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We present speleothem fluid inclusion δ18Of and δ2Hf values from Larga Cave, Puerto Rico, that cover the interval between 46.2 and 15.3 ka on the millennial scale, including the Last Glacial Maximum (LGM) and several stadial and interstadial cycles. The data set can be divided in two main clusters of stable isotope compositions of the fluid inclusion water with respect to the global meteoric water line (GMWL), which coincide with strong variations in the water content of the stalagmite. In particular, this clustering is found to be climate related, where one cluster comprises samples from cold and dry periods, such as the Heinrich and Greenland stadials (HSs and GSs), as well as parts of the LGM, which exhibit very high δ18Of and δ2Hf values. We interpret this enrichment as being caused by evaporation inside the cave due to enhanced cave ventilation during these colder and drier times. In contrast, in most samples corresponding to warmer and wetter Greenland interstadials (GIs), but also for some from HS 2 and 3, the δ18Of and δ2Hf values plot on the meteoric water line and modification of fluid inclusion water due to “in-cave” evaporation are found to be negligible. Consequently, variations of recent glacial hydro-climate and temperatures in the western tropical Atlantic can be constrained. In general, δ18Of values from fluid inclusions are up to 3 ‰ higher than those of modern drip water, which is interpreted as a weaker atmospheric convective activity during the last glacial period. In addition, reconstructed temperatures suggest an average cooling of 2–3 ∘C during the LGM compared to modern cave temperatures. Reconstructed cave temperatures yield an average cooling of −1.4 ± 2.8 ∘C for HS 2 and −3.6 ± 2.2 ∘C for HS 3. Higher δ18Of values of these samples further suggest that the drip water was dominated by orographic rainfall and/or cold fronts, along with weak or even absent convective activity. In contrast, during interstadial phases, reconstructed temperatures reached nearly modern values, and convective activity was comparable to or only slightly weaker than today.

The global development and modern distribution of arid zones in subtropical regions (drylands) are likely associated with the global cooling marking the dawn of the Quaternary (~2.6 Ma). This coincides with global shifts in ocean circulation patterns, the intensification of the Walker-Hadley circulation, declining atmospheric CO2, the initiation of glacial–interglacial cycles and the intensification of Northern Hemisphere glaciation, the combination of which has led to the current global distribution of non-polar deserts at ~30° latitude. Although modern drylands represent Earth’s largest terrestrial biome, covering ~46% of global land surfaces and supporting a global population of ~3 billion people, it is currently unclear how drylands will change under future climate change scenarios. Speleothems, preserved in arid-zone caves, are particularly useful terrestrial climate archives as they act as underground rain gauges, which require a minimum of ~300 mm a-1 precipitation, pedogenesis and vegetation cover to form. Moreover, they can be accurately and precisely dated and are subsequently a valuable tool in identifying past large-scale hydrological and vegetation changes in ancient drylands. Here, we present new data from speleothems during past ‘warm periods’ from the Arabian hyper-arid zone. We apply a novel technique of extracting speleothem fluid inclusions waters to reconstruct the isotopic composition (d18O and d2H) of ‘fossil rainwater’ preserved in the speleothem fabric pristinely over millions of years. Speleothem evidence suggests that during the last 7 million years, the Sahara-Arabian desert experienced numerous intermittent humid phases, typically occurring with periods of low global ice-volume and warmer global temperatures. We further explore tropical push-pull mechanisms driving heating of the deep tropics and subsequent expansion of the tropical zone and synchronicity of humid phases regionally. These results have significant implications for understanding the drivers of dryland aridity in non-polar deserts globally., EGUsphere

We present speleothem fluid inclusion ��18Of and ��2Hf values from Larga Cave, Puerto Rico, that cover the interval between 46.2 and 15.3 ka on the millennial scale, including the Last Glacial Maximum (LGM) and several stadial and interstadial cycles. The data set can be divided in two main clusters of stable isotope compositions of the fluid inclusion water with respect to the global meteoric water line (GMWL), which coincide with strong variations in the water content of the stalagmite. In particular, this clustering is found to be climate related, where one cluster comprises samples from cold and dry periods, such as the Heinrich and Greenland stadials (HSs and GSs), as well as parts of the LGM, which exhibit very high ��18Of and ��2Hf values. We interpret this enrichment as being caused by evaporation inside the cave due to enhanced cave ventilation during these colder and drier times. In contrast, in most samples corresponding to warmer and wetter Greenland interstadials (GIs), but also for some from HS 2 and 3, the ��18Of and ��2Hf values plot on the meteoric water line and modification of fluid inclusion water due to ���in-cave��� evaporation are found to be negligible. Consequently, variations of recent glacial hydro-climate and temperatures in the western tropical Atlantic can be constrained. In general, ��18Of values from fluid inclusions are up to 3 ��� higher than those of modern drip water, which is interpreted as a weaker atmospheric convective activity during the last glacial period. In addition, reconstructed temperatures suggest an average cooling of 2���3 ���C during the LGM compared to modern cave temperatures. Reconstructed cave temperatures yield an average cooling of ���1.4 �� 2.8 ���C for HS 2 and ���3.6 �� 2.2 ���C for HS 3. Higher ��18Of values of these samples further suggest that the drip water was dominated by orographic rainfall and/or cold fronts, along with weak or even absent convective activity. In contrast, during intersta-dial phases, reconstructed temperatures reached nearly modern values, and convective activity was comparable to or only slightly weaker than today.

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 the LGM, which exhibit very high δ18Of and δ2Hf values. We interpret this enrichment as caused by evaporation inside the cave due to enhanced cave ventilation during these colder and drier times. In contrast, in most samples corresponding to warmer and wetter Greenland interstadials, but also for some from Heinrich Stadial 2 and 3, the δ18Of and δ2Hf values plot on the meteoric water line and modification of fluid inclusion water due to “in-cave” evaporation is found negligible. Consequently, variations of last glacial hydro-climate and temperature in the western tropical Atlantic can be constrained. In general, δ18Of values from fluid inclusions are up to 3 ‰ higher than those of modern drip water, which is interpreted as a weaker atmospheric convective activity during the last glacial period. In addition, reconstructed temperatures suggest an average cooling of c. 3 °C during the LGM compared to modern cave temperature. During Heinrich Stadials 2 and 3, reconstructed cave temperatures yield an additional cooling of 2.9 ± 2.6 °C and 4.4 ± 0.6 °C, respectively. Higher δ18Of values of these samples further suggest that the drip water was dominated by orographic rainfall and/or cold fronts, along with weak or even absent convective activity. In contrast, during interstadial phases, reconstructed temperatures reached nearly modern values, and convective activity was comparable or only slightly weaker than today.

Although quantitative isotope data from speleothems has been used to evaluate isotope-enabled model simulations, currently no consensus exists regarding the most appropriate methodology through which to achieve this. A number of modelling groups will be running isotope-enabled palaeoclimate simulations in the framework of the Coupled Model Intercomparison Project Phase 6, so it is timely to evaluate different approaches to using the speleothem data for data-model comparisons. Here, we illustrate this using 456 globally distributed speleothem delta O-18 records from an updated version of the Speleothem Isotopes Synthesis and Analysis (SISAL) database and palaeoclimate simulations generated using the ECHAM5-wiso isotope-enabled atmospheric circulation model. We show that the SISAL records reproduce the first-order spatial patterns of isotopic variability in the modern day, strongly supporting the application of this dataset for evaluating model-derived isotope variability into the past. However, the discontinuous nature of many speleothem records complicates the process of procuring large numbers of records if data-model comparisons are made using the traditional approach of comparing anomalies between a control period and a given palaeoclimate experiment. To circumvent this issue, we illustrate techniques through which the absolute isotope values during any time period could be used for model evaluation. Specifically, we show that speleothem isotope records allow an assessment of a model's ability to simulate spatial isotopic trends. Our analyses provide a protocol for using speleothem isotope data for model evaluation, including screening the observations to take into account the impact of speleothem mineralogy on delta O-18 values, the optimum period for the modern observational baseline and the selection of an appropriate time window for creating means of the isotope data for palaeo-time-slices. European Geosciences Union - W2017/413; Irish Centre for Research in Applied Geosciences (iCRAG); European Association of Geochemistry (Early Career Ambassadors program 2017); Quaternary Research Association UK; Navarino Environmental Observatory, Stockholm University; University College Dublin, Savillex (UK) - SF1428; Ibn Zohr University, Morocco; University of Reading; European Research Council - 694481; Natural Environment Research Council (JPI-Belmont project "PAleao-Constraints on Monsoon Evolution and Dynamics (PACMEDY)"); Geological Survey Ireland - 2017-SC-056; Royal Irish Academy; Deutsche Forschungsgemeinschaft - RE3994/2-1; Past Global Changes (PAGES) programme; info:eu-repo/semantics/publishedVersion

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. The LOP S∕V and C∕V ratios, which are usually used to differentiate between angiosperm and gymnosperm and woody and non-woody vegetation, show complex patterns suggesting additional influencing factors, such as transport and microbiological effects. The drip water from a fast drip site shows a seasonal pattern of LOPs with low LOP concentrations in winter and higher LOP concentrations in summer. These results indicate the potential of LOPs as a new proxy for vegetational and environmental changes in speleothems but also demonstrate the complexity and the current limitations of our understanding of the transport of lignin from the soil into the cave and the speleothems.

Speleothem δ18O values are commonly used to infer past climate variability. However, both non-linear karst hydrological processes and in-cave disequilibrium isotope fractionation are recognised and hinder the interpretation of δ18O values. In recent years, proxy system models (PSMs) have emerged to quantitatively assess the confounding effects of these processes. This study presents the first integrated stalagmite δ18O PSM (Karstolution) by coupling an existing karst hydrology with an in-cave fractionation PSM. The new modelling framework not only couples the two models, but also includes diffuse flow modelling, coupling of drip rate with infiltration, linking of surface with cave temperature, and incorporates cave seasonality effects. We test Karstolution using a cave monitoring dataset from Golgotha Cave, SW Australia. The predictive capacity of the model is assessed by comparing the output to stalagmite δ18O values. By comparing with observed stalagmite δ18O values, this study is also the first to quantify in-cave disequilibrium both kinetic isotopic fractionation in a speleothem and informs the conclusion that hydroclimatic processes contributes more to the variability of stalagmite δ18O values at Golgotha Cave than does in-cave processes. This is further supported via a sensitivity analysis performed by simulating the impacts of a wider range of cave temperature, ventilation, drip interval and pCO2 values than measured.

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 observatory at Hohenpeißenberg (southern Germany; ~ 48° N, 11° E). The measured nine δ2HLM tree-ring series (common period of overlap 1916-2015) show a strong coherency as indicated by highly significant (p 2HLM chronology shows highest correlations with annually averaged data of δ2Hprecip as well as temperature particularly when using the year defined from previous September to current August (r = 0.73 and 0.56, respectively, p 2HLM chronology shows enhanced correlations with land and sea surface air temperature for multiple (broadly combined) areas across Western Europe (r > 0.6, p 2HLM chronology (r = 0.71, p n = 100). Therefore, δ2HLM values of mid-latitudinal tree-ring archives are considered suitable for large-scale mean annual temperature reconstructions and are therefore able to improve the paleoclimatic potential of Late Holocene tree-ring archives.

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-assisted alkaline CuO oxidation step to yield monomeric LOPs. The LOPs are extracted via SPE and finally analyzed via ultrahigh-performance liquid chromatography (UHPLC) coupled to electrospray ionization (ESI) and high-resolution Orbitrap mass spectrometry (HRMS). The method was applied to stalagmite samples with a sample size of 3–5 g and cave drip water samples with a sample size of 100–200 mL from the Herbstlabyrinth-Advent Cave in Germany. In addition, fresh plant samples, soil water, and powdered lignin samples were analyzed for comparison. The concentration of the sum of eight LOPs (Σ8) was in the range of 20–84 ng g−1 for the stalagmite samples and 230–440 ng L−1 for the cave drip water samples. The limits of quantification for the individual LOPs ranged from 0.3–8.2 ng per sample or 1.5–41.0 ng mL−1 of the final sample solution. Our method represents a new and powerful analytical tool for paleo-vegetation studies and has great potential to identify the pathways of lignin incorporation into 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 oxygen and carbon (δ18O, δ13C) measurements are referenced by distance from the top or bottom of the speleothem. Additional tables provide information on dating, including information on the dates used to construct the original age model and sufficient information to assess the quality of each data set and to erect a standardized chronology across different speleothems. The metadata table provides location information, information on the full range of measurements carried out on each speleothem and information on the cave system that is relevant to the interpretation of the records, as well as citations for both publications and archived data. The compiled data are available at http://dx.doi.org/10.17864/1947.147 .

A flight of marine terraces along the Cuban coast records Quaternary sea-level highstands and a general slowly uplifting trend during the Pleistocene. U/Th dating of these limestone terraces is difficult because fossil reef corals have been affected by open system conditions. Terrace ages are thus often based on geological and geomorphological observations. In contrast, the minimum age of the terraces can be constrained by dating speleothems from coastal mixing (flank margin) caves formed during past sea-level highstands and carving the marine limestones. Speleothems in Santa Catalina Cave have ages >360ka and show various cycles of subaerial-subaqueous corrosion and speleothem growth. This suggests that the cave was carved during the MIS 11 sea-level highstand or earlier. Some stalagmites grew during MIS 11 through MIS 8 and were submerged twice, once at the end of MIS 11 and then during MIS 9. Phreatic overgrowths (POS) covering the speleothems suggest anchialine conditions in the cave during MIS 5e. Their altitude at 16m above present sea level indicates a late Pleistocene uplift rate of