope records from speleothems provide information on past climate changes, most particularly information that can be used to reconstruct past changes in precipitation and atmospheric circulation. These records are increasingly being used to provide “out-of-sample” evaluations of isotope-enabled climate models. SISAL (Speleothem Isotope Synthesis and Analysis) is an international working group of the Past Global Changes (PAGES) project. The working group aims to provide a comprehensive compilation of speleothem isotope records for climate reconstruction and model evaluation. The SISAL database contains data for individual speleothems, grouped by cave system. Stable isotopes of oxyg…

Coherent South American Monsoon variability during the last millennium revealed through high‐resolution proxy records

Evidence of warm and humid interstadials in central Europe during early MIS 3 revealed by a multi-proxy speleothem record

Marine Isotope Stage 3 (MIS 3, 57-27 ka) was characterised by numerous rapid climate oscillations (i.e., Dansgaard-Oeschger (D/O-) events), which are reflected in various climate archives. So far, MIS 3 speleothem records from central Europe have mainly been restricted to caves located beneath temperate Alpine glaciers or close to the Atlantic Ocean. Thus, MIS 3 seemed to be too cold and dry to enable speleothem growth north of the Alps in central Europe. Here we present a new speleothem record from Bunker Cave, Germany, which shows two distinct growth phases from 52.0 (+0.8, -0.5) to 50.9 (+0.6, -1.3) ka and 473 (+1.0, -0.6) to 42.8 (+/- 0.9) ka, rejecting this hypothesis. These two growth…

Coarsely crystalline cryogenic cave carbonate – a new archive to estimate the Last Glacial minimum permafrost depth in Central Europe

Abstract. Cryogenic cave carbonate (CCC) represents a specific type of speleothem whose precipitation is triggered by freezing of mineralized karst water. Coarsely crystalline CCC, which formed during slow freezing of water in cave pools, has been reported from 20 Central European caves located in Germany, the Czech Republic, Slovakia and Poland. All these caves are situated in an area which was glacier-free during the Weichselian. Whereas the formation of usual types of speleothems in caves of this region usually ceased during the glacials, coarsely crystalline CCC precipitation was restricted to glacial periods. Since this carbonate type represents a novel, useful paleoclimate proxy, data…

Evaluating the potential of tree-ring methodology for cross-dating of three annually laminated stalagmites from Zoolithencave (SE Germany)

Abstract Three small stalagmites from Zoolithencave (southern Germany) show visible laminae, which consist of a clear and a brownish, pigmented layer pair. This potentially provides the opportunity to construct precise chronologies by counting annual laminae. The growth period of the three stalagmites was constrained by the 14C bomb peak in the youngest part of all three stalagmites and 14C-dating of a piece of charcoal in the consolidated base part of stalagmite Zoo-rez-2. These data suggest an age of AD 1970 for the top laminae and a lower age limit of AD 1973–1682 or AD 1735–1778. Laminae were counted and their thickness determined on scanned thin sections of all stalagmites. On stalagmi…

Speleothems from the Middle East: An Example of Water Limited Environments in the SISAL Database

The Middle East (ME) spans the transition between a temperate Mediterranean climate in the Levant to hyper-arid sub-tropical deserts in the southern part of the Arabian Peninsula (AP), with the complex alpine topography in the northeast feeding the Euphrates and Tigris rivers which support life in the Southeastern Fertile Crescent (FC). Climate projections predict severe drying in several parts of the ME in response to global warming, making it important to understand the controls of hydro-climate perturbations in the region. Here we discuss 23 ME speleothem stable oxygen isotope (δ18Occ) records from 16 sites from the SISAL_v1 database (Speleothem Isotope Synthesis and Analysis database), …