0000000000136815

AUTHOR

Detlev K. Richter

Bunker Cave stalagmites: an archive for central European Holocene climate variability

Holocene climate was characterised by variability on multi-centennial to multi-decadal time scales. In central Europe, these fluctuations were most pronounced during winter. Here we present a record of past winter climate variability for the last 10.8 ka based on four speleothems from Bunker Cave, western Germany. Due to its central European location, the cave site is particularly well suited to record changes in precipitation and temperature in response to changes in the North Atlantic realm. We present high-resolution records of δ<sup>18</sup>O, δ<sup>13</sup>C values and Mg/Ca ratios. Changes in the Mg/Ca ratio are attributed to past meteoric p…

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Sensitivity of Bunker Cave to climatic forcings highlighted through multi-annual monitoring of rain-, soil-, and dripwaters

The last two decades have seen a considerable increase in studies using speleothems as archives of past climate variability. Caves under study are now monitored for a wide range of environmental parameters and results placed in contextwith speleothemdata. The present study investigates trends froma seven year longmonitoring of Bunker Cave, northwestern Germany, in order to assess the hydraulic response and transfer time of meteoric water fromthe surface to the cave. Rain-, soil-, and dripwaterwere collected fromAugust 2006 to August 2013 at a monthly to bimonthly resolution and their oxygen and hydrogen isotope composition wasmeasured. Furthermore, drip rates were quantified. Due to differe…

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The magnesium isotope record of cave carbonate archives

Here we explore the potential of magnesium (δ<sup>26</sup>Mg) isotope time-series data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco), the warm-temperate (Germany), the equatorial-humid (Peru) and the cold-humid (Austria) climate zones. Changes in the calcite magnesium isotope signature with time are compared against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a …

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Reconstruction of drip-water δ<sup>18</sup>O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany)

Abstract. The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past dri…

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High‐Resolution Proxy Records From Two Simultaneously Grown Stalagmites From Zoolithencave (Southeastern Germany) and their Potential for Palaeoclimate Reconstruction

Two small annually laminated stalagmites from Zoolithencave (southeastern Germany) grew between CE 1821 and 1970 (Zoo‐rez‐1) and CE 1835 and 1970 (Zoo‐rez‐2), respectively. Trace element concentrations were determined by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA‐ICP‐MS). Samples for δ13C and δ18O analyses were micromilled on annual and subannual resolution. Soil and host rock samples were analyzed by X‐Ray Diffraction (XRD) and their elemental concentrations determined via inductively coupled plasma optical emission spectrometer (ICP‐OES). Trace element concentrations in the stalagmites show two groups in the principal component analyses: one with Mg, Ba, and Sr and an…

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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…

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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…

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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…

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Detection and origin of different types of annual laminae in recent stalagmites from Zoolithencave, southern Germany: Evaluation of the potential for quantitative reconstruction of past precipitation variability

Abstract. An arrangement of three stalagmites from Zoolithencave (southern Germany) was analysed for different types of annual laminae using both microscopic and geochemical methods. The speleothems show visible laminae (consisting of a clear and a brownish, pigmented layer pair) as well as fluorescent and elemental laminae. The age of the speleothems was constrained to 1800 to 1970 AD by 14C-dating of a charcoal piece below the speleothems, detection of the 14C bomb peak, as well as counting of annual laminae. Dating by the 230Th/U-method was impossible due to detrital contamination. On the annual time-scale, the variability of Mg, Ba, and Sr is controlled by Prior Calcite Precipitation (P…

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Reorganization of the North Atlantic Oscillation during early Holocene deglaciation

Laurentide ice-sheet retreat continued into the mid-Holocene. Speleothem-based precipitation records suggest the cessation of melt led to the establishment of the present precipitation patterns associated with the North Atlantic Oscillation. The North Atlantic Oscillation is the dominant atmospheric pressure mode in the North Atlantic region and affects winter temperature and precipitation in the Mediterranean, northwest Europe, Greenland, and Asia1. The index1 that describes the sea-level pressure difference between Iceland and the Azores is correlated with a dipole precipitation pattern over northwest Europe and northwest Africa. How the North Atlantic Oscillation will develop as the Gree…

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Monitoring Bunker Cave (NW Germany): A prerequisite to interpret geochemical proxy data of speleothems from this site

Summary Monitoring cave environments is important to understand processes in karst systems. If stalagmites from a specific cave are used as archives of past climate variability, a quantitative understanding of the soil–karst–speleothem system is crucial. The monitoring program performed in Bunker Cave (NW Germany), which includes monthly collection of climatological data as well as air and water samples from the cave and the overlying soil since 2006, is a prerequisite for the interpretation of speleothem data from the cave in terms of climate variability. The results show that Bunker Cave is a homogeneously ventilated cave with rather low pCO2 values of 580–1200 ppmv, which lacks strong se…

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Hydrogeochemistry and fractionation pathways of Mg isotopes in a continental weathering system: Lessons from field experiments

Abstract The potential of magnesium isotope records from cave carbonate archives (speleothems) has been documented but remains underexplored. This is due to the limited knowledge regarding the complex suite of physico-chemical and biological disequilibrium fractionation processes affecting meteoric fluids in the soil zone, the carbonate hostrock and calcite precipitation in the cave. This study presents δ 26  Mg data from a monitored cave in Germany (Bunker Cave) including rain water (δ 26  Mg: − 0.70 ± 0.14‰), soil water (δ 26  Mg: − 0.51 ± 0.10‰) and drip waters (δ 26  Mg: − 1.65 ± 0.08‰) sampled between November 2009 and May 2011. Field precipitation experiments, i.e., calcite precipitat…

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Unusual internal structure of cm-sized coldwater calcite: Weichselian spars in former pools of the Zinnbergschacht Cave (Franconian Alb/SE Germany)

The investigation of the internal structure of calcite crystals is a new focus in speleothem science, especially in the range of crystallization temperatures close to 0°C. Recently found calcite spars from Zinnbergschacht Cave of the Franconian Alb (SE Germany) are ideal for multi-method investigation. The elongated calcites (up to 6 cm in length) with three to six lateral faces and basal triangular faces at the ends are observed in collapse-zones in the cave. 230Th/U-ages of 38.9 ka suggest formation during the periglacial Weichselian, between the Scandinavian and Alpine Glaciations. The δ18O and δ13C values of the calcite spars vary from -11.18 to -16.11‰ V-PDB and from -4.78 to -6.13‰ V-…

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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…

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Physicochemical characteristics of drip waters: Influence on mineralogy and crystal morphology of recent cave carbonate precipitates

Speleothems are one of the most intensively explored continental archives for palaeoclimate variability. The parameters, however, that control speleothem petrography and its changes with time and space, specifically calcite crystal morphology and carbonate mineralogy, are still poorly understood. In order to shed light on processes and their products, precipitation experiments of recent carbonate crystals on watch glasses and glass plates were performed in seven selected caves. Drip water sites were analysed for their fluid Mg/Ca molar ratio, pH, degree of saturation for calcite and aragonite and drip rates. Corresponding precipitates were analysed with respect to their mineralogy, calcite …

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Coarse-grained cryogenic aragonite as end-member of mineral formation in dolomite caves

Abstract Cryogenic carbonate particles (single crystals and aggregates) have recently been recognized as important witnesses of permafrost dynamics, as they can be used to estimate the thickness and timing of development of permafrost. In this study, the petrography and geochemistry of coarse-grained cryogenic aragonite (CGCAr) identified in Zoolithen Cave in NE Bavaria, Germany, are described in detail for the first time. We provide a sequence of carbonate precipitation during freezing, where CGCAr mark the final crystallization phase in freezing water on ice. Our results support the notion that host rock composition, solution chemistry, and cave ventilation play an important role for arag…

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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…

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Moroccan speleothem and tree ring records suggest a variable positive state of the North Atlantic Oscillation during the Medieval Warm Period

We present a magnesium (Mg) and strontium (Sr) record from an aragonitic speleothem (Grotte de Piste, Morocco, 34‬°N; 04°W) providing a reconstruction of effective rainfall from 619 to 1962 AD. The corresponding drip site was monitored over 2 yr for drip water Mg/Ca and Sr/Ca ratios. Results show evidence for prior aragonite precipitation, which can explain negative correlations between speleothem Mg and Sr concentrations. The data shown here have important climate implications concerning the evolution of the North Atlantic Oscillation (NAO). A comparison of the stalagmite data from Grotte de Piste with an updated tree ring based drought reconstruction from Morocco and other NAO related pro…

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