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Rationale: The first-row transition metals Cu, Ni, and Co show a strong binding affinity to natural organic matter. Compared to dissolved elements and stable water isotopes, they may be transported rapidly through the soil and host rock into caves in response to infiltration events. This study aims to assess the potential of transition metal ratios as indicators for infiltration changes in response to the seasonal and/or event-based rainfall variation., Methods: We developed a protocol to analyze Cu, Ni, and Co in the cave drip water using collision cell ICP-QMS without extensive sample pretreatment. The high Ca matrix leads to significant isobaric interferences on all isotope masses. Our method includes a correction of these matrix effects and yields results with comparable accuracy and reproducibility to other published methods. We applied this protocol to drip water samples from Larga Cave (Puerto Rico) covering at least two full annual cycles between 2014 and 2019 on a bimonthly scale., Results: The analysis of external reference materials yielded a reproducibility between 4.7% and 9.2% (relative standard deviation), validating the accuracy of the matrix correction method. The limit of detection is <0.04 ppb for Cu, <0.02 ppb for Ni, and <0.008 ppb for Co. The analysis of drip water samples from Larga Cave reveals pronounced changes of several orders of magnitude in all Element (El) to Ca, Cu/Ni, and Cu/Co ratios in response to seasonal infiltration changes. In addition, we observe a partly even stronger response after major tropical storms and heavy precipitation events of the period of record, for example, tropical storm "Bertha" (2014) and the category 5 hurricanes "Irma" and "Maria" (both 2017)., Conclusions: Transition metal ratios can be accurately measured in cave drip waters with high Ca matrix. At our tropical site, these are promising tracers of infiltration changes in response to changes in the amount of rainfall, providing the first step toward tropical cyclone reconstruction using trace elements in speleothems., (© 2022 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.)

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 another with Y, P, and Al, respectively. The second group reflects the content of detrital material. Increased weathering of soil minerals seems to have a strong influence on the silicate/carbonate weathering ratio controlling the variability of Mg, Ba, and Sr. Meteorological and Global Network of Isotopes in Precipitation (GNIP) station data were used to calculate the δ18O values of the drip water (infiltration‐weighted, mean annual, and the mean of the winter precipitation δ18O values) as well as the corresponding speleothem calcite. The δ18O values calculated by the infiltration‐weighted model show similar patterns and amplitudes as the measured δ18O values of the two stalagmites. This suggests that the δ18O values of speleothem calcite reflect the δ18O values of infiltration‐weighted annual precipitation, which zis related to mean annual temperature, resulting in a significant correlation between mean annual temperature and the measured δ18O values of stalagmite Zoo‐rez‐2. This relationship could potentially be used for quantitative climate reconstruction in the future by extending the time series back in time with further stalagmites from Zoolithencave. Key Points: Silicate versus carbonate weathering has an influence on speleothem trace elementsYttrium, phosphorus, and aluminum reflect detrital content of the speleothemsδ18O values of the stalagmites are a proxy for mean annual temperature [ABSTRACT FROM AUTHOR]

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 hydrological cycle. During Heinrich stadials and the Younger Dryas, climatic conditions in Cuba were comparably cool and/or dry. In contrast, warm Dansgaard/Oeschger cycles were accompanied by wetter conditions. This is in agreement with previous evidence for the Holocene, when North Atlantic cold (warm) events coincided with drier (wetter) conditions in Cuba. However, our record suggests that this connection was less dominant during MIS 4 to 2, displayed by a weaker response of Cuban precipitation proxies to North Atlantic climatic shifts than during MIS 5 in particular. We hypothesize that this weaker connection was mediated by the southerly shifted ITCZ inducing a weakening of the northern branch of the Caribbean Low Level Jet which usually transports moisture into the northern Caribbean. This is strikingly evident during the deglacial, when driest and/or coolest conditions prevailed in western Cuba from HS 1 into the Younger Dryas, including the Bølling/Allerød interstadial. • We present a speleothem stable isotope and trace element record from Cuba covering the last 96 ka. • Our results confirm the link of Caribbean precipitation to NA climate, insolation and the AMOC. • Last glacial NA cold (warm) (inter)-stadials coincided with drier (wetter) conditions in Cuba. • During the LGM, our data suggest a shift to more abundant C4 vegetation and/or reduced soil activity. • We observe a weaker sensitivity to NA climate during MIS 4 to 2 compared to MIS5 and the Holocene. [ABSTRACT FROM AUTHOR]

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 records are in general agreement with the NGRIP δ18O record on millennial time scales indicating that speleothem δ18O values at the Herbstlabyrinth reflect large-scale climate variability in the North Atlantic area. The 8.2 ka event is clearly visible as a pronounced negative excursion in the δ18O records. In all other proxies, it is not reflected as a major excursion. Correlation and principal component analysis enable us to disentangle the various processes affecting the stable isotope and trace element signals. Phases with higher P, Ba and U concentrations and more negative δ13C values are interpreted as reflecting more productive vegetation above the cave. The negative correlation of Mg with P, Ba and U and the positive correlation with δ13C indicate more recharge during phases of more productive vegetation, probably because of increased rainfall. The majority of the observed phases of reduced vegetation productivity and drier climate coincide with cooler periods in the polar North Atlantic as reflected by a higher abundance of hematite-stained grains (i.e. the Bond events), suggesting a close relationship between terrestrial climate in Central Europe and the polar North Atlantic. [ABSTRACT FROM AUTHOR]

Abstract: 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 193nm Nd:YAG lasers. They are small for refractory lithophile elements, in particular for the 193nm laser (<5%). For chalcophile/siderophile trace elements with low boiling points, however, these effects are large (up to 40% and 20% for the 213 and 193nm lasers, respectively), and variable for the NIST glasses and carbonates. In this paper, a protocol for precise and accurate LA-ICP-MS analysis of calcium carbonates is established. Isotopes for interference-free measurements at low (M/ΔM ~300) and medium (M/ΔM ~4000) mass resolution have been identified. The NIST glasses are suitable for calibration of refractory lithophile element concentrations. However, matrix-matched calibration with carbonate reference materials, such as USGS MACS-1 or MACS-3, is necessary for accurate analysis of chalcophile/siderophile elements with low boiling points. Analytical reproducibility (RSD) is a factor of ~2 better using the 193nm laser than the 213nm laser. As shown by the analysis of MACS-1 and MACS-3, LA-ICP-MS analyses yield results that agree with the reference values within relative uncertainties of ca. 5–10% at the 95% confidence level. We have applied LA-ICP-MS for the determination of trace element concentrations in calcite and aragonite layers of a stalagmite and found large variations for Mg, Zn, Sr, and U. In ostracod shells, the concentrations of some trace elements (e.g., Sr and Ba) vary significantly, indicating the potential for paleoclimate research. [Copyright &y& Elsevier]

The Late Holocene was characterized by several centennial-scale climate oscillations including the Roman Warm Period, the Dark Ages Cold Period, the Medieval Warm Period and the Little Ice Age. The detection and investigation of such climate anomalies requires paleoclimate archives with an accurate chronology as well as a high temporal resolution. Here, we present 230Th/U-dated high-resolution multi-proxy records (δ13C, δ18O and trace elements) for the last 2500 years of four speleothems from Bunker Cave and the Herbstlabyrinth cave system in Germany. The multi-proxy data of all four speleothems show evidence of two warm and two cold phases during the last 2500 years, which coincide with the Roman Warm Period and the Medieval Warm Period, as well as the Dark Ages Cold Period and the Little Ice Age, respectively. During these four cold and warm periods, the δ18O and δ13C records of all four speleothems and the Mg concentration of the speleothems Bu4 (Bunker Cave) and TV1 (Herbstlabyrinth cave system) show common features and are thus interpreted to be related to past climate variability. Comparison with other paleoclimate records suggests a strong influence of the North Atlantic Oscillation at the two caves sites, which is reflected by warm and humid conditions during the Roman Warm Period and the Medieval Warm Period, and cold and dry climate during the Dark Ages Cold period and the Little Ice Age. The Mg records of speleothems Bu1 (Bunker Cave) and NG01 (Herbstlabyrinth) as well as the inconsistent patterns of Sr, Ba and P suggests that the processes controlling the abundance of these trace elements are dominated by site-specific effects rather than being related to supra-regional climate variability. [ABSTRACT FROM AUTHOR]

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 'whole event'. The timing and duration of the 8.2 ka event are different for the individual records, which may, however, be related to dating uncertainties. Whereas stalagmite Bu4 from Bunker Cave also shows a negative anomaly in the δ13C values and Mg content during the event, the two speleothems from the Herbstlabyrinth cave system do not show distinct peaks in the other proxies. This may suggest that the speleothem δ18O values recorded in the three stalagmites do not primarily reflect climate change at the cave site, but rather large-scale changes in the North Atlantic. This is supported by comparison with climate modelling data, which suggest that the negative peak in the speleothem δ18O values is mainly due to lower δ18O values of precipitation above the cave and that temperature only played a minor role. Alternatively, the other proxies may not be as sensitive as δ18O values to record this centennial-scale cooling event. This may particularly be the case for speleothem δ13C values as suggested by comparison with a climate modelling study simulating vegetation changes in Europe during the 8.2 ka event. Based on our records, it is not possible to resolve which of these hypotheses is most appropriate, but our multi-proxy dataset shows that regional climate evolution during the event was probably complex, although all δ18O records show a clear negative anomaly. • Three speleothems show pronounced negative peaks in δ18O values during 8.2 ka event. • All records can be divided into a 'whole event' and a 'central event'. • Other proxies show no distinct consistent peaks during the 8.2 ka event. • Magnitude of δ18O peaks can be explained by change in δ18O values of precipitation. • Speleothem δ18O values reflect large-scale changes in the North Atlantic. [ABSTRACT FROM AUTHOR]

Two stalagmites from B7-Cave in northwest Germany, which is part of the same cave system as the intensively studied Bunker Cave, were re-dated by multi collector inductively coupled plasma mass spectrometry (MC-ICPMS) 230Th/U-dating. Furthermore, the concentration of Mg, Sr, Ba, P, Y, Zn, and Al were determined at high-resolution by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Stalagmite B7-1 grew from 10.8 to 5.8 ka BP. Stalagmite B7-7 grew during three growth phases from 11.0 to 6.2, 3.13 to 2.86 (late Bronze Age), and 1.27 to 1.15 ka BP (early Medieval Period). Aluminium is a proxy for detrital material and corresponds very well with the visible detrital layers in stalagmite B7-1 and the oldest growth phase of stalagmite B7-7. The two younger growth phases of stalagmite B7-7 are very clean and show very low Al concentrations. Phosphorus, Y, and Zn show positive correlations in both stalagmites and all growth phases, but do not show a relationship to temperature or precipitation. This may be related to the elevated detrital content in both stalagmites. Barium and Sr also show a positive correlation in both stalagmites and all growth phases, which is related to their dependency on growth rate. Magnesium is most probably influenced by prior calcite precipitation and therefore a proxy for past precipitation/infiltration. The Mg records of stalagmite B7-1 and of the oldest growth phase of stalagmite B7-7 show decreasing Mg concentration with time reflecting decreasing prior calcite precipitation and therefore increasing precipitation during the Early to Mid-Holocene. This is consistent with other climate reconstructions from Central Europe. [ABSTRACT FROM AUTHOR]

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 (D Mg and D Sr) 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 speleothem calcite D Mg and D Sr. The datasets cover a large range of climatic and geological settings resulting in a large range of drip water Mg/Ca ratios. Speleothem calcite D Sr shows a positive correlation with the calcite Mg/Ca ratio. Furthermore, D Mg shows a clear temperature dependence (D Mg = 0.013*e0.035*T). Previous work proposed that the slope of a trend line through a plot of ln(Sr/Ca) versus ln(Mg/Ca) of a speleothem trace element dataset is between 0.709 and 1.003 if dominated by PCP. However, this only holds true if the initial drip water Mg/Ca and Sr/Ca ratios as well as D Sr and D Mg are constant for the whole dataset. We use an excel-based PCP model (see Electronic Annex) to assess the potential influence of PCP on drip water and speleothem Mg/Ca and Sr/Ca ratios and simulate different initial drip water Ca, Mg, and Sr concentrations corresponding to limestone, dolostone, and mixed host rock compositions. In the case of enhanced PCP and high Mg/Ca ratios, calcite D Sr increases progressively with the mean Mg/Ca ratio of the speleothem time series resulting in steeper slopes of ln(Sr/Ca) versus ln(Mg/Ca) of up to 1.45. We show that PCP can induce slopes ranging from 0.709 (or even shallower) up to 1.45. This large range suggests that the previously applied criteria to detect PCP in speleothem records were too strict and may lead to unjustified exclusion of PCP as a potential interpretation of speleothem and drip water trace element ratios. Thus, the number of speleothem Mg/Ca and Sr/Ca datasets that potentially reflect past changes in effective rainfall may be larger than previously suggested. [ABSTRACT FROM AUTHOR]

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 230 Th/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 significant anti-correlation of speleothem Mg/Ca ratios with autumn/winter (October to March) precipitation (r = −0.61, p < 0.01), which is statistically robust when considering age uncertainties and auto-correlation. This relationship is used to develop a quantitative reconstruction of autumn/winter precipitation. During the late Holocene, our data suggest a heterogeneous pattern of past regional winter hydroclimate in the Carpathian/Balkan realm, along with intermittent weakening of the dominant influence of North Atlantic forcing. In agreement with other regional paleo-hydrological reconstructions, the observed variability reveals periodically occurring strong NW–SE hydro-climate gradients. We hypothesize, that this pattern is caused by shifts of the eastern edge of the area of influence of the NAO across central-eastern Europe due to the confluence of North Atlantic forcing, and other climatic features such as the East Atlantic/Western Russia (EAWR) pattern. [ABSTRACT FROM AUTHOR]

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 in aragonitic speleothems (derived D U = 3.74 ± 1.13). Because our calculated D U is considerably above 1 increased prior aragonite precipitation due to increased karst water residence time should strongly control stalagmite aragonite U/Ca values. Consequently, uranium concentrations in aragonitic speleothems should act as excellent proxies for effective rainfall. We test this using a high-resolution ICP-MS derived trace element dataset from a Belizean stalagmite. YOK-G is an aragonitic stalagmite from Yok Balum cave in Belize with an extremely robust monthly-resolved chronology built using annual δ 13 C cycles. We interpret seasonal U/Ca variations in YOK-G as reflecting changes in the amount and seasonality of prior aragonite precipitation driven by variable rainfall amounts. The U/Ca record strongly suggests that modern drying has occurred in Belize, and that this drying was primarily caused by a reduction in wet season rainfall. This is consistent with published stable isotope data from YOK-G also very strongly suggesting modern rainfall reductions, previously interpreted as the result of southward ITCZ displacement. Our results strongly suggest that U/Ca values in aragonitic speleothems are excellent proxies for rainfall variability. This new tool, combined with the exceptional chronological control characteristic of aragonitic stalagmites and the high spatial resolution afforded by modern microanalytical techniques, should facilitate the construction of new exquisitely resolved rainfall records, providing rare insights into seasonality changes as well as long-term changes in local recharge conditions. [ABSTRACT FROM AUTHOR]

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 sequence and their adjacent <50 μm and >50 μm dust fractions across a selection of 41 major and trace elements. This approach is used to investigate samples from three fully arid deserts: the An Nafud in Saudi Arabia, the Negev in Israel, and the Mojave in the USA, which are compared to the significantly different environment of the semi-arid Knersvlakte in South Africa. A new in situ trace element analysis protocol was developed to perform femto- and nanosecond sector-field LA-ICP-MS microanalyses at high-spatial resolution, which allows us to measure the most recent varnish layers for their comparison with recent dust. In agreement with previous studies, all varnishes are enriched in Mn, Pb, Ce, Co, Ba, Zn, Ni, and the Rare-Earth Elements (REE). Here we demonstrate that fine (<50 μm) dust is characterized by similar trace element trends as the varnishes, at overall lower mass fractions. Dust >50 μm has low trace element mass fractions, and enrichment patterns plotting distinctly away from varnish and fine dust. Based on these geochemical patterns, our results indicate a general enrichment mechanism from fine dust to varnish. Previous studies suggested dust to play an integral role in providing the trace elements that are incorporated into the varnish by pH-Eh fluctuations in short-term rain and fog events. We amalgamate and refine previous growth models by providing direct evidence that leaching of about 10% of the Mn and other trace elements from clay minerals in rain or fog droplets at pH ~5 and subsequent scavenging on varnish surfaces at pH ~8 leads integrated over time to the distinct enrichment patterns of the varnish, while initial Mn oxyhydroxide formation is suggested to follow pathways of metal oxide mediated photo-catalysis. For the semi-arid occurrence in the Knersvlakte we present a distinct growth model as both environment, varnish, and dust composition differ significantly from the arid settings. Here, thick, metallic-looking varnish occurs mainly on the rim of quartz pebbles, lacks microlamination, and likely has upscaled growth processes. Among other aspects, we suggest a more complex interplay between photo-catalysis, nocturnal condensation events on quartz pebbles with subsequent water trapping at the rock-soil-atmosphere interface, due to a salic top-soil layer, to mainly account for these differences. Unlabelled Image • First systematic study comparing youngest varnish layers to different fractions of recent dust • Higher similarity of varnish and fine dust excludes coarse fractions from varnish growth process. • Airborne and soil dust are geochemically alike, explaining similarities in varnishes from different geomorphological niches. • Differences between varnishes arise from environmental aspects, geomorphological position, and dust mineral assemblage. • Mn accumulation via 10% leaching from clays and metal-oxide-mediated photooxidation explain subaerial varnish growth. [ABSTRACT FROM AUTHOR]

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 centennial-scale fluctuations, which were probably driven by local hydrological processes. In contrast, variations in the stalagmite δ18O values reflect integrated changes in rainfall amount from the ISM. The KPC1 record agrees with other speleothem δ18O records of Southeast Asian summer monsoon from the last millennium, as well as the lake multi-proxy and tree-ring PDSI data from Mainland Southeast Asia, but diverges from records from the Indo-Pacific equatorial regions and the western Pacific. We conclude that hydroclimate variability at the western side of Mainland Southeast Asia is mainly driven by changes in moisture transport of the ISM. On socially relevant timescales, the KPC1 data set shows that a period of stable rainfall (850–1150 CE) coincides with the early success of the early empires (e.g., Pagan, Angkor, and Dai Viet) in Mainland Southeast Asia. In line with previous studies in the region, we speculate that the high variability in rainfall between 1150 and 1300 CE and droughts during 1300–1550 CE played a significant role in the demise of ancient societies in Southeast Asia. • Stalagmite multi-proxy record of Thailand covering the last 1400 years. • Unstable conditions with long varying dry and wet phases during 500–850 CE and 1150–1300 CE. • Stable rainfall in 850–1150 CE and dry conditions since 1300 CE. [ABSTRACT FROM AUTHOR]

Speleothem records have been successfully calibrated against instrumental data, e.g., using stable oxygen isotope or annual growth lamina data considered as reliable recorders of air temperature or precipitation amount. We present the first high-resolution trace element (Mg/Ca, Sr/Ca, Ba/Ca) record providing the potential for quantitative climate reconstruction, deduced from stalagmites from Clo¸sani Cave, SW Romania.The calibration approach relies on a precise age control - in particular for the last 250 years, where the chronology is based on three independent dating methods. Chemical lamina counting is combined with the identification of the 20th century 14C bomb peak and 230Th/U dating. Long-term cave monitoring and model simulations of drip water and speleothem elemental variability support the inference that precipitation-relatedprocesses are the main drivers of speleothem Mg/Ca ratios. Calibration against instrumental climate data shows a significant anti-correlation of speleothem Mg/Ca ratios with autumn/winter (October to March) precipitation (r = -0.61, p < 0.01), which is statistically robust whenconsidering age uncertainties and auto-correlation. This relationship is then used to develop a quantitative reconstruction of Holocene autumn/winter precipitation.During the last 3.6 ka, our data suggest a heterogeneous pattern of past regional winter hydroclimate in the Carpathian/Balkan realm, along with intermittent weakening of the dominant influence of North Atlantic forcing. In agreement with other regional paleo-hydrological reconstructions, the observed variability reveals periodically occurring strong NW-SE hydro-climate gradients. We hypothesize, that this pattern is caused by shifts of theeastern edge of the area of influence of the NAO across central-eastern Europe due to the confluence of North Atlantic forcing, and other climatic features such as the East Atlantic/Western Russia (EAWR) pattern. [ABSTRACT FROM AUTHOR]