230Th/U dating of Last Interglacial brain corals from Bonaire (southern Caribbean) using bulk and theca wall material

Abstract We compared the suitability of two skeletal materials of the Atlantic brain coral Diploria strigosa for 230Th/U-dating: the commonly used bulk material comprising all skeletal elements and the denser theca wall material. Eight fossil corals of presumably Last Interglacial age from Bonaire, southern Caribbean Sea, were investigated, and several sub-samples were dated from each coral. For four corals, both the ages and the activity ratios of the bulk material and theca wall agree within uncertainty. Three corals show significantly older ages for their bulk material than for their theca wall material as well as substantially elevated 232Th content and (230Th/238U) ratios. The bulk mat…

In-situ high spatial resolution LA-MC-ICPMS 230Th/U dating enables detection of small-scale age inversions in speleothems

Abstract We present an in-situ method for Th and U isotope measurements by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) to determine possible age inversions of stalagmites, using a 213 nm Nd:YAG laser connected to an MC-ICPMS. Due to the low ion beam intensity of 230 Th (20–120 counts per second, cps), we carefully optimized the operating parameters to get highest possible ion beam intensities, i.e., laser fluence (25 J cm −2 ), spot size (110 μm), pulse repetition rate (20 Hz), scan speed (4 μm s −1 ), integration time (1000 s), and He and Ar gas flow (∼0.9 L min −1 and ∼0.6 L min −1 respectively). A precision (2 relative standard error, 2RSE) o…

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…

Modelling carbon isotopes of carbonates in cave drip water

Abstract C isotopes in cave drip water are affected by both the C isotope composition of soil air and host rock carbonate. Furthermore, the C isotope composition of cave drip water strongly depends on the calcite dissolution system, i.e., open, closed and intermediate conditions. Here, we present a calcite dissolution model, which calculates the 14C activity and δ13C value of the dissolved inorganic carbon of the drip water. The model is based on the chemical equations describing calcite dissolution ( H 2 O + CaCO 3 + CO 2 ⇔ Ca 2 + + 2HCO 3 - ). The most important improvement, relative to previous models, is the combination of the open and closed system conditions in order to simulate the C…

Persistent link between Caribbean precipitation and Atlantic Ocean circulation during the Last Glacial revealed by a speleothem record from Puerto Rico

The sensitivity of tropical Atlantic precipitation patterns to the mean position of the Intertropical Convergence Zone (ITCZ) at different time scales is well‐known. However, recent research suggests a more complex behavior of the northern hemispheric tropical rain belt related to the ITCZ in the western tropical Atlantic. Here we present a precisely dated speleothem multi‐proxy record from a well‐monitored cave in Puerto Rico, covering the period between 46.2 and 15.3 ka. The stable isotope and trace element records document a pronounced response of regional rainfall to abrupt climatic excursions in the North Atlantic across the Last Glacial such as Heinrich stadials and Dansgaard/Oeschger…

StalAge – An algorithm designed for construction of speleothem age models

Abstract Here we present a new algorithm ( StalAge ), which is designed to construct speleothem age models. The algorithm uses U-series ages and their corresponding age uncertainty for modelling and also includes stratigraphic information in order to further constrain and improve the age model. StalAge is applicable to problematic datasets that include outliers, age inversions, hiatuses and large changes in growth rate. Manual selection of potentially inaccurate ages prior to application is not required. StalAge can be applied by the general, non-expert user and has no adjustable free parameters. This offers the highest degree of reproducibility and comparability of speleothem records from …

Quantification of lignin oxidation products as vegetation biomarkers in speleothems and cave drip water

Here we present a sensitive method to analyze lignin oxidation products (LOPs) in speleothems and cave drip water to provide a new tool for paleo-vegetation reconstruction. Speleothems are valuable climate archives. However, compared to other terrestrial climate archives, such as lake sediments, speleothems contain very little organic matter. Therefore, very few studies on organic biomarkers in speleothems are available. Our new sensitive method allows us to use LOPs as vegetation biomarkers in speleothems. Our method consists of acid digestion of the speleothem sample followed by solid-phase extraction (SPE) of the organic matter. The extracted polymeric lignin is degraded in a microwave-a…

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Abstract Understanding the relationship between stable isotope signals recorded in speleothems (δ 13 C and δ 18 O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO 2 . The water entering the cave flows as a thin film towards the drip site. CO 2 degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scal…

Effects of dating errors on nonparametric trend analyses of speleothem time series

A fundamental problem in paleoclimatology is to take fully into account the various error sources when examining proxy records with quantitative methods of statistical time series analysis. Records from dated climate archives such as speleothems add extra uncertainty from the age determination to the other sources that consist in measurement and proxy errors. This paper examines three stalagmite time series of oxygen isotopic composition (δ18O) from two caves in western Germany, the series AH-1 from the Atta Cave and the series Bu1 and Bu4 from the Bunker Cave. These records carry regional information about past changes in winter precipitation and temperature. U/Th and radiocarbon dat…

The Palaeoanthropocene – The beginnings of anthropogenic environmental change

Abstract As efforts to recognize the Anthropocene as a new epoch of geological time are mounting, the controversial debate about the time of its beginning continues. Here, we suggest the term Palaeoanthropocene for the period between the first, barely recognizable, anthropogenic environmental changes and the industrial revolution when anthropogenically induced changes of climate, land use and biodiversity began to increase very rapidly. The concept of the Palaeoanthropocene recognizes that humans are an integral part of the Earth system rather than merely an external forcing factor. The delineation of the beginning of the Palaeoanthropocene will require an increase in the understanding and …

230Th/U-dating of a late Holocene low uranium speleothem from Cuba

We present 22 U-series ages for a stalagmite from north-western Cuba based on multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) and thermal ionisation mass spectrometry (TIMS). Our results reveal that the stalagmite continuously grew within the last ~1400a. Low uranium content of the sample and thus, extremely low 230Th concentrations limit the precision and accuracy of 230Th/U-dating by TIMS. Samples measured by MC-ICPMS show a high variability of 232Th content along the growth axis with some sections significantly affected by initial 230Th from a detrital phase. An a-priori bulk earth ratio for (238U/232Th) cannot be used to accurately account for this initial 230Th.…

Caribbean hydroclimate and vegetation history across the last glacial period

Abstract We present a new speleothem trace element and stable isotope record, which extends previous paleoclimate evidence from Cuban speleothems to the last 96 ka. Multiple proxies were used to reconstruct Caribbean hydroclimate and vegetation variability on orbital to millennial timescales. In particular, our proxies indicate a shift to more abundant C4 (compared to C3) vegetation and/or reduced soil activity during the Last Glacial Maximum. Our results confirm the close link of Caribbean precipitation to North Atlantic climate variability, insolation and the strength of the AMOC. The associated variations in Caribbean SSTs and the shift of the ITCZ led to substantial changes of the hydro…

Climate variations of Central Asia on orbital to millennial timescales

AbstractThe extent to which climate variability in Central Asia is causally linked to large-scale changes in the Asian monsoon on varying timescales remains a longstanding question. Here we present precisely dated high-resolution speleothem oxygen-carbon isotope and trace element records of Central Asia’s hydroclimate variability from Tonnel’naya cave, Uzbekistan and Kesang cave, western China. On orbital timescales, the supra-regional climate variance, inferred from our oxygen isotope records, exhibits a precessional rhythm, punctuated by millennial-scale abrupt climate events, suggesting a close coupling with the Asian monsoon. However, the local hydroclimatic variability at both cave sit…

Sensitivity of whole wood stable carbon and oxygen isotope values to milling procedures

RATIONALE Milling of wood samples is a widely applied preparation method for pooling tree-rings from different trees or periods of several years for determination of δ13C and δ18O values. In this study, whole wood samples were milled using different procedures in order to evaluate potential effects of this preparation method on δ13C and δ18O values. METHODS Subsamples of a 5 cm3 wood piece of a single tree-ring from a lowland white fir were used. The samples were milled with different setups: (i) two and three stainless-steel balls, (ii) 3, 5 and 8 min milling time, and (iii) discontinuous and continuous milling. The δ13C values were measured using an elemental analyser connected to an IsoP…

Opposite Trends in Holocene Speleothem Proxy Records From Two Neighboring Caves in Germany: A Multi-Proxy Evaluation

Holocene climate in Central Europe was characterized by variations on millennial to decadal time scales. Speleothems provide the opportunity to study such palaeoclimate variability using high temporal resolution proxy records, and offer precise age models by U-series dating. However, the significance of proxy records from an individual speleothem is still a matter of debate, and limited sample availability often hampers the possibility to reproduce proxy records or to resolve spatial climate patterns. Here we present a palaeoclimate record based on four stalagmites from the Hüttenbläserschachthöhle (HBSH), western Germany. Two specimens cover almost the entire Holocene, with a short hiatus …

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…

Chronology for the Cueva Victoria fossil site (SE Spain): Evidence for Early Pleistocene Afro-Iberian dispersals

Cueva Victoria has provided remains of more than 90 species of fossil vertebrates, including a hominin phalanx, and the only specimens of the African cercopithecid Theropithecus oswaldi in Europe. To constrain the age of the vertebrate remains we used paleomagnetism, vertebrate biostratigraphy and (230)Th/U dating. Normal polarity was identified in the non-fossiliferous lowest and highest stratigraphic units (red clay and capping flowstones) while reverse polarity was found in the intermediate stratigraphic unit (fossiliferous breccia). A lower polarity change occurred during the deposition of the decalcification clay, when the cave was closed and karstification was active. A second polarit…

230Th/U-dating of carbonate deposits from ancient aqueducts

Abstract Carbonate deposits in aqueducts, known as calcareous sinter, can reach a considerable thickness and are commonly annually laminated. Environmental and palaeoclimate proxies measured in calcareous sinter samples, such as stable oxygen and carbon isotopes and trace elements, can provide important high-resolution information on hydrological conditions, temperature, and local precipitation in the catchment area of an aqueduct. In order to utilize the proxy data for palaeoclimate reconstruction, the sinter deposits must be dated by annual laminae counting and more precisely by 230 Th/U-dating. The major problem of 230 Th/U-dating of calcareous sinter in aqueducts is the relatively large…

Revealing the pace of river landscape evolution during the Quaternary: recent developments in numerical dating methods

During the last twenty years, several technical developments have considerably intensified the use of numerical dating methods for the Quaternary. The study of fluvial archives has greatly benefited from these enhancements, opening new dating horizons for a range of archives at distinct time scales and thereby providing new insights into previously unanswered questions. In this contribution, we separately present the state of the art of five numerical dating methods that are frequently used in the fluvial context: radiocarbon, Luminescence, Electron Spin Resonance (ESR), 230Th/U and terrestrial cosmogenic nuclides (TCN) dating. We focus on the major recent developments for each technique th…

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…

Modelling fractionation of stable isotopes in stalagmites

Abstract High resolution δ13C and δ18O profiles recorded in precisely dated speleothems are widely used proxies for the climate of the past. Both δ13C and δ18O depend on several climate related effects including meteorological processes, processes occurring in the soil zone above the cave and isotope fractionation processes occurring in the solution layer on the stalagmite surface. Here we model the latter using a stalagmite isotope and growth model and determine the relationship between the stable isotope values in speleothem calcite and cave parameters, such as temperature, drip interval, water p CO 2 and a mixing coefficient describing mixing processes between the solution layer and the …

Microanalytical methods for in-situ high-resolution analysis of rock varnish at the micrometer to nanometer scale

Abstract A wide range of analytical techniques were used to investigate rock varnish from different locations (Negev, Israel; Knersvlakte, South Africa; Death Valley and Mojave Desert, California): a 200 nm-femtosecond laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS), an electron probe microanalyzer (EPMA), focused ion beam (FIB) slicing, and scanning transmission X-ray microscopy–near edge X-ray absorption fine structure spectroscopy (STXM–NEXAFS). This combination enables comprehensive high-spatial-resolution analysis of rock varnish. Femtosecond LA-ICP-MS and EPMA were used for quantitative determination of element concentrations. In-situ measurements were conducte…

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…

Annually resolved δ<sup>2</sup>H tree-ring chronology of the lignin methoxyl groups from Germany reflects averaged Western European surface air temperature changes

Abstract. Stable hydrogen isotopes ratios of lignin methoxyl groups (expressed as δ2HLM) of wood have been shown to reflect the climate-sensitive δ2H values of precipitation (expressed as δ2Hprecip) modulated by a large uniform negative isotope fractionation. However, a detailed calibration study among temporal variabilities of δ2HLM in tree-ring series, site-specific δ2Hprecip and climate parameters has not been performed yet. Here, we present annually resolved δ2HLM values from nine tree-ring series (derived from four Fagus sylvatica L. trees) collected near stations of the Global Isotope Network of Isotopes in Precipitation (GNIP) and the Deutsche Wetterdienst (DWD) meteorological observ…

Modelling the δ18O value of cave drip water and speleothem calcite

Abstract Stable isotope signals recorded in speleothems have provided important insights about past climate variability in recent years. Quantitative reconstruction of mean annual temperature and the amount of precipitation, however, remains difficult because the stable isotope signals are influenced by various processes. Here we present a drip water model, which shows how these climate parameters affect the oxygen isotope signal of cave drip water. In the model the dependence of the δ 18 O value of drip water on mean annual temperature is established by correlation to the amount of winter precipitation and winter temperature. Application of the model to two caves in western Germany reveals…

Last Interglacial Hydroclimate Seasonality Reconstructed From Tropical Atlantic Corals

The seasonality of hydroclimate during past periods of warmer than modern global temperatures is a critical component for understanding future climate change scenarios. Although only partially analogous to these scenarios, the last interglacial (LIG, Marine Isotope Stage 5e, ~127–117 ka) is a popular test bed. We present coral δ18O monthly resolved records from multiple Bonaire (southern Caribbean) fossil corals (Diploria strigosa) that date to between 130 and 118 ka. These records represent up to 37 years and cover a total of 105 years, offering insights into the seasonality and characteristics of LIG tropical Atlantic hydroclimate. Our coral δ18O records and available coral Sr/Ca-sea surf…

Improved constraints on open-system processes in fossil reef corals by combined Th/U, Pa/U and Ra/Th dating: A case study from Aqaba, Jordan

Abstract Here we present 230Th/U, 231Pa/U as well as 226Ra/230Th isotope ratios from five fossil reef corals of Last Interglacial origin from the Gulf of Aqaba, Northern Red Sea. The results show clear evidence for open-system behaviour with strongly elevated δ234U values and U concentrations indicating post-depositional U addition. The combined application of all isotope systems enables us to better constrain the nature and timing of the open-system processes than only based on the 230Th/U data. Quantitative modelling of the diagenetic processes allowed us to reproduce the trends in the isotope ratios. Two of the five corals were probably affected by two separate phases of U addition with …

Tropical Atlantic temperature seasonality at the end of the last interglacial

The end of the last interglacial period, ~118 kyr ago, was characterized by substantial ocean circulation and climate perturbations resulting from instabilities of polar ice sheets. These perturbations are crucial for a better understanding of future climate change. The seasonal temperature changes of the tropical ocean, however, which play an important role in seasonal climate extremes such as hurricanes, floods and droughts at the present day, are not well known for this period that led into the last glacial. Here we present a monthly resolved snapshot of reconstructed sea surface temperature in the tropical North Atlantic Ocean for 117.7±0.8 kyr ago, using coral Sr/Ca and δ18O records. W…

Last interglacial temperature seasonality reconstructed from tropical Atlantic corals

Abstract Reconstructions of last interglacial (LIG, MIS 5e, ∼127–117 ka) climate offer insights into the natural response and variability of the climate system during a period partially analogous to future climate change scenarios. We present well preserved fossil corals (Diploria strigosa) recovered from the southern Caribbean island of Bonaire (Caribbean Netherlands). These have been precisely dated by the 230Th/U-method to between 130 and 120 ka ago. Annual banding of the coral skeleton enabled construction of time windows of monthly resolved strontium/calcium (Sr/Ca) temperature proxy records. In conjunction with a previously published 118 ka coral record, our eight records of up to 37 …

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 …

Diagenesis of speleothems and its effect on the accuracy of 230 Th/U-ages

Abstract Speleothems can be precisely dated by U-series disequilibrium methods. One basic assumption of the 230Th/U-dating method is that the system remains closed and U and Th isotopes are neither lost nor added after deposition. For stalagmites, this requirement is usually fulfilled due to their protected environment in caves. However, undersaturated drip water may lead to diagenesis of speleothem CaCO3 and altered 230Th/U-ages. Here we present a detailed petrographic investigation using thin sections and 230Th/U-ages of a stalagmite from the Riesenberghohle, northern Germany, which grew during Marine Isotope Stages 5e, c and a. The occurrence of a mosaic fabric in large parts of the stal…

Speleogenesis of the Hermannshöhle cave system (Austria): Constraints from 230Th/U-dating and palaeomagnetic analysis

Hermannshöhle is a show cave located near Kirchberg/Wechsel in Lower Austria. Together with three nearby and genetically connected caves, it forms the Hermannshöhlen cave system (HHS). With a length of 5 km, the HHS is the longest cave in the Lower Austroalpine unit. It is arranged as an extreme three-dimensional maze on a ground area of 200 x 200 x 82 m. Speleothems are abundant in this cave and represent the focus of this study. Low carbon isotope values indicate the presence of a soil-covered catchment above the HHS during times of speleothem deposition. 28 samples were dated by the 230Th/U-method and, in combination with palaeomagnetic data from a 5 m-high sediment profile, indicate mul…

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…

Development of a Method for Anodic Degradation of Lignin for the Analysis of Paleo‐Vegetation Proxies in Speleothems

A comparison of different methods for speleothem age modelling

Abstract Speleothems, such as stalagmites and flowstones, can be dated with unprecedented precision in the range of the last 650,000 a by the 230Th/U-method, which is considered as one of their major advantages as climate archives. However, a standard approach for the construction of speleothem age models and the estimation of the corresponding uncertainty has not been established yet. Here we apply five age modelling approaches ( StalAge , OxCal, a finite positive growth rate model and two spline-based models) to a synthetic speleothem growth model and two natural samples. All data sets contain problematic features such as outliers, age inversions, large and abrupt changes in growth rate a…

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…

NanoSr - A New Carbonate Microanalytical Reference Material for In Situ Strontium Isotope Analysis

The in situ measurement of Sr isotopes in carbonates by MC‐ICP‐MS is limited by the availability of suitable microanalytical reference materials (RMs), which match the samples of interest. Whereas several well‐characterised carbonate reference materials for Sr mass fractions > 1000 µg g−1 are available, there is a lack of well‐characterised carbonate microanalytical RMs with lower Sr mass fractions. Here, we present a new synthetic carbonate nanopowder RM with a Sr mass fraction of ca. 500 µg g−1 suitable for microanalytical Sr isotope research (‘NanoSr’). NanoSr was analysed by both solution‐based and in situ techniques. Element mass fractions were determined using EPMA (Ca mass fraction),…

Annually resolved δ2H tree-ring chronology of the lignin methoxyl groups from Germany reflects averaged Western European surface air temperature changes

Stable hydrogen isotopes ratios of lignin methoxyl groups (expressed as δ2HLM) of wood have been shown to reflect the climate-sensitive δ2H values of precipitation (expressed as δ2Hprecip) modulated by a large uniform negative isotope fractionation. However, a detailed calibration study among temporal variabilities of δ2HLM in tree-ring series, site-specific δ2Hprecip and climate parameters has not been performed yet. Here, we present annually resolved δ2HLM values from nine tree-ring series (derived from four Fagus sylvatica L. trees) collected near stations of the Global Isotope Network of Isotopes in Precipitation (GNIP) and the Deutsche Wetterdienst (…

Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly?

South-eastern Spain is one of the driest regions in Europe and thus, prone to drought. Terrestrial climate records covering the late Glacial and Holocene from this area are sparse. Here, we present a flowstone record from Cueva Victoria, south-eastern Spain, which covers the late Glacial (15 ka) to the mid-Holocene (7 ka) including the Younger Dryas (YD). Between the onset of the Bølling/Allerød (B/A) and the early Holocene, flowstone δ18O values progressively decrease in accordance with sea-surface temperatures in the Alboran Sea, indicating an increase in precipitation in south-eastern Spain and a supra-regional signal of North Atlantic temperature change. At the same time, decreasing δ13…

Holocene climate variability in north-eastern Italy: potential influence of the NAO and solar activity recorded by speleothem data

Abstract. Here we present high-resolution stable isotope and lamina thickness profiles as well as radiocarbon data for the Holocene stalagmite ER 76 from Grotta di Ernesto (north-eastern Italy), which was dated by combined U-series dating and lamina counting. ER 76 grew between 8 ka (thousands of years before 2000 AD) and today, with a hiatus from 2.6 to 0.4 ka. Data from nine meteorological stations in Trentino show a significant influence of the North Atlantic Oscillation (NAO) on winter temperature and precipitation in the cave region. Spectral analysis of the stable isotope signals of ER 76 reveals significant peaks at periods of 110, 60–70, 40–50, 32–37 and around 25 a. Except for the …

Human adaptation strategies to abrupt climate change in Puerto Rico ca. 3.5 ka

The connection between climatic change and social response is complex because change articulates a number of inter-related factors. Human decisions are filtered by social buffers – including social memory, risk perception, and cultural priorities – and the rate and scale of climate change is usually much larger than the scale of human decision-making. In this article, we provide information on climate change based on precisely dated speleothems with the response evident in archaeological sites that have radiocarbon date ranges within the same time frame. A stalagmite recovered from within the catchment area for aquifer recharge of the Pre-Arawak site of Angostura in Barceloneta, Puerto Ric…

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…

Lignin oxidation products in soil, dripwater and speleothems from four different sites in New Zealand

Lignin oxidation products (LOPs) are widely used as vegetation proxies in climate archives, such as sediment and peat cores. The total LOP concentration, Σ8, provides information on the abundance of vegetation, while the ratios C/V and S/V of the different LOP groups also provide information on the type of vegetation. Recently, LOP analysis has been successfully applied to speleothem archives. However, there are many open questions concerning the transport and microbial degradation of LOPs on their way from the soil into the cave system. These processes could potentially alter the original source-dependent LOP signals, in particular the C/V and S/V ratios, and thus complicate their interpre…

Simulated European stalagmite record and its relation to a quasi-decadal climate mode

Abstract. A synthetic stalagmite record for the Bunker cave is constructed using a combined climate-stalagmite modeling approach. The power spectrum of the simulated speleothem calcite δ18O record has a pronounced peak at quasi-decadal time scale. Interestingly, mixing processes in the soil and karst above the cave represent a natural low-pass filter of the speleothem climate archive. We identify a quasi-decadal mode characterized by a "tripole pattern" of sea surface temperature affecting stalagmite δ18O values. This pattern, which is well-known in literature as the quasi-decadal mode in the North Atlantic, propagates eastwards and affects western European temperature surrounding the cave.…

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…

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…

Western Mediterranean Climate Response to Dansgaard/Oeschger Events: New Insights From Speleothem Records

The climate of the western Mediterranean was characterized by a strong precipitation gradient during the Holocene driven by atmospheric circulation patterns. The scarcity of terrestrial paleoclimate archives has precluded exploring this hydroclimate pattern during Marine Isotope Stages 5 to 3. Here we present stable carbon and oxygen isotope records from three flowstones from southeast Iberia, which show that Dansgaard/Oeschger events were associated with more humid conditions. This is in agreement with other records from the Iberian Peninsula, the Mediterranean, and western Europe, which all responded in a similar way to millennial‐scale climate variability in Greenland. This general incre…

Hydroclimate variability of western Thailand during the last 1400 years

Mainland Southeast Asia is located on the moisture transport route of the Indian summer monsoon (ISM) where hydroclimate records from speleothems have rarely been investigated. Here, we present a new multi-proxy (δ18O and δ13C values, trace element concentrations, and grayscale values) data set of stalagmite KPC1 from Khao Prae cave in western Thailand spanning the last 1400 years (500–1900 CE; the Common Era). These multi-proxy data reveal a high variability between the wet and dry periods during 500–850 CE and 1150–1300 CE, stable climate conditions during 850–1150 CE, and overall dry conditions since 1300 CE. The δ13C values, trace elements concentrations, and grayscale values show cente…

StalAge – an algorithm especially designed for construction of speleothem age models

Geochemical insights into the relationship of rock varnish and adjacent mineral dust fractions

Abstract Rock varnishes are μm-thin, dark, manganese(Mn)-rich crusts that accrete in the order of few μm/ka on weathering-resistant lithologies. Although these crusts can form in all climates, they are best known in arid to semi-arid settings. Aeolian dust is understood as a major contributor to the distinct trace metal and REE enrichments in rock varnish. However, the exact proportions of abiotic and biotic formation mechanisms that may explain the oxidation-reactions of Mn2+ to Mn4+, present as Mn oxyhydroxides in the varnish, are still a matter of ongoing debate. We present here the first systematic study of trace element enrichment processes between the uppermost layer of the varnish se…

Tree-ring δ2H values from lignin methoxyl groups indicate sensitivity to European-scale temperature changes

Abstract Stable hydrogen isotope ratios of lignin methoxyl groups (δ2HLM) of wood have been shown to reflect climate-sensitive δ2H values of precipitation (δ2Hprecip). However, a detailed calibration study between high-resolution δ2HLM and δ2Hprecip data has not been performed yet. Here, we present annually resolved δ2HLM values from nine tree-ring series (derived from four Fagus sylvatica L. trees) collected near a station of the Global Isotope Network of Isotopes in Precipitation (GNIP) and the meteorological observatory at Hohenpeisenberg (Germany; ~48°N, 11°E). The nine δ2HLM tree-ring series show highly significant inter-series correlations (Rbar = 0.52) over the common period of overl…

TERMITE: AnRscript for fast reduction of laser ablation inductively coupled plasma mass spectrometry data and its application to trace element measurements

RATIONALE High spatial resolution Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) determination of trace element concentrations is of great interest for geological and environmental studies. Data reduction is a very important aspect of LA-ICP-MS, and several commercial programs for handling LA-ICPMS trace element data are available. Each of these software packages has its specific advantages and disadvantages. METHODS Here we present TERMITE, an R script for the reduction of LA-ICPMS data, which can reduce both spot and line scan measurements. Several parameters can be adjusted by the user, who does not necessarily need prior knowledge in R. Currently, ten reference m…

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…

Warfare dendrochronology: Trees witness the deployment of the German battleship Tirpitz in Norway

Abstract War has an immediate and obvious effect on people and communities, but its impacts on local ecology can be more subtle. This paper shows how one military encounter in the Second World War has left a clear legacy in the northern forests of Norway, trackable more than seventy years later. We used annual growth rings of ∼180 pine and ∼30 birch trees as witnesses of the deployment of the German battleship Tirpitz at the Kafjord. The Tirpitz was the target of several Allied air attacks, but the Kriegsmarine (German navy from 1935 to 1945) used artificial smoke, consisting of chlorosulfonic acid and zinc/hexachloroethane, to hide the ship. These smoke-screen actions throughout 1944 cause…

Accurate trace element analysis of speleothems and biogenic calcium carbonates by LA-ICP-MS

The high spatial resolution of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) microanalysis of speleothems and biogenic calcium carbonates makes it possible to improve our understanding of past climatic conditions. However, there are analytical problems associated with this method, such as molecular interferences, elemental fractionation, and mass-load-dependent matrix effects, when using NIST silicate reference glasses for calibration. Our study with a sector-field ICP-MS shows that many masses are affected by interferences, such as 24Mg+ by 48Ca++ or 31P+ by 15N16O+. Elemental fractionation and mass-load-dependent matrix effects have been detected for both 213 and…

Cuban stalagmite suggests relationship between Caribbean precipitation and the Atlantic Multidecadal Oscillation during the past 1.3 ka

Here we present the first high-resolution δ18O record of a stalagmite from western Cuba. The record reflects precipitation variability in the northwestern Caribbean during the last 1.3 ka and exhibits a correlation to the Atlantic Multidecadal Oscillation (AMO). This suggests a relationship between Caribbean rainfall intensity and North Atlantic sea-surface temperature (SST) anomalies. A potential mechanism for this relationship may be the strength of the Thermohaline Circulation (THC). For a weaker THC, lower SSTs in the North Atlantic possibly lead to a southward shift of the Intertropical Convergence Zone and drier conditions in Cuba. Thus, this Cuban stalagmite records drier conditions…

Climate and structure of the 8.2 ka event reconstructed from three speleothems from Germany

Abstract The most pronounced climate anomaly of the Holocene was the 8.2 ka cooling event. We present new 230Th/U-ages as well as high-resolution stable isotope and trace element data from three stalagmites from two different cave systems in Germany, which provide important information about the structure and climate variability of the 8.2 ka event in central Europe. In all three speleothems, the 8.2 ka event is clearly recorded as a pronounced negative excursion of the δ18O values and can be divided into a ‘whole event’ and a ‘central event’. All stalagmites show a similar structure of the event with a short negative excursion prior to the ‘central event’, which marks the beginning of the …

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…

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…

Control of Seasonality and Interannual to Centennial Climate Variability in the Caribbean During the Holocene—Combining Coral Records, Stalagmite Records and Climate Models

This study aimed at quantifying the amplitudes of seasonality and interannual to centennial climate variability in the Caribbean region throughout the Holocene, by using marine (shallow-water corals) and terrestrial (speleothems) climate archives, and climate model simulations (COSMOS). Sea-surface temperature (SST) variability on interdecadal to multidecadal timescales was more pronounced during the mid-Holocene compared to the late Holocene. The amplitude of the SST annual cycle was within the present-day range throughout most of the last 6,000 years. Exceptions include slightly increased SST seasonality at 6,200 years ago, which can be attributed mainly to insolation forcing on orbital t…

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…

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…

Opposite trends in Holocene speleothem proxy records from two neighboring caves in Germany : a multi-proxy evaluation

Monitoring of Cueva Larga, Puerto Rico—A First Step to Decode Speleothem Climate Records

This study presents results of an ongoing cave monitoring program at Cueva Larga, Puerto Rico. The monitoring includes monthly analyses of stable isotope ratios of rain and drip water, and trace element ratios of drip water and cave air parameters. Drip sites are above growing speleothems offering the unique chance to calibrate geochemical variations in speleothems in order to reconstruct past climate conditions. Seasonal rainfall patterns above Cueva Larga show characteristic stable isotope values. The wet season is characterized by more negative δ18O and δD values and a maritime deuterium excess (+10‰). The dry season has more positive δ18O and δD values and elevated deuterium excess (>15…

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…

Hurricane Impact on Seepage Water in Larga Cave, Puerto Rico

Holocene climate variability in Central Germany and a potential link to the polar North Atlantic: A replicated record from three coeval speleothems

Here, we present high-resolution trace element and stable isotope records from three coeval Holocene stalagmites from the Herbstlabyrinth cave system, Central Germany. All stalagmites were precisely dated using MC-ICPMS 230Th/U-dating. One stalagmite started to grow at 13.62 ± 0.13 ka BP, covering the late Glacial; the other two speleothems started to grow at 11.13 ± 0.08 and 10.26 ± 0.08 ka BP, respectively. The combined record covers the entire Holocene. The interpretation of the different climate proxies is supported by data from a detailed cave monitoring programme. Cold conditions during the Younger Dryas are reflected by intermittent stalagmite growth at the Herbstlabyrinth. The δ18O…

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-…

Reconstruction of late Holocene autumn/winter precipitation variability in SW Romania from a high-resolution speleothem trace element record

We present the first high-resolution trace element (Mg/Ca, Sr/Ca, Ba/Ca) record from a stalagmite in southwestern Romania covering the last 3.6 ka, which provides the potential for quantitative climate reconstruction. Precise age control is based on three independent dating methods, in particular for the last 250 yr, where chemical lamina counting is combined with the identification of the 20th century radiocarbon bomb peak and Th-230/U dating. Long-term cave monitoring and model simulations of drip water and speleothem elemental variability indicate that precipitation-related processes are the main drivers of speleothem Mg/Ca ratios. Calibration against instrumental climate data shows a si…

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…

Supplement_Budsky – Supplemental material for Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly?

Supplemental material, Supplement_Budsky for Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly? by Alexander Budsky, Denis Scholz, Jasper A Wassenburg, Regina Mertz-Kraus, Christoph Spötl, Dana FC Riechelmann, Luis Gibert, Klaus Peter Jochum and Meinrat O Andreae in The Holocene

Determination of aragonite trace element distribution coefficients from speleothem calcite–aragonite transitions.

The processes that govern the incorporation of (trace) elements into speleothems can often be linked to environmental changes. Although element incorporation into speleothem calcite is now reasonably well understood, current knowledge regarding trace element variability in speleothem aragonite is very limited. Of particular interest is whether trace element distribution coefficients are above or below one in order to assess the extent to which prior aragonite precipitation has affected speleothem aragonite trace element records. This study uses nine calcite-to-aragonite transitions in seven speleothems from diverse environmental settings to derive the first quantitative estimates of the dis…

Stable isotope fractionation in speleothems: Laboratory experiments

Abstract In recent years, stalagmites have become important archives for paleoclimate. Several studies applying carbon and oxygen isotopes of stalagmites show a simultaneous increase of δ 13 C and δ 18 O along individual growth layers, which is interpreted as being indicative of isotope fractionation under disequilibrium conditions. In order to obtain robust paleoclimatic information from calcite precipitated under these non-equilibrium conditions it is important to improve the quantitative understanding of the corresponding isotope fractionation processes. Here we present laboratory experiments simulating calcite precipitation under cave-analogue conditions. The major focus was the investi…

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…

On the generation and degradation of emerged coral reef terrace sequences: First cosmogenic 36Cl analysis at Cape Laundi, Sumba Island (Indonesia)

(IF 4.45: Q1); International audience; The emerged coral reef terrace sequence at Cape Laundi, on the north coast of Sumba Island (Indonesia), with at least 18 successive strandlines, remains poorly dated in spite of numerous previous data. The age discrepancies within these coral reef terraces (CRTs) were previously explained by their polycyclic nature, triggered by marine erosion and reoccupation of old coral colonies by new ones. This study aims at highlighting these processes, as well as the continental denudation that participates in the partial stripping of the thin superficial coral reef layer overlying the pre-existing surface, exhuming older coral colonies. For this purpose, we use…

Intra- and inter-annual uranium concentration variability in a Belizean stalagmite controlled by prior aragonite precipitation: A new tool for reconstructing hydro-climate using aragonitic speleothems

Aragonitic speleothems are increasingly utilised as palaeoclimate archives due to their amenability to high precision U–Th dating. Proxy records from fast-growing aragonitic stalagmites, precisely dated to annual timescales, can allow investigation of climatic events occurring on annual or even sub-annual timescales with minimal chronological uncertainty. However, the behaviour of many trace elements, such as uranium, in aragonitic speleothems has not thus far been as well constrained as in calcitic speleothems. Here, we use uranium concentration shifts measured across primary calcite-to-aragonite mineralogical transitions in speleothems to calculate the distribution coefficient of uranium …

Sr-isotope analysis of speleothems by LA-MC-ICP-MS: High temporal resolution and fast data acquisition

Speleothems are well established climate archives. A wide array of geochemical proxies, including stable isotopes and trace elements are present within speleothems to reconstruct past climate variability. However, each proxy is influenced by multiple factors, often hampering robust interpretation. Sr isotope ratios (87Sr/86Sr) can provide useful information about water residence time and water mixing in the host rock, as they are not fractionated during calcite precipitation. Laser ablation multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) has rarely been used for determination of Sr isotope signatures in speleothems, as speleothems often do not possess appropriate…

Trace element variability in single ostracod valves as a proxy for hydrochemical change in Nam Co, central Tibet, during the Holocene

Ostracod shells, belonging to three taxa (Leucocytherella sinensis Huang, 1982, ?Leucocythere dorsotuberosa Huang, 1982 and ?L. dorsotuberosa f. postilirata sensu Pang, 1985), were collected from two sediment cores from Lake Nam Co, on the central Tibetan Plateau. Two variants of LA–ICP–MS (laser ablation–inductively coupled plasma–mass spectrometry), spot and line-scan analyses, were used to investigate trace element concentrations (Mg, Sr, Ba, U and rare earth elements [REEs]) in single ostracod shells. The results suggest that the line-scan method can provide better precision than the spot analysis and is therefore preferred. No significant difference in trace element composition between…

A 4000-year long Late Holocene climate record from Hermes Cave (Peloponnese, Greece)

The societal and cultural development during the Bronze Age and the subsequent Iron Age was enormous in Greece, however interrupted by two significant transformations around 4200 years b2k (Early Helladic II/III; b2k refers to years before 2000 CE) and 3200 years b2k (end of Late Helladic III). Artefacts and building remains provide some insights into the cultural evolution, but only little is known about environmental and climatic changes on a detailed temporal and spatial scale. Here we present a 4000-year long stalagmite record (GH17-05) from Hermes Cave, Greece, located on Mount Ziria in the close vicinity of the Late Bronze Age citadel of Mycenae and the Classical-Hellenistic polis of …

Cave bear occupation in Schwabenreith Cave, Austria, during the early last glacial: constraints from 230 Th/U‐dated speleothems

The cave bear was a prominent member of the Upper Pleistocene fauna in Eurasia. While breakthroughs were recently achieved with respect to its phylogeny using ancient DNA techniques, it is still challenging to date cave bear fossils beyond the radiocarbon age range. Without an accurate and precise chronological framework, however, key questions regarding the palaeoecology cannot be addressed, such as the extent to which large climate swings during the last glacial affected the habitat and possibly even conditioned the final extinction of this mammal. Key to constraining the age of cave bear fossils older than the lower limit of radiocarbon dating is to date interlayered speleothems using 23…

Characterization and differentiation of rock varnish types from different environments by microanalytical techniques

© 2017 Elsevier B.V. We investigated rock varnishes collected from several locations and environments worldwide by a broad range of microanalytical techniques. These techniques were selected to address the challenges posed by the chemical and structural complexity within the micrometer- to nanometer-sized structures in these geological materials. Femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs LA-ICP-MS), scanning transmission X-ray microscopy-near edge X-ray adsorption fine structure spectroscopy (STXM-NEXAFS) in combination with scanning electron microscopy (SEM) of focused ion beam (FIB) ultra-thin (100–200 nm) sections, conventional and polarization microscop…

Calcium Carbonate and Phosphate Reference Materials for Monitoring Bulk and Microanalytical Determination of Sr Isotopes

In situ laser ablation analyses rely on the microanalytical homogeneity of reference materials (RMs) and a similar matrix and mass fraction between unknown samples and RMs to obtain reliable results. Suitable carbonate and phosphate RMs for determination of Sr isotope ratios in such materials are limited. Thus, we determined Sr-87/Sr-86 ratios of several carbonate (JCt-1, JCp-1, MACS-1, MACS-3) and phosphate (MAPS-4, MAPS-5, NIST SRM 1400, NIST SRM 1486) international RMs using dissolved samples and two different multi-collector inductively coupled plasma-mass spectrometers (MC-ICP-MS). Our Sr isotope data are in agreement with published data and have an improved measurement precision for s…

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…

Speleothems in a north Cuban cave register sea-level changes and Pleistocene uplift rates

Vegetation and environmental changes in tropical South America from the last glacial to the Holocene documented by multiple cave sediment proxies

Abstract δ 18 O values in speleothems have been utilized to document past changes in South American monsoon intensity. However, changes in regional vegetation and ecosystems have not been part of this discussion, and other cave proxies such as speleothem δ 13 C values, a useful proxy for vegetation reconstruction, have been neglected due to interpretive complexities. Here we report δ 13 C values and 87Sr/86Sr ratios in stalagmites, together with XRF-derived elemental chemistry, δ 13 Corg values and carbon content from a sedimentary profile from the same cave where the stalagmites were collected. In combination with a previously published δ 18 O record, this enables us to clarify climate and…

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…

Chemical separation and MC-ICPMS analysis of U, Th, Pa and Ra isotope ratios of carbonates

Diagenetic alteration of fossil reef corals may have severe effects on the reliability of 230Th/U-ages. The widely applied criteria introduced to test for the reliability of coral 230Th/U-ages are often not sufficient to identify all altered ages. The combination of 230Th/U- with 231Pa/U-dating has been suggested as a promising method to identify altered ages. Furthermore, 226Ra/230Th ratios can provide information about the diagenetic history during the last 10 000 years. Here we present a method to chemically separate U, Th, Pa and Ra from the same aliquot of a carbonate sample. The isotope ratios of our mixed U–Th–Pa–Ra spike are calibrated using a secular equilibrium material treated in…

Lignin oxidation products as a potential proxy for vegetation and environmental changes in speleothems and cave drip water – a first record from the Herbstlabyrinth, central Germany

Here, we present the first quantitative speleothem record of lignin oxidation products (LOPs), which has been determined in a Holocene stalagmite from the Herbstlabyrinth Cave in central Germany. In addition, we present LOP results from 16 months of drip water monitoring. Lignin is only produced by vascular plants and therefore has the potential to be an unambiguous vegetation proxy and to complement other vegetation and climate proxies in speleothems. We compare our results with stable isotope and trace element data from the same sample. In the stalagmite, LOP concentrations show a similar behavior to P, Ba and U concentrations, which have previously been interpreted as vegetation proxies.…

Last glacial millennial-scale hydro-climate and temperature changes in Puerto Rico constrained by speleothem fluid inclusion δ<sup>18</sup>O and δ<sup>2</sup>H values

Abstract. We present speleothem fluid inclusion δ18Of and δ2Hf values from Larga Cave, Puerto Rico, that covers the interval between 46.2 to 15.3 ka before present on millennial scale, including the Last Glacial Maximum (LGM) and several stadial and interstadial cycles. The dataset can be divided in two main clusters of stable isotope compositions of the fluid inclusion water with respect to the global meteoric water line which coincide with strong variations in the water content of the stalagmite. In particular, this clustering is found to be climate related, where the first cluster comprises samples from cold and dry periods, such as Heinrich and Greenland stadials, as well as parts of th…

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…

Holocene interaction of maritime and continental climate in Central Europe: New speleothem evidence from Central Germany

Central European climate is strongly influenced by North Atlantic (Westerlies) and Siberian High circulation patterns, which govern precipitation and temperature dynamics and induce heterogeneous climatic conditions, with distinct boundaries between climate zones. These climate boundaries are not stationary and shift geographically, depending on long-term atmospheric conditions. So far, little is known about past shifts of these climate boundaries and the local to regional environmental response prior to the instrumental era.\ud \ud High resolution multi-proxy data (stable oxygen and carbon isotope ratios, S/Ca and Sr/Ca) from two Holocene stalagmites from Bleßberg Cave (Thuringia) are used…

Millennial-scale climate variability during the last 12.5 ka recorded in a Caribbean speleothem

Abstract We present a speleothem stable oxygen isotope record for the last 12.5 ka based on two stalagmites from western Cuba. The δ18O signal is interpreted to represent past precipitation variability. Both stalagmites show a pronounced transition from higher δ18O values (indicating drier conditions) to more negative δ18O values (suggesting wetter conditions) between 10 and 6 ka. This transition is also visible in a planktonic δ18O record off Haiti. On orbital timescales, the δ18O value of Caribbean precipitation, thus, strongly resembles the oxygen isotope composition of Caribbean surface water. On millenial timescales, the speleothem δ18O record shows a high correlation to a North Atlant…

Carbonate deposits from the ancient aqueduct of Béziers, France — A high-resolution palaeoenvironmental archive for the Roman Empire

Abstract Carbonate deposits from a Roman aqueduct in Beziers, southern France, record environmental conditions during the late first century C.E. These deposits formed in a steep section of the aqueduct with a high flow velocity, which caused rapid deposition of up to 11 mm of calcite per year over a period of 22–24 years. The microstructure, trace element and stable isotope composition show that regular deposition was interrupted by high-discharge events, probably in response to heavy rainfall during autumn and winter, transporting colloidally- and particle-bound elements and depositing calcite with elevated δ 18 O values. Individual autumn high-discharge events coincide with abrupt decrea…

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…

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…

Presence of cave bears in western Austria before the onset of the Last Glacial Maximum: new radiocarbon dates and palaeoclimatic considerations

Tischoferhohle and Pendling-Barenhohle near Kufstein, Tyrol, are among the only locations where remains of cave bear, Ursus spelaeus-group, were found in the western part of Austria. One sample from each site was radiocarbon-dated four decades ago to ca. 28 14C ka BP. Here we report that attempts to date additional samples from Pendling-Barenhohle have failed due to the lack of collagen, casting doubts on the validity of the original measurement. We also unsuccessfully tried to date flowstone clasts embedded in the bone-bearing sediment to provide maximum constraints on the age of this sediment. Ten cave bear bones from Tischoferhohle showing good collagen preservation were radiocarbon-date…

Lignin oxidation products as a vegetation proxy in stalagmite and drip water samples from the Herbstlabyrinth, Germany

Here we present the first quantitative record of lignin oxidation products (LOPs) in a Holocene stalagmite from the Herbstlabyrinth Cave in central Germany, as well as LOP results from 16 months of drip water monitoring. Lignin is only produced by vascular plants and is therefore an unambiguous vegetation proxy, which can help to better interpret other vegetation and climate proxies in speleothems. We compared our results with stable isotope and trace element data from the same samples. The drip water monitoring reveals a seasonal pattern of LOPs in a fast drip site with low LOP concentrations in winter and higher LOP concentrations in summer, which is opposite to the behaviour of the drip …

(Supplementary Table 1) 230Th/U results for stalagmite Cuba Grande (CG) from Pinar del Rio

We present 22 U-series ages for a stalagmite from north-western Cuba based on multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) and thermal ionisation mass spectrometry (TIMS). Our results reveal that the stalagmite continuously grew within the last ~1400a. Low uranium content of the sample and thus, extremely low 230Th concentrations limit the precision and accuracy of 230Th/U-dating by TIMS. Samples measured by MC-ICPMS show a high variability of 232Th content along the growth axis with some sections significantly affected by initial 230Th from a detrital phase. An a-priori bulk earth ratio for (238U/232Th) cannot be used to accurately account for this initial 230Th.…

(Supplement Table S2) Results of 230Th/U-dating

We compared the suitability of two skeletal materials of the Atlantic brain coral Diploria strigosa for 230Th/U-dating: the commonly used bulk material comprising all skeletal elements and the denser theca wall material. Eight fossil corals of presumably Last Interglacial age from Bonaire, southern Caribbean Sea, were investigated, and several sub-samples were dated from each coral. For four corals, both the ages and the activity ratios of the bulk material and theca wall agree within uncertainty. Three corals show significantly older ages for their bulk material than for their theca wall material as well as substantially elevated 232Th content and (230Th/238U) ratios. The bulk material sam…

Stable isotopes covering 96-7 ka BP from stalagmite CM (Santo Tomas Cave, Cuba)

We present a new speleothem trace element and stable isotope record, which extends previous paleoclimate evidence from Cuban speleothems to the last 96 ka. Stable isotope samples were micromilled at a resolution of 0.10-0.33mm, and measured using an IRMS equipped with a Gasbench. Line scans of Element/Calcium ratios of the speleothem were measured by laser ablation ICPMS and were reduced to the resolution of the stable isotope records.

Trace element data covering 96-7 ka BP from stalagmite CM (Santo Tomas Cave, Cuba)

We present a new speleothem trace element and stable isotope record, which extends previous paleoclimate evidence from Cuban speleothems to the last 96 ka. Stable isotope samples were micromilled at a resolution of 0.10-0.33mm, and measured using an IRMS equipped with a Gasbench. Line scans of Element/Calcium ratios of the speleothem were measured by laser ablation ICPMS and were reduced to the resolution of the stable isotope records.

Monthly Bonaire coral Sr/Ca and oxygen isotope data from 118 kyr ago (coral BON-5-D)

The end of the last interglacial period, ~118 kyr ago, was characterized by substantial ocean circulation and climate perturbations resulting from instabilities of polar ice sheets. These perturbations are crucial for a better understanding of future climate change. The seasonal temperature changes of the tropical ocean, however, which play an important role in seasonal climate extremes such as hurricanes, floods and droughts at the present day, are not well known for this period that led into the last glacial. Here we present a monthly resolved snapshot of reconstructed sea surface temperature in the tropical North Atlantic Ocean for 117.7±0.8 kyr ago, using coral Sr/Ca and d18O records. W…