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Lamalunga Cave (Altamura, Southern Italy) is renowned for the discovery in 1993 of an excellently preserved Neanderthal skeleton. Given the importance of the findings and the potential use of Lamalunga speleothems for paleoclimate reconstructions, a detailed monitoring program was undertaken to investigate the connections between microclimate parameters and speleothem growth. The cave air temperature is characterized by annual sinusoidal cycles with increasing phase shift and decreasing thermal amplitude from ± 2.1°C to ± 0.04°C as a function of increasing rock overburden, and daily to sub-daily cycles induced by surface air pressure (SAP) variations characterized by strong 24-hour and 12-hour solar harmonic frequencies, with thermal amplitude decreasing from 0.0054°C to 0.0021°C in the deeper parts of the cave. The ventilation regime is mainly controlled by SAP fluctuations. Fast SAP rises can trigger "emptying events" during which most of the cave air is replaced and the CO2 concentration falls towards near-atmospheric values. The steady and gentle ventilation created by SAP fluctuations also influences the growth and morphology of calcite coralloids, with larger popcorn assemblages concentrated in the northern galleries and delicate branching morphologies prevailing along the South Gallery where stable temperature and relative humidity conditions occur. The study is a seminal example of how high-precision measurements of cave air temperature can provide a wealth of information on cave ventilation and thermal regime and provide valuable support for robust paleoclimate reconstruction from speleothems. [ABSTRACT FROM AUTHOR]

This study utilizes speleothem trace elements as climate proxies to reconstruct hydroclimate variability over approximately 350 years in the Southern Cook Islands. Stalagmites Pu17 and Pu4 from Pouatea cave were analyzed using high-resolution LA-ICP-MS for trace elements (Mg, Na, Sr, P, U, Y). By monitoring cave dripwater and conducting regression analysis, we found that Mg, Sr, and Na in Pouatea dripwater mostly originated from marine aerosols, while Sr and Ba were primarily from bedrock, with additional Ba coming from marine aerosols and weathered oceanic basalt leaching. Mg was identified as the most reliable element for hydroclimate reconstruction due to its predominantly marine aerosol origin. Infiltration, via dilution of marine aerosols and bedrock inputs, was identified as the main driver of trace element variations in Pouatea at a seasonal scale. Transfer functions were established between each trace element and effective infiltration was calculated, with Mg showing the strongest correlation. The reconstructed infiltration data were compared with climate indices, showing an overarching role of the SPCZ and ENSO in controlling rainfall in the South Pacific. This research demonstrates the potential of speleothem trace elements for paleohydroclimate reconstructions, improving understanding of rainfall variability in the climatically vulnerable South Pacific Islands over the past millennia. [ABSTRACT FROM AUTHOR]

Cave carbonate mineral deposits (speleothems) contain trace elements that are intensively investigated for their significance as palaeoclimate and environmental proxies. However, chlorine, which is abundant in marine and meteoric waters, has been overlooked as a potential palaeo-proxy, while cosmogenic 36Cl could, in principle, provide a solar irradiance proxy. Here, total Cl concentrations analysed from various speleothems were low (3–14 mg/kg), with variations linked to crystal fabrics. High-resolution synchrotron radiation micro X-ray fluorescence (μ-XRF) trace element mapping showed Cl often associated with Na, Si, and Al. We propose that speleothems incorporate Cl in two fractions: (1) water soluble (e.g., fluid inclusions) and (2) water insoluble and strongly bound (e.g., associated with detrital particulates). However, disparities indicated that alternate unidentified mechanisms for Cl incorporation were present, raising important questions regarding incorporation of many trace elements into speleothems. Our first measurements of 36Cl/Cl ratios in speleothems required large samples due to low Cl concentrations, limiting the potential of 36Cl as a solar irradiance proxy. Critically, our findings highlight a knowledge gap into how Cl and other trace elements are incorporated into speleothems, how the incorporation mechanisms and final elemental concentrations are related to speleothem fabrics, and the significance this may have for how trace elements in speleothems are interpreted as palaeoclimate proxies. [ABSTRACT FROM AUTHOR]

The 8.2 ka event is the most significant global climate anomaly of the Holocene epoch, but a lack of records from Mainland Southeast Asia (MSEA) currently limits our understanding of the spatial and temporal extent of the climate response. A newly developed speleothem record from Tham Doun Mai Cave, Northern Laos provides the first high‐resolution record of this event in MSEA. Our multiproxy record (δ18O, δ13C, Mg/Ca, Sr/Ca, and petrographic data), anchored in time by 9 U‐Th ages, reveals a significant reduction in local rainfall amount and weakening of the monsoon at the event onset at ∼8.29 ± 0.03 ka BP. This response lasts for a minimum of ∼170 years, similar to event length estimates from other speleothem δ18O monsoon records. Interestingly, however, our δ13C and Mg/Ca data, proxies for local hydrology, show that abrupt changes to local rainfall amounts began decades earlier (∼70 years) than registered in the δ18O. Moreover, the δ13C and Mg/Ca also show that reductions in rainfall continued for at least ∼200 years longer than the weakening of the monsoon inferred from the δ18O. Our interpretations suggest that drier conditions brought on by the 8.2 ka event in MSEA were felt beyond the temporal boundaries defined by δ18O‐inferred monsoon intensity, and an initial wet period (or precursor event) may have preceded the local drying. Most existing Asian Monsoon proxy records of the 8.2 ka event may lack the resolution and/or multiproxy information necessary to establish local and regional hydrological sensitivity to abrupt climate change. Plain Language Summary: The most significant global climate event in the last ∼11,000 years occurred ∼8,200 years ago (the "8.2 ka event"). Many globally distributed records of past climate (paleoclimate) document significant changes during the event, but there are few from Mainland Southeast Asia available to reconstruct the climate impacts in this region. We present a new speleothem (cave sample) record from Tham Doun Mai Cave, Northern Laos that uses multiple geochemical and physical signals (proxies) to document local and regional climate effects of the 8.2 ka event at a high resolution. Using oxygen isotopes, we find that the 8.2 ka event weakened regional monsoon intensity for at least ∼170 years, which resembles findings from other studies. However, other proxies suggest local rainfall changed abruptly decades before the signal of monsoon weakening. Additionally, local drying may have lasted much longer than current estimates of 8.2 ka event responses. Most proxy records of the 8.2 ka event in monsoon regions lack similar multiproxy information and/or do not have high enough resolution to fully capture the climatic response. Additional records like ours from monsoon regions may assist in establishing how sensitive local and regional rainfall is to abrupt climate change. Key Points: High‐resolution speleothem record of the 8.2 ka event in northern Laos shows weakened monsoon intensity and reduced local rainfall amountsMultiproxy data suggest the disruption to local rainfall amounts started decades before the weakened monsoon intensity inferred from δ18OPrevious monsoon records of the event lack the resolution and/or multiproxy dimensions needed to reconstruct local hydrologic changes [ABSTRACT FROM AUTHOR]

Annually laminated speleothems have the potential to provide information on high‐frequency climate variability and, simultaneously, provide good chronological constraints. However, there are distinct types of speleothem annual laminae, from physical to chemical, and a common mechanism that links their formation has yet to be found. Here, we analyzed annually laminated stalagmites from 23 caves and 6 continents with the aim to find if there are common mechanisms underlying their development. Annually laminated stalagmites are least common in arid and semiarid climates, and most common in regions with a seasonality of precipitation. At a global scale, we observe faster growth rates with increasing mean annual temperature and decreasing latitude. Changepoints in average growth rates are infrequent and age‐depth relationships demonstrate that growth rates can be approximated to be constant. In general, annually laminated stalagmites are characterized by centennial‐scale stability in calcite precipitation due to a sufficiently large and well‐mixed water source, a time series spectrum showing first‐order autoregression due to mixing of stored water and annual recharged water, and an inter‐annual flickering of growth acceleration, bringing growth rates back to the long‐term mean. Climate forcing of growth rate variations is observed where a multi‐year climate signal is strong enough to be the dominant control on calcite growth rate variability, such that it retains a climate imprint after smoothing of this signal by mixing of stored water. In contrast, long‐term constant growth rate of laminated stalagmites adds further robustness to their unparalleled capacity to improve accuracy of chronology building. Plain Language Summary: Growth layers, or laminae, are found in many biological and geological records. Stalagmites, mineral precipitates found in caves, can contain annual laminae. Stalagmites grow upwards from water which drips onto them from overlying fractures and voids. For annually laminated stalagmites, it is not known where and for how long they form, and why. Here, we review and statistically analyze a global data set of laminated stalagmites. They are less common in water‐limited climates and are only found in regions with seasonal precipitation. The annual average laminated stalagmite vertical growth is 0.093 mm, increasing with warmer temperatures. Stalagmite accumulation rate is relatively unchanging over time. This is because their drip water source has enough volume and a stable chemical composition to be a buffer to rapid changes. Year‐to‐year, we see a "flickering," where accumulation rate returns toward the long‐term average, also due to this buffering effect. For an environmental signal to be preserved in stalagmite laminae thickness requires a large perturbation, such as wet or dry years associated with the El Niño‐Southern Oscillation, that can override the buffering of the overlying water source. The long‐term constant growth rate of laminated stalagmites provides an unparalleled capacity for precise chronology building. Key Points: Laminated stalagmites are characterized by centennial‐scale stability in accumulation rateStrong multi‐year climate signals may retain an imprint in annual growth rate after smoothing of this signal by mixing with stored waterLong‐term constant growth rate of laminated stalagmites benefits accurate chronology building [ABSTRACT FROM AUTHOR]

Synchrotron high‐resolution and micro‐X‐ray fluorescence elemental mapping of two coeval coralloid speleothems from Lamalunga Cave (Italy) are complemented with petrographic, morphological and microstratigraphic studies. The importance of these speleothems relies on their direct and indirect association with a complete Neanderthal skeleton ('Altamura Man') found inside the cave. The coralloids grew discontinuously between 64·6 ka and the Holocene and reveal exceptionally high concentrations of Mg, Sr and Si, particularly on convex surfaces, where evaporation is more intense. The incorporation of trace elements depends on several factors including location, shape and geometrical evolution during their growth, as well as climate and environmental parameters. This resulted in calcite precipitation with Sr compositions from 100 to 1200 ppm and an average concentration of 7000 ppm Mg. An unusually high Si content (up to 16%) is possibly derived from volcanic ash transported as particulate and in solution inside the cave. The most common fabrics observed consist of non‐fluorescent elongated columnar calcite forming clean isopachous bands and fluorescent fibre‐like crystals associated with laminated, lenticular bands high in Sr, Mg and Si. Variability in Sr, Mg and Si concentrations appears to induce fabric changes in the coralloids. Elongation and lattice distortion of the crystals was found to coincide with high Mg concentrations. The transition from compact elongated to open to fibre‐like, is here interpreted as due to high concentrations of Si and Sr, which are preferentially incorporated in the speleothem at crystal boundaries and intra‐laminae. It is here inferred that coralloid fabric changes and their elemental content potentially record local rainfall variations through time, with the clean compact calcite marking high infiltration and open fibre‐like and micrite fabrics recording dry periods. [ABSTRACT FROM AUTHOR]

Investigation by high resolution Transmission Electron Microscopy (HR-TEM) and Synchrotron-Radiation based micro X-ray fluorescence (SR-μXRF) of diagenesis in carbonates imposes uncertainties on the boundary between stages of crystal growth and post-depositional processes. Speleothems and dolomite are exemplars of the entire range of processes that result in solid materials consisting of crystals. HR-TEM investigation of speleothems suggests that there are many possible pathways of crystallization comprising classical ion-mediated, particle-mediated and formation of metastable phases. Diverse pathways influence the potential of a primary carbonate to undergo post-depositional transformation, with consequences on the accuracy of the preservation of original chemical and physical properties. The capability to date speleothems with U-series techniques is unique amongst other archives of Earth's history. It has been observed that U mobilization, which results in age inversions and uncertainties, is dependent on both crystallization and diagenetic pathways. Here, it is also proposed that the presence of organic colloids, mostly consisting of humic substances (HS), influences the extent to which U may be mobilized, as well as the capacity of original speleothem fabric to undergo dissolution and re-precipitation. Our hypothesis that colloidal HS protect the initial products of crystallization from subsequent diagenesis could explain the existence of primary dolomite preserved in Triassic sabkha facies influenced by fluvial input of siliciclastics. Primary dolomite nanocrystal aggregates coexist with single crystals, highlighting that multiple formation mechanisms were possible, which explains the variety of micro and nanostructures observed by conventional TEM investigations in dolomites. Similarly, we observed calcite nanocrystal aggregates and single crystals preserved in Triassic shallow marine facies, which are famous for their preservation of original aragonite, influenced by continental siliciclastic input. Our new data on the Triassic carbonates suggest that when HS colloids are abundant, nanocrystal aggregates are commonly preserved, possibly because of a protective coating by organic substances. These hinder both the transformation of the aggregates into larger crystals and multiple-steps diagenetic transformation that obliterate primary environmental signals. As opposed to textbook assumptions, it is here proposed that the existence of multiple crystallization pathways for carbonates within the same depositional environment, such as a cave setting or a sabkha, have repercussion on the early diagenetic processes and the extent to which diagenesis significantly resets the original chemical and physical signals. By using speleothems as paradigm for carbonates formed in natural environments where organic compounds are ubiquitous, the present review corroborates the notion that most mechanisms of carbonate crystallization, when the carbonate is not a biomineral, follow inorganic pathways. However, the role of organic substances, as inhibitors of growth and diagenesis, has profound influences on preservation of initial states of crystal formation. [ABSTRACT FROM AUTHOR]

Terrestrial data spanning the Last Glacial Maximum (LGM) and deglaciation from the southern Australian region are sparse and limited to discontinuous sedimentological and geomorphological records with relatively large chronological uncertainties. This dearth of records has hindered a critical assessment of the role of the Southern Hemisphere mid-latitude westerly winds on the region's climate during this time period. In this study, two precisely dated speleothem records for Mairs Cave, Flinders Ranges, are presented, providing for the first time a detailed terrestrial hydroclimatic record for the southern Australian drylands during 23-15 ka. Recharge to Mairs Cave is interpreted from the speleothem record by the activation of growth, physical flood layering, and δ18O and δ13C minima. Periods of lowered recharge are indicated by 18O and 13C enrichment, primarily affecting δ18O, argued to be driven by evaporation of shallow soil/epikarst water in this water-limited environment. A hydrological driver is supported by calcite fabric changes. These include the presence of laminae, visible organic colloids, and occasional dissolution features, related to recharge, as well as the presence of sediment bands representing cave floor flooding. A shift to slower-growing, more compact calcite and an absence of lamination is interpreted to represent reduced recharge. The Mairs Cave record indicates that the Flinders Ranges were relatively wet during the LGM and early deglaciation, particularly over the interval 18.9-15.8 ka. This wetter phase ended abruptly with a shift to drier conditions at 15.8 ka. These findings are in agreement with the geomorphic archives for this region, as well as the timing of events in records from the broader Australasian region. The recharge phases identified in the Mairs Cave record are correlated with, but antiphase to, the position of the westerly winds interpreted from marine core MD03-2611, located 550 km south of Mairs Cave in the Murray Canyons region. The implication is that the mid-latitude westerlies are located further south during the period of enhanced recharge in the Mairs Cave record (18.9-16 ka) and conversely are located further north when greater aridity is interpreted in the speleothem record. A further comparison with speleothem records from the northern Australasian region reveals that the availability of tropical moisture is the most likely explanation driving enhanced recharge, with further amplification of recharge occurring during the early half of Heinrich Stadial 1 (HS1), possibly influenced by a more southerly displaced Intertropical Convergence Zone (ITCZ). A rapid transition to aridity at 15.8 ka is consistent with a retraction of this tropical moisture source. [ABSTRACT FROM AUTHOR]

Speleothems and other carbonate deposits such as tufa containing high proportions of detrital material can be difficult to chemically date due to detrital thorium levels causing a high level of error in conventional U-Th disequilibrium dating. Here we investigate the use of an alternative technique centring on radiocarbon dating of organic matter preserved within the detrital fraction. Non-acid soluble humic, particulate and detritally absorbed organic matter was recovered from eight samples from a flowstone sinter formed within a roman aqueduct at Trento in Italy with a maximum age of 100 CE (1850 cal yr BP), and two repeat samples from a dripstone formed within the 20th Century on a wire fence at Lilly-Pilly Cave, Buchan Caves Reserve in Victoria, Australia. In the aqueduct samples the median calibrated 14 C ages ranged from 2232 to 2889 cal yr BP, with 95.4% probability age range in the youngest and oldest samples of 2153–2337 and 2342–3449 cal yr BP respectively. The median age of the more modern dripstone was 336 cal yr BP, with a 95.4% probability age range of 148–486 cal yr BP. These results provide very approximate ball-park estimates of the age of the sample, but are consistently too old when compared to the known maximum ages of formation. It is hypothesised that this offset is due to a combination of the nature of the organic carbon transported from the source organic matter pools, and reworking of both modern and old organic carbon by in situ microbial communities. [ABSTRACT FROM AUTHOR]

Modern to Holocene tropical Pacific stalagmites are commonly difficult to date with the U-series, the most commonly used dating method for speleothems. When U-series does not provide robust age models, due to multiple sources of 230Th or little U, radiocarbon is, potentially, the best alternative. The 14C content of two stalagmites (Pu17 and Nu16) collected from Pouatea and Nurau caves in the Cook Island Archipelago of the South Pacific were measured to obtain accurate chronology for their most modern parts. The bomb-pulse soil continuum modelling indicates that bomb radiocarbon in Pu17 onsets in 1956 and reaches its maximum in 1966 CE, suggesting a fast transfer of atmospheric carbon to the stalagmite of <1 year. The modelling for Pu17 suggests a 20% contribution from C 1 - an instantaneous carbon source, which renders possible an immediate transfer of atmospheric signal into the cave. Nu16 shows a slower transfer of atmospheric carbon to the stalagmite than Pu17, with bomb radiocarbon onsetting in 1957 CE and peaking in 1972 CE. The less negative δ13C values in Nu16 than Pu17, and also the modelling corroborated this, which points out no contribution from the instantaneous carbon source. The radiocarbon age models and laminae counting age models were then spliced to achieve a single master chronology for the top part of each stalagmite. This study is an example of 14C age modelling combined with visible physical and chemical laminae counting and how it can improve the accuracy and precision of dating for otherwise hard-to-date tropical Pacific speleothems. Such accurate and precise age models pave the way to obtain sub-annually resolved paleoclimate records by further improving the calibration of climate proxy data with the current and instrumental weather parameters. [ABSTRACT FROM AUTHOR]

The quality of climate proxy data from speleothem archives depends to varying degrees on crystallization processes, which result in diverse fabrics. Here, we document shifts in calcite growth mechanisms, from ion-by-ion to nanoparticle/nanocrystal attachment, in stalagmites from the tropical island of Atiu (South Pacific). Changes in solution stoichiometry and organic matter content result in the development of two columnar fabrics that are common elsewhere in settings characterized by seasonal contrast. A porous columnar fabric, characterized by intracrystalline micro and nanoporosity grows via a non-classical pathway through amorphous calcium carbonate (ACC) nanoparticles (∼2–4 nm in diameter) and calcite nanocrystal attachment. Despite subsequent transformation of nanoparticles/crystals into a large calcite crystal, the porous columnar fabric appears to preserve a δ18O signal that faithfully reflects that of the parent fluid via quasi-equilibrium fractionation. Furthermore, the porous fabric shows random and fuzzy lateral distributions of Sr, another hydrological proxy, yet this element's incorporation follows equilibrium partitioning. The chemical properties of compact columnar fabrics, which appear to grow by classical ion-by-ion attachment, may not directly reflect those of the original depositional environment because of degassing, the presence of growth inhibitors (such as Na) and very early diagenetic modifications. Columnar porous calcite fabrics that formed through non-classical pathways in other settings may faithfully record the original properties of the parent drip water, whereas compact fabrics that formed through classical pathways elsewhere may not. It is concluded that the study of fabrics at the nano-scale is a necessary complement to speleothem research to identify the influence of crystallization pathways on the accuracy of proxy data. • Stalagmite calcite forms through complex crystallization pathways. • Both classical and non-classical processes are involved. • Particle and nanocrystal attachment operate to yield a porous fabric. • Columnar porous calcite may faithfully record the original properties of the parent drip water. • Oxygen isotopes and trace element concentration correlate with fabrics through crystallization. [ABSTRACT FROM AUTHOR]

The reconstruction of robust past climate records from speleothems requires a prior understanding of the environmental and hydrological conditions that lead to speleothem formation and the chemical signals encoded within them. On regional-scales, there has been little quantification of the dependency of cave dripwater geochemistry on meteorology (net infiltration, temperature), environmental and geographical factors (elevation, latitude, soil activity, vegetation cover, atmospheric aerosol composition) and geological properties of the aquifer (lithology, porosity and thickness). In the present study, we analysed over 200 karst waters collected in 11 caves of the Trentino region (NE Italy). The caves span sub-humid Mediterranean to cold-humid temperate climates and infiltration elevations ( Z inf ) ranging from 355 to 2400 m a.s.l., corresponding to infiltration mean annual temperatures (MAT inf ) between 12 and 0 °C. Since all the caves developed in pure carbonate rocks, soil pCO 2 is found to be the main factor controlling the carbonate dissolution. For this reason, the parameters controlling the carbonate–carbonic acid system and calcite saturation state (SI CC ) are directly correlated with the MAT inf , which influences the vegetation zones and eventually the production of CO 2 in the soil. SI CC linearly depends on MAT inf (SI CC = 0.09 MAT inf − 0.4) and SI CC = 0 is reached at Z inf = 1.66 km a.s.l., corresponding to a MAT inf = 4.4 °C. This point identifies the “ speleothem limit ” defined here as the elevation (or corresponding MAT inf ) above which no sparitic speleothem precipitation usually occurs. We demonstrate that due to temperature-forced changes in the soil and vegetation and subsequently SI CC , the speleothem limit shifts to higher altitudes during maximum interglacial conditions. Speleothems from high altitude caves (1.5–2.5 km a.s.l.) thus can identify optimum interglacial periods. By contrast, speleothems formed at lower altitudes are better suited as archives of hydrological proxies. At altitudes below 1.2 km a.s.l., prior calcite precipitation (PCP) modifies percolating waters, particularly during periods of reduced infiltration. We introduce the use of the SiO 2 /Ca and SO 4 /Ca ratios in cave waters to complement Mg/Ca and Sr/Ca ratios as markers of PCP. SO 4 and SiO 2 are derived from atmospheric deposition and siliciclastic minerals in the soil zone, rather than carbonate host rocks (as in the case of Mg and Sr). By combing shifts to higher Mg/Ca, SiO 2 /Ca and SO 4 /Ca ratios along their characteristics PCP lines, we improve the robustness of the interpretation that this resulted from increasing PCP, rather than incongruent calcite dissolution (ICD). Our method permits the quantification of PCP between 0% and 40% for low elevation cave waters. This novel approach has important implications for speleothem-based paleoclimate studies where the distinction between PCP and ICD can be ambiguous and, in combination with Mg/Ca and Sr/Ca ratios, permits the quantification of net infiltration and/or rainfall amount from speleothem records. [ABSTRACT FROM AUTHOR]

Sulphate concentrations in speleothems identify major volcanic eruptions, provide useful information on soil and aquifer dynamics and, in similar fashion to the 14 C bomb peak, its Anthropocene peak can be used to date recent cave formations. However, the transmission of S from the atmosphere to cave dripwater and its incorporation in speleothems is subjected to biogeochemical cycling and accurate studies of each cave site are needed in order to assess how the S atmospheric signal is modified and eventually encoded in speleothems. This study investigates the role of biogeochemical cycling and aquifer hydrology by utilising published and new dripwater and speleothem data from Grotta di Ernesto (ER) in northern Italy. Here we provide the first long-term record of sulphate concentration in cave dripwater based on over 20 years of measurements. Fast drip site st-ER1 is characterised by a continuous decrease in SO 4 concentration from a high of 7.5 ± 0.8 mg/l in 1993–1994 to a low of 2.2 ± 0.2 mg/l in 2013–2014, and replicates with a delay of ∼15 years the decline in the atmospheric SO 2 emissions. The S-series of slow flow ER78 site is further delayed by ∼4.5 years in relation to the S retention in the aquifer matrix. The dripwater data are used to extend the previously published S record (1810–1998 AD) of stalagmite ER78 and reconstruct the anthropogenic S-peak: this displays a delay of ∼20 years with respect to the atmospheric S emission peak due to biogeochemical cycling and aquifer storage. However, sulphur recycling above the cave did not operate with the same degree of efficiency through time, which resulted in a variable time delay between S deposition and incorporation into the stalagmite. In the pre-Anthropocene era, and in particular during the cold Little Ice Age, biogeochemical cycling was far less efficient than today, and the fast transmission of the atmospheric signal allowed capture of S released during major volcanic eruptions by stalagmites. [ABSTRACT FROM AUTHOR]

The hydroclimate of the South Pacific is highly variable on a range of timescales, however, the brevity of instrumental data in the region complicates the detection and attribution of this variability. Annually laminated speleothems may fill this knowledge gap by providing paleo-hydroclimate proxy data extending beyond the instrumental period. In this study, replicated oxygen isotope (δ18O) time series from two stalagmites from Pouatea (Pu17) and Nurau (Nu16) caves in the southern Cook Islands were used to reconstruct the variability of effective infiltration over the past 350 years (1672–2019 CE) based on observational rainfall data and cave monitoring and calcite farming experiments. The reconstructed infiltration was then compared to available reconstructions of known climate drivers of the South Pacific. Significant dry and wet periods over the last 350 years were identified based on the δ18O signal of compact/porous calcite fabric and their δ13C signals. The hydroclimate significance of these proxies was validated through comparison with the instrumental records. We could not reach an annual resolution of reconstructed infiltration, due to a combination of stable isotope sampling limitations and mixing effects within the aquifer. Nevertheless, the combined δ18O record of Pu17 and Nu16 identifies that the main driver of infiltration and, hence rainfall variability, in the southern Cook Islands is the location of the South Pacific Convergence Zone (SPCZ), which in turn is modulated by the El Niño Southern Oscillation (ENSO). This study demonstrates the hydroclimate significance of speleothem fabrics when combined with O and C stable isotopes, and adds paleoclimate information to a region that has a paucity of data. • ENSO and movements of the SPCZ are the main drivers of rainfall in the southern Cook Islands. • Joint use of speleothem fabrics, δ18O and δ13C serves as a proxy of effective infiltration. • Reconstruction of effective infiltration variability over the past 350 years (1672–2019 CE). • Insights into large-scale controls on rain and speleothem δ18O variability. [ABSTRACT FROM AUTHOR]

Carbon dioxide (CO2) concentrations in caves and parent soils in the Italian Alps have been studied along a 2100 m altitudinal range - corresponding to a mean annual temperature (MAT) range of 12°C - in order to investigate the relationship between MAT, soil pCO2 and cave air pCO2, and to test the influence of soil pCO2 on speleothem growth and fabric to ultimately gain insight into their palaeoclimatic significance in temperate climate settings. Our findings indicate that soil CO2 is linearly correlated to MAT and its mean annual concentration is described by the equation: soil CO2 (ppmv) = 1112 + 460 MAT. Soil pCO2 can also be exponentially correlated to actual evapotranspiration. The pCO2 in the aquifer is linearly correlated to MAT at the infiltration site and is more influenced by summer soil pCO2. Cave air CO2 in the innermost part of the caves exhibits a similar seasonal pattern, and commonly reaches concentrations of about 15% to 35%, with respect to the corresponding soil values, and is exponentially correlated to the MAT at the infiltration site. The combination of these parameters (soil pCO2, dripwater pCO2 and cave air pCO2) results in speleothem growth and controls their fabrics which are typical of four MAT/elevation belts broadly corresponding to the present-day vegetation zones. In the lower montane zone [100-800 m above sea level (a.s.l.)] speleothems mostly consist of columnar fabric, in the upper montane zone (800-1600 m a.s.l.) both columnar and dendritic fabrics are common, the Subalpine zone (1600-2200 m a.s.l.) is characterized mostly by moonmilk deposits, whereas in the Alpine zone (above 2200 m a.s.l.) no speleothems are forming today. Therefore, fabric changes in fossil speleothem can potentially be used to reconstruct MAT changes in temperate climate karst areas. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract: Determination of annual lamination provides important additional constraints to radiometric dates on speleothems, both for dating the duration of specific growth intervals and optimizing growth models. In the absence of visible laminae, however, speleothem age models are reliant upon curve fitting through discretely dated points and are therefore inherently more uncertain than annual chronologies from laminae. Given that the impact of seasonality on speleothems is expected to be strong enough to generate an annual pulse in trace element chemistry regardless of whether or not visible or fluorescent growth laminae are visible, we demonstrate the potential for deriving high-resolution stalagmite chronologies from non-laminated samples using annual chemical variations in stalagmites from two Alpine caves (Obir, Austria and Ernesto, NE Italy). Trace element data were obtained by ion microprobe analyses for H, P, Mg, Na, Sr and Ba and the annual signal was sought using spectral and wavelet analysis. An automated chemical peak-counting software tool was developed in MATLAB©. It counts significant annual peaks using criteria of minimum amplitude in relation to the local standard deviation of signal variation and minimum separation between peaks determined by the thickness of the preceding layers. Verification of the tool using visibly laminated samples suggests the software is a reliable and accurate method of chronology building, with hit ratios greater than 0.93 and less than 0.75% false alarm occurrences. Used in conjunction with other dating methods such as radiocarbon, U–Th and sulphur peak dating, the automated chemical laminae chronology-building approach provides a more meaningful alternative to simple age-depth curve fitting for non-laminated samples. [Copyright &y& Elsevier]

Past climate archives show the Last Interglacial (LIG) period as similar to slightly warmer than current temperatures. However, there is a lack of LIG proxy evidence regarding variations of the climate across large topographic features and how this manifests at different altitudes. Here, we analysed two flowstones from Bigonda Cave, northeast Italy, to reconstruct LIG climate conditions in a region where precipitation is strongly influenced by the presence of the Alps. Stable isotope ratios, trace element concentrations and speleothem petrography from 133 ka to 105 ka allowed the detection of various hydroclimate and environmental conditions. Composite speleothem δ18O records from northeast Italy were found to closely follow the Northern Hemisphere summer insolation curve, attesting to the influence of solar isolation on Earth's hydroclimate. Our reconstructions indicate a northward shift of the Intertropical Convergence Zone during the LIG maximum, permitting Atlantic-derived moisture to travel further east across North Africa than at present, before being directed north towards the Alps. The latter part of the LIG exhibited frequent, extreme precipitation events in the SE Prealps due to orographic lifting of moisture from both the Atlantic and Mediterranean seas. Socio-economic planning must prepare for extreme autumnal flooding events and serious summer droughts, particularly important in vulnerable mountainous regions. • Last Interglacial speleothem multi-proxy records from the NE Italian Prealps. • Three infiltration sources identified permits robust hydroclimate reconstruction. • Solar insolation was the main forcing mechanism of the oxygen isotope record. • The LIG was punctuated by hot dry summers and extreme cave flooding events. [ABSTRACT FROM AUTHOR]

Abstract: Precise dating and correlation of past key volcanic eruptions over a wide geographic area in archives of past climate variability is necessary to support a direct causality between volcanism and climate changes. Research has mostly focused on ice cores and varved sediments, which capture a record of volcanic eruptions in geochemistry and the presence of tephra and criptotephra. Precisely dated cave carbonate deposits, collectively known as speleothems are other valuable palaeoclimate archives, and encode information on past volcanism in their sulphate concentration variability. Due to the physical characteristic of speleothems, detection of sulphate concentration variability requires techniques capable of high spatial resolution, very low limit of detection (ppm to ppb) and low background noise. Synchrotron radiation-based (SR) micro X-ray fluorescence (µXRF) and X-ray absorption near-edge spectrometry prove to be one of the most effective techniques to detect short-lived pulses of sulphate concentration increase, which may be interpreted as being related to atmospheric load due to volcanic eruptions. Here, we provide an overview of existing work as well as a novel interpretation of a SR µXRF-based sulphate series in an annually laminated stalagmite with robust chronology. Sulphate concentration peaks in the years 1815–1816, 1844 and 1947, possibly coinciding with Tambora, Krakatau, and Hekla eruptions. It is concluded that sulphate concentration in speleothems expand the potential to correlate volcanic eruption events at a global scale. [Copyright &y& Elsevier]

Stalagmite SV1 from Grotta Savi, located at the SE margin of the European Alps (Italy), is the first Alpine speleothem that continuously spans the past c . 17 kyr. Extension rate and δ 18 O c record for the Lateglacial probably reflect a combination of temperature and rainfall, with rainfall exerting the dominant effect. Low speleothem calcite δ 18 O c values were recorded from c . 14.5 and 12.35 kyr, during GI-1 (Bølling–Allerød) interstadial, which, in our interpretation, was warm and wet. The GS-1 (Younger Dryas) was characterized by a shift to heavier δ 18 O c , coinciding with δ 13 C c enrichment and extremely low extension rate ( [ABSTRACT FROM AUTHOR]

Annual growth rates and the ratio of dark to light-colored calcite within single annual laminae in three contemporaneously deposited Holocene speleothems from Grotta di Ernesto, an Alpine cave in northern Italy, respond to changes in surface temperature rather than precipitation. Based on monitoring of present-day calcite growth, and correlation with instrumental data for surface climatic conditions, we interpret a higher ratio of dark to light-colored calcite and the simultaneous thinning of annual laminae as indicative of colder-than-present winters. Such dark and thin laminae occur in those parts of the three stalagmites deposited from AD 1650 to 1713 and from AD 1798 to 1840, as reconstructed through lamina counting. These periods correspond to the well-known Maunder and Dalton Minima of solar activity. An 11-yr cyclicity in growth rate, coupled with reduced calcite deposition during the historic minima of solar activity, is indicative of a solar influence on lamina thickness. Spectral analysis of the lamina thickness data also suggests that the North Atlantic Oscillation variability influenced winter temperatures. Based on the present-day controls on cave calcite formation, we infer that high-frequency changes in solar activity modulated the seasonal duration of soil CO2 production. [Copyright &y& Elsevier]

The so-called "Altamura Man" is a Neanderthal skeleton found in 1993 in the Lamalunga karstic system (southern Italy). The skeleton, dated between 172 and 130 ka, still lies deep within a spectacular cave setting, partly embedded within speleothems and extensively covered by coralloid concretions. These peculiar location and conditions would entail major difficulties in excavating and preserving ex-situ this skeleton. Moreover, a decision-making impasse among the institutions involved complicates the problem. Yet, this specimen is one of the best preserved human fossils known. From 2016 to 2020 we conducted extensive in situ investigations of the specimen. Digital techniques and equipment specifically designed for or adapted to the difficult underground context were used in carrying out the most detailed assessment possible of the skeleton. The data thus collected provide an insight into human evolution in Europe, and a first glance at the amount of information this amazing specimen could provide. In this contribution, we want to update the information on the problematic context of Lamalunga, and address the innovative solutions put in place in 2016–2020 to study and preserve the Neanderthal skeleton in this fragile environment. • The so-called "Altamura Man" is one of the most complete Neanderthal fossils. • The site and condition of preservation have made the study problematic for decades. • New studies in situ allowed a better characterization of the fossil and its context. • We review what is currently known of the specimen and its site in southern Italy. • We also present some of the innovative methods used for the study. [ABSTRACT FROM AUTHOR]

Annual lamination in trace elements content allows to improve speleothem chronology as well as to extract paleoclimate information about fluctuations of the seasonal signal through time. Given the relatively slow growth and textural heterogeneity intrinsic in most speleothems, only high-resolution mapping techniques provide a viable approach to resolve trace elements variability at annual to sub-annual scale. Synchrotron radiation X-ray fluorescence microscopy (SR-μXRF) is, to date, the ideal technique as it provides quantitative, non-destructive fast scanning of large samples at the necessary high spatial resolution (0.5 – 5 μm).Here we present SR-μXRF investigation of U/Th dated stalagmites from caves in different geographic and climate setting including semi-arid (Flinders Ranges, South Australia), temperate (Central Italy) and tropical humid (Cook Islands, Northern Laos) climates.SR-μXRF analyses were coupled with high-resolution petrographic observation and LA-ICP-MS elemental analyses in order to verify the XRF elemental quantification and to test the relationship between fabric and trace element incorporation.All the analysed stalagmites revealed faint to sharp annual lamination in Sr, and, occasionally, in other elements such as Br, Cu and Zn. In climate setting characterised by strong seasonal contrast stalagmites often exhibit fabric changes at annual to centennial scale that are reflected in the internal porosity as well as in the incorporation of trace elements. Fabric control and spatial heterogeneity is also evident in the intensity of the annual cycles and, in some cases, the amplitude of Sr cycles vary considerably from one line scan to the adjacent ones. This poses the question of the significance and reproducibility of trace element analyses in speleothems characterised by fabric heterogeneity. [ABSTRACT FROM AUTHOR]

Crystallization pathways are at the core of incorporation of chemical species by calcium carbonate minerals. This is particularly important in speleothems where the classical equilibrium precipitation approach and the theoretical partition coefficient are not always applicable. In fact, in several speleothems non classical nucleation plays an active role and an empiric "speleothem enrichment factor" better describes the incorporation of different chemical species. Here we present the first attempt to calibrate chemical parameters on the base of speleothem fabrics for active and Late Holocene stalagmites taken from two caves in Atiu, Cook Islands. Our multi-proxy analysis integrates high-resolution petrography, trace element and stable isotope analysis of stalagmites characterised by growth rates ranging from 20 up to 1000 µm/yr, which have been dated by U-Th series and lamina counting. In-situ calcite farming experiments yielded calcite crystals of the order of ten nanometer from the slow drips, whereas colloidal calcite particulate (2-3 nm crystals) associated to organic and inorganic colloids formed from the fast drips. Fast/variable and slow/constant drip rate end members generate active forming stalagmite fabrics with fast growing opaque open/porous calcite and translucent compact columnar calcite respectively. In the compact fabric soluble species are incorporated within the calcite lattice, whilst OM colloids are expelled or isolated in the crystal defects. This allows using a partition coefficient for soluble elements, but not for elements adsorbed on colloids. In the open/porous fabric calcite crystals seem to grow by attachment of particles and there is a large number of sites where colloids, particulate and even solute elements can be adsorbed and incorporate outside the calcite lattice. This results in an enhanced incorporation of trace elements and thus, the theoretical partition coefficient cannot be utilized to reconstruct the original chemistry of the dripwater.In two Late Holocene stalagmites LA-ICP-MS analyses reveal specific patterns in the elemental distribution. Most of the solute elements (Mg, Sr, Ba, Na) show a positive covariance and can be potentially be utilized as palaeo-hydrological proxy. This is corroborated by the negative correlation with colloidally transported elements such as Y and P, and the general trend of δ13C that is consistent with Mg and Sr. During wet condition (low Mg and Sr), δ13C shifts toward more negative values (down to -11‰). In contrast, dry conditions are characterised by less negative δ13C and higher concentration of Mg and Sr suggesting the influence of kinetic effects and/or evapotranspiration. However, the higher incorporation of solute elements during dry phases is further enhanced in the open/porous fabric and a fabric-specific elemental enrichment factor has to be taken into account. [ABSTRACT FROM AUTHOR]

Carbonate-associated sulphate (CAS) is a useful carrier of palaeoenvironmental information throughout the geologic record, particularly through its stable isotope composition. However, a paucity of experimental data restricts quantitative understanding of sulphate incorporation into carbonates, and consequently CAS concentrations and their diagenetic modifications are rarely interpreted. However, in the case of calcite speleothems, the remarkably high-resolution CAS records which are obtainable via modern microanalytical techniques represent a potentially invaluable source of palaeoenvironmental information. Here, we describe the results of controlled experiments of sulphate co-precipitation with calcite in freshwater solutions where pH, saturation state, and sulphate concentration were varied independently of each other. Solution pH is confirmed as the principal control on sulphate incorporation into calcite. The relative efficiency of incorporation was calculated as a partition coefficient D SO 4  = (mSO 4 /mCO 3 ) solid /(mSO 4 /mCO 3 ) solution . High crystal growth rates (driven by either pH or saturation state) encouraged higher values of D SO 4 because of an increasing concentration of defect sites on crystal surfaces. At low growth rates, D SO 4 was reduced due to an inferred competition between sulphate and bicarbonate at the calcite surface. These experimental results are applied to understand the incorporation of sulphate into speleothem calcite. The experimentally determined pH-dependence suggests that strong seasonal variations in cave air PCO 2 could account for annual cycles in sulphate concentration observed in stalagmites. Our new experimentally determined values of D SO 4 were compared with D SO 4 values calculated from speleothem-drip water monitoring from two caves within the Austrian and Italian Alps. At Obir cave, Austria, D SO 4 (×10 5 ) varies between 11.1 (winter) and 9.0 (summer) and the corresponding figures for Ernesto cave, Italy, are 15.4 (winter) and 14.9 (summer). These values approximate predicted D SO 4 values based on our chamber experiments containing both low (2 ppm) and high (20 ppm) sulphate concentrations. Our experimental values of D SO 4 obtained at crystal growth rates typical of stalagmites, closely match those observed in other cave sites from around the world. This validates the universality of the controls behind D SO 4 and will enhance the use of speleothem CAS as a palaeoenvironmental proxy. [ABSTRACT FROM AUTHOR]

Speleothem records of past environmental change provide an important opportunity to explore fire frequency and intensity in the past, and the antecedent climatic conditions leading to fire events. Here, fire sensitive geochemical signals in a stalagmite from Yonderup Cave, a shallow cave in Western Australia, are compared to well-documented wildfire events that occurred in recent decades. The results are extended to identify wildfires during the growth interval of the speleothem (1760 CE–2005 CE). Principal component analysis of the stalagmite time-series revealed distinct peaks in a combination of phosphorus and metal (aluminium, zinc, copper and lead) concentrations in response to known fire events, which are interpreted to have come from ash. Varying responses in the geochemical signal in the pre- and post-European colonisation period are likely linked to changes in land management, fire frequency and fire intensities. Of note is what we infer to be a particularly intense fire event concluded to have occurred in 1897 ± 5 CE, which climate sensitive proxies (δ18O and bedrock-derived elements) indicate was preceded by a multi-decadal dry period that began in the late 1860s. The intensity of the deduced fire event is supported by a peak in P that is 6.3 times higher than elsewhere in the speleothem, accompanied by a peak in Zn. It was also inferred that changes to the surface-cave hydrology occurred as a result of this event, indicated by increased input of colloidal organic material onto the stalagmite that was interpreted to be caused by shallow karst bedrock fracturing from the heat-induced deformation that is observed after intense fires. These findings show the potential for speleothems to provide dated records of fire intensity and recurrence intervals. Further development could lead to a better understanding of the climate-fire relationship and the effects of land-management practices on wildfire frequency and intensity. [ABSTRACT FROM AUTHOR]

Speleothems are usually considered as one of the most amenable palaeoclimate archives for U-series dating. A number of studies in recent years, however, report cases of diagenetic alteration which compromises the use of U-series systematics in speleothems, resulting in inaccurate U-Th ages. Here we present the results of a high-resolution U-Th dating study of a stalagmite (CC26) from Corchia Cave in Italy where we document a number of departures from an otherwise well-defined age-depth model, and explore potential causes for these outliers. Unlike examples illustrated in previous studies, CC26 contains no visible evidence of neomorphism, and appears, at least superficially, ideally suited to dating. Good reproducibility obtained between multi-aliquot U-Th analyses removes any possibility of analytical issues contributing to these outliers. Furthermore, replicate analyses of samples from the same stratigraphic layer yielded ages in stratigraphic sequence, implying very localized open-system behavior. Uranium loss is suggested as a causative mechanism on account of the fact that all the outliers are older than their assumed true age. A limited number of micro-voids were observed under micro-CT analyses, and it is proposed that these were pathways for U loss. Uranium-loss modelling allows us to constrain the possible timing of diagenetic alteration and indicates that the precursor for the outlier with the largest age discrepancy (309%) must have been aragonite. This study indicates that visibly unaltered speleothems may still contain small domains that have experienced post-depositional alteration. Such “cryptic” diagenesis, as recorded in this stalagmite, has implications for the constancy of accuracy of the U-series dating technique, and suggests a need for careful examination of speleothems prior to dating, particularly in low-resolution U-Th studies. [ABSTRACT FROM AUTHOR]

Abstract: This paper aims to establish evidence for the widespread existence of metal binding and transport by natural organic matter (NOM) in karst dripwaters, the imprint of which in speleothems may have important climatic significance. We studied the concentration of trace metals and organic carbon (OC) in sequentially filtered dripwaters and soil leachates from three contrasting sites: Poole''s Cavern (Derbyshire, UK), Lower Balls Green Mine (Gloucestershire, UK) and Grotta di Ernesto (Trentino, Italy). The size-distribution of metals in the three soils was highly similar, but distinct from that found in fractionated dripwaters: surface-reactive metals were concentrated in the coarse fraction (>100nm) of soils, but in the fine colloidal (<100nm) and nominally dissolved (<1nm) fractions of dripwaters. The concentration of Cu, Ni and Co in dripwater samples across all sites were well correlated (R2 =0.84 and 0.70, Cu vs. Ni, Cu vs. Co, respectively), indicating a common association. Furthermore, metal ratios (Cu:Ni, Cu:Co) were consistent with NICA-Donnan n1 humic binding affinity ratios for these metals, consistent with a competitive hierarchy of binding affinity (Cu>Ni>Co) for sites in colloidal or dissolved NOM. Large shifts in Cu:Ni in dripwaters coincided with high fluxes of particulate OC (following peak infiltration) and showed increased similarity to ratios in soils, diagnostic of qualitative changes in NOM supply (i.e. fresh inputs of more aromatic/hydrophobic soil organic matter (SOM) with Cu outcompeting Ni for suitable binding sites). Results indicate that at high-flows (i.e. where fracture-fed flow dominates) particulates and colloids migrate at similar rates, whereas, in slow seepage-flow dripwaters, particulates (>1μm) and small colloids (1–100nm) decouple, resulting in two distinct modes of NOM–metal transport: high-flux and low-flux. At the hyperalkaline drip site PE1 (in Poole''s Cavern), high-fluxes of metals (Cu, Ni, Zn, Ti, Mn, Fe) and particulate NOM occurred in rapid, short-lived pulses following peak infiltration events, whereas low-fluxes of metals (Co and V>Cu, Ni and Ti) and fluorescent NOM (< ca. 100nm) were offset from infiltration events, probably because small organic colloids (1–100nm) and solutes (<1nm) were slower to migate through the porous matrix than particulates. These results demonstrate the widespread occurrence of both colloidal and particulate NOM–metal transport in cave dripwaters and the importance of karst hydrology in affecting the breakthrough times of different species. Constraints imposed by soil processes (colloid/particle release), direct contributions of metals and NOM from rainfall, and flow-routing (colloid/particle migration) are expected to determine the strength of correlations between NOM-transported metals in speleothems and climatic signals. Changes in trace metal ratios (e.g. Cu:Ni) in speleothems may encode information on NOM composition, potentially aiding in targeting of compound-specific investigations and for the assessment of changes in the quality of soil organic matter. [Copyright &y& Elsevier]

Abstract: Diverse interpretations have been made of carbon isotope time series in speleothems, reflecting multiple potential controls. Here we study the dynamics of 13C and 12C cycling in a particularly well-constrained site to improve our understanding of processes affecting speleothem δ13C values. The small, tubular Grotta di Ernesto cave (NE Italy) hosts annually-laminated speleothem archives of climatic and environmental changes. Temperature, air pressure, pCO2, dissolved inorganic carbon (DIC) and their C isotopic compositions were monitored for up to five years in soil water and gas, cave dripwater and cave air. Mass-balance models were constructed for CO2 concentrations and tested against the carbon isotope data. Air advection forces winter pCO2 to drop in the cave air to ca. 500ppm from a summer peak of ca. 1500ppm, with a rate of air exchange between cave and free atmosphere of approximately 0.4days. The process of cave ventilation forces degassing of CO2 from the dripwater, prior to any calcite precipitation onto the stalagmites. This phase of degassing causes kinetic isotope fractionation, i.e. 13C-enrichment of dripwater whose δ13CDIC values are already higher (by about 1‰) than those of soil water due to dissolution of the carbonate rock. A subsequent systematic shift to even higher δ13C values, from −11.5‰ in the cave drips to about −8‰ calculated for the solution film on top of stalagmites, is related to degassing on the stalagmite top and equilibration with the cave air. Mass-balance modelling of C fluxes reveals that a very small percentage of isotopically depleted cave air CO2 evolves from the first phase of dripwater degassing, and shifts the winter cave air composition toward slightly more depleted values than those calculated for equilibrium. The systematic 13C-enrichment from the soil to the stalagmites at Grotta di Ernesto is independent of drip rate, and forced by the difference in pCO2 between cave water and cave air. This implies that speleothem δ13C values may not be simply interpreted either in terms of hydrology or soil processes. [Copyright &y& Elsevier]

Abstract: Sulphur emitted into the atmosphere from industrial activity is regarded as a key mechanism in forcing recent climate and has impacts upon the environment and human health at both local and regional scales. Trace amounts of sulphate present within speleothem carbonate can be used to provide an emissions inventory for regional sulphur loading to the atmosphere where sulphur isotopes can be extracted and used as a tool for provenance. However, speleothem sulphur concentrations are low and manual techniques for sulphur isotope analysis allow only low sampling resolution. SIMS (Secondary Ionisation Mass Spectrometry) is used here to develop records of sulphur isotopic change in speleothems from the Italian and Austrian Alps, where annual laminae are less than 100µm thick. Analysis at annual resolution over the past 100years demonstrates an excursion in sulphur isotopic composition from values close to the carbonate bedrock end-member composition in the pre-industrial era, to values isotopically depleted in 34 S. This trend is mirrored by increasing concentrations of sulphate and is suggested to reflect the increase in SO2 emissions with industrial activity. Subsequent decline in speleothem sulphate concentrations in one of the stalagmites reflects the recent European decline in industrial atmospheric SO2 content and is matched by a rebound in sulphur isotopic composition to values more enriched in 34 S. Superimposed on this general secular trend are smaller (annual) variations in concentration reflecting cave environmental conditions. High magnitude events of short duration, potentially reflect volcanic inputs of SO2 or the incorporation of dust particulates into the speleothem carbonate. This is the first micro-analysis of carbonate-associated sulphate (CAS) sulphur isotopes by SIMS. SIMS analysis of δ 34S–SO4 in speleothem carbonate reveals a high resolution archive depicting a regional sulphur emissions inventory for SO2 loading to the atmosphere. [Copyright &y& Elsevier]

Conturines cave opens at the base of a cirque wall at 2775 m a.s.l. in the Dolomites(Northern Italy). Large parts of the cave floor are covered by an extensive and unusuallythick (up to 3.4 m) flowstone. This and other speleothems are inactive, corrodedand cut by fractures. Eight drill cores covering the entire stratigraphy of the basalflowstone were obtained along the course of the gallery. Four methods were applied toestablish a chronological framework of this unique long-term paleoenvironmentalarchive. 230Th ages on several cores demonstrate that calcite deposition had terminatedbefore 650 ka BP. U-Pb dating was attempted but yielded unfavourably low U/Pbratios. Polarity determinations of demagnetised samples were carried out on the full length offour cores. Most cores show already reverse magnetisation in their top parts. Two long coresdrilled in the proximal part of the speleothem show replicated evidence of several polaritychanges, providing a strong indication that the flowstone reaches back at least to thePliocene. Finally, pollen was extracted from flowstone samples in order to establish independentpalynostratigraphic constraints. The pollen density is low, but the presence of Nyssa indicatesan Early Pleistocene or Pliocene age. [ABSTRACT FROM AUTHOR]