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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]

The author will try to develop the notion of 'valence' ('Aufforderungscharakter'), first introduced in psychology by the work of K. Lewin, from a phenomenological point of view. In a first approximation, an object has valence insofar as it prompts us to action. Valence is an important – although in contemporary philosophy of mind quite neglected – feature of our practical experience. Here we will concentrate on the consciousness of valence and its descriptive features. After distinguishing, on the one hand, 'valence' from 'value', and pointing out how, on the other hand, 'valence' should also not be confused with J.J. Gibson's 'affordance', we will try to develop the implications of this notion beyond the original scope of Lewin's experimental psychology: on the one hand, by introducing the idea of 'passive valence' and, on the other hand, by investigating the relation between valence and emotion and discussing the possibility of 'emotional valence'. [ABSTRACT FROM AUTHOR]

Tropical Pacific stalagmites are commonly affected by dating uncertainties because of their low U concentration and/or elevated initial 230Th content. This poses problems in establishing reliable trends and periodicities for droughts and pluvial episodes in a region vulnerable to climate change. Here we constrain the chronology of a Cook Islands stalagmite using synchrotron µXRF two-dimensional mapping of Sr concentrations coupled with growth laminae optical imaging constrained by in situ monitoring. Unidimensional LA-ICP-MS-generated Mg, Sr, Ba and Na variability series were anchored to the 2D Sr and optical maps. The annual hydrological significance of Mg, Sr, Ba and Na was tested by principal component analysis, which revealed that Mg and Na are related to dry-season, wind-transported marine aerosols, similar to the host-rock derived Sr and Ba signatures. Trace element annual banding was then used to generate a calendar-year master chronology with a dating uncertainty maximum of ± 15 years over 336 years. Our approach demonstrates that accurate chronologies and coupled hydroclimate proxies can be obtained from speleothems formed in tropical settings where low seasonality and problematic U–Th dating would discourage the use of high-resolution climate proxies datasets. [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]

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]

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]

In this study, the ‘dead carbon proportion’ (DCP) calculated from combined U-Th and radiocarbon analyses was used to explore the carbon isotope systematics in Corchia Cave (Italy) speleothems, using the example of stalagmite CC26 which grew during the last ∼12 ka. The DCP values in CC26 are among the highest ever recorded in a stalagmite, spanning the range 44.8–68.8%. A combination of almost closed-system conditions and sulphuric acid dissolution (SAD) are proposed as major drivers in producing such a high DCP with minor contribution from old organic matter from the deep vadose zone. The long-term decrease in both DCP and δ 13 C most likely reflects post-glacial soil recovery above the cave, with a progressive increase of soil CO 2 contribution to the total dissolved inorganic carbon (DIC). Pronounced millennial-scale shifts in DCP and relatively small coeval but antipathetic changes in δ 13 C are modulated by the effects of hydrological variability on open and closed-system dissolution, SAD and prior calcite precipitation. Hence, the DCP in Corchia Cave speleothems represents an additional proxy for rainfall amount. [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 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]

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]

Trace amounts of sulphur in speleothems suggest that stalagmites may act as archives of sulphur deposition, thereby recording aspects of atmospheric variability in sulphur content. Accurate interpretation of this novel sulphur archive depends upon understanding how biogeochemical cycling in the soil and epikarst above the cave may modify the precursor atmospheric values of sulphur concentration and isotopic composition prior to incorporation into the speleothem record. Dual isotope analysis of δS-SO and δO-SO is used to trace biogeochemical transformations of atmospheric sulphur through the cave system at Grotta di Ernesto in the Italian Alps and builds towards a framework for interpretation of speleothem sulphur archives which depends on overlying ecosystem dynamics and karst hydrological properties. A three component model of atmospheric sulphate signal modification is proposed to be driven by (1). vegetation and soil cycling, (2). the degree of groundwater mixing in the karst aquifer; and (3). redox status. The relative influence of each process is specific to individual drip flow sites and associated stalagmites, rendering each sulphur archive a unique signal of environmental conditions. Under conditions found in the soil and epikarst above Grotta di Ernesto, the dual isotope signatures of sulphate sulphur and oxygen incorporated into speleothem carbonate, closely reflect past conditions of industrial sulphur loading to the atmosphere and the extent of signal modification through biogeochemical cycling and aquifer mixing. [ABSTRACT FROM AUTHOR]

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]

Annually laminated stalagmites are an exceptional archive of high-resolution past hydroclimate changes and provide robust annually-resolved age models. Stalagmite chemical annual laminae are invisible through optical and fluorescence microscopy, but are revealed by X-ray fluorescence or mass-spectrometry techniques. Synchrotron radiation based micro-X-ray fluorescence (S-μXRF) has the unique advantage of creating 2-dimensional maps of element distribution, which allows visualizing lateral heterogeneity and porosity that pose problems when one dimensional line-scanning techniques, such as LA-ICP-MS, are used. Here, we show how S-μXRF fast element mapping allows obtaining robust age models and palaeoclimate data from stalagmites otherwise difficult to date. Analytical challenges and solution to problems are discussed for both thick polished slabs and thin sections. The elements detectable through the fast acquisition mode (dwell time 1 to 4 ms) are typically Ca, Sr, Br, while Fe, Zn, Ni, Cu, Mn, Y, and Rb are occasionally detected in few distinctive layers or, in association with grain inclusions and porosity. Only Sr, however, exhibits a consistent and clear annual cyclicity. At incident angles of 90° the attenuation depth for Sr is ca. 240 μm and, therefore thick samples are preferable as they produce stronger fluorescence signal and sharper images unaffected by non-linear drift. On the other hand, thick samples are more affected by geometric and edge effects that can be particularly severe in the presence of irregular lamination and when the laminae are dipping with variable angle within the sample. The Sr concentration in the tropical stalagmites analysed in this study varied from 15 to 600 ppm, which strongly influences the dwell time needed to obtain high-quality maps. For Sr concentration below 20 ppm the ideal dwell time exceeds 20 ms and this renders the acquisition of large maps (> 20 Megapixels) hardly feasible. For concentrations above 20 ppm the fast mapping (dwell time < 5 ms) through S-μXRF is by far the best methodology to visualise chemical annual cycles in stalagmites. [Display omitted] • Synchrotron μXRF is the optimal technique for mapping chemical annual laminae in stalagmites. • Synchrotron μXRF mapping provides calendar chronologies in tropical stalagmites. • Sr is the best element that marks annual cycles • Inelastic and elastic scattering maps highlight crystal structure, growth defects and porosity. [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]

Abstract: Stalagmite ER78, from Grotta di Ernesto cave in NE Italy displays clear annual lamination consistent with its shallow depth below a forest ecosystem subject to autumnal peaking of water infiltration. Synchrotron radiation scanning micro-X-ray fluorescence analyses of heavy elements at European Synchrotron Radiation Facility beamline ID22, and light elements at ID21, with 1–3μm resolution has been combined with data from ion microprobe analyses to reveal chemical variability across the visible layers of these annual laminae. A series of elements display a symmetrical peak, centered around the thin, dark layer at the top of each lamina. The peak concentration is ordered Y>Zn, Cu and Pb>P and Br. This hierarchy is thought to reflect the selectivity of transport of these elements, possibly by organic colloids flushed from the soil zone during autumn infiltration. Ion microprobe analysis indicates Na and F also increase, as does H, the latter reflecting increased microporosity. Sr displays a trough around the dark and thin autumn layer implying that its incorporation may be limited by competition with other elements. Mg and S show a different pattern of annual variation and Fe displays none. The trace metals, Br and Y display peak abundance in the early 20th century, which appears to reflect a period of tree-felling rather than a climatic anomaly. The results demonstrate the power of the high spatial resolution and low detection limits of the synchrotron technique, and its ability to produce quantitative maps that allow distinction of layered structure from that of isolated particles, or irregular inhomogeneities. [Copyright &y& Elsevier]

Abstract: Fabric and stable isotopic composition of a Holocene stalagmite (CR1) from a cave in northern Sicily record changes in paleorainfall in the early Holocene. High δ13C stable isotope values in the calcite deposited from ca. 8500 to ca. 7500 yr ago are interpreted as reflecting periods of high rainfall. The wet phase was interrupted by two periods of multi-century duration characterized by relatively cool and dry winters centered at ca. 8200 and ca. 7500 yr ago, highlighted by low δ13C and δ18O values. A high variability of δ13C values is recorded from ca. 7500 to ca. 6500 yr ago and indicates that the transition from a pluvial early Holocene to the present-day climate conditions was punctuated by decadal-scale periods of relatively dry winters. In northern Sicily, the traditional elements of the Neolithic appear at ca. 7700 yr ago. It is possible that changes in rainfall influenced the passage from hunter-gathering to farming and sheep-herding economies. [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]

Abstract: We report here the first speleothem time-series of the variability of sulphate, a species whose abundance in catchments is strongly influenced by atmospheric anthropogenic and volcanic sources. Annually-resolved archives of S, Mg, Si and P were generated by applying synchrotron radiation micro X-Ray Fluorescence (XRF) to two speleothems from different sites in northern Italy. X-ray absorption-edge spectrometry proves that the S is in the form of sulphate and XRF mapping demonstrates that S is within calcite and enriched zones are predominantly as layers. A post-1850 A.D. record from the Ernesto cave shows a substantial rise in sulphate, interpreted as reflecting the largely anthropogenically-forced variation of sulphate of the atmospheric boundary layer, moderated by some ecosystem storage. Analysis of the circa 5.2 to circa 5.0 ka interval of a speleothem from Savi cave, where ecosystem retention of S is likely to have been minimal, shows a spiky sulphate record, resembling that of ice cores. A series of sulphate peaks suggest that multiple volcanic sulphate aerosol emissions at that time. This probably enhanced summer temperature cooling thus favouring the preservation of the human mummy of Neolithic–Copper age, the “Iceman” on the watershed between Italy and Austria. Both examples illustrate the power of speleothems to record atmospheric sulphate variability. [Copyright &y& Elsevier]

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]

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]

Debate about sedimentary structures found in intertidal zones of highly evaporative environments such as sabkhas, has commonly been focused on the interpretation of their morphology as purely abiotic or microbial. This is relevant to the study of early signs of Life on Earth, of the resilience of Life in extreme environments and for the search of signs of Life on Mars and exoplanets. Critically, ancient rocks likely underwent multiple diagenetic phases that may have partially overprinted primary features, yet microbially-influenced structures may be stabilized by micrite and micrite itself can be stabilized by organic molecules.The aim of the present study is to investigate the best chemical tracer that highlights primary (or very early diagenetic) depositional features by utilising Synchrotron Radiation based micro-X Ray Fluorsecence (SR-µXRF) mapping. Here we present the first SR-µXRF investigation of living microbial mats collected in the Dohat Faishakh Sabkha (DF) of Qatar compared with a similar fossil counterpart, the loferite facies from the Late Triassic Dolomia Principale (DP) in the Brenta Dolomites (Italy).In the modern DF sample we found that As, Br, Fe and Mn were associated with the dark, microbial laminae (organic part), whilst Sr was associated with the "mineral" part, along with Ca and Rb. This pattern has been already observed by SR-µXRF investigation of continental microbial mats.In the Late Triassic DP laminated facies - commonly interpreted as fossilized cyanobacterial microbial mats that originally thrived in an evaporative environment similar to that of the Qatar sabkha - the laminae consist of dolomite, whose genesis is a matter of debate. However, novel nanostructural investigations of the laminites suggest that some primary structures are preserved and, critically, the SR-µXRF maps revealed that Sr is associated with micrite outlining "microbial laminae".It is well known that Sr is immobilized by calcification and totally related to the mineral parts of the mats. By contrast, other elements, such as Br are in the "organic part", and are preferentially carried away during diagenesis. Sr distribution in the DP is very similar to that in the DF samples, which, coupled with modern growth rates of the mat, hints to the idea that it marks primary carbonate deposition as related to annual cycles in environmental parameters. At the same time, it is interesting to note that all the elements associated with "organics" are not detectable in the Triassic samples.This finding provides a new tool for both assessing existence of a primary mineral component of a microbial mat in fossil samples and for understanding annual-scale processes that drove the formation of "lofer" facies. [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]

Complete Neanderthal skeletons are almost unique findings. A very well-preserved specimen of this kind was discovered in 1993 in the deepest recesses of a karstic system near the town of Altamura in Southern Italy. We present here a detailed description of the cranium, after we virtually extracted it from the surrounding stalagmites and stalactites. The morphology of the Altamura cranium fits within the Neanderthal variability, though it retains features occurring in more archaic European samples. Some of these features were never observed in Homo neanderthalensis, i.e. in fossil specimens dated between 300 and 40 ka. Considering the U-Th age we previously obtained (>130 ka), the morphology of Altamura suggests that the archaic traits it retains may have been originated by geographic isolation of the early Neanderthal populations from Southern Italy. 3D reconstruction of a human cranium held within a deep cave in Italy is achieved with advanced virtual anthropology techniques; its features indicate that geographic isolation contributed to variation and evolution along the Neanderthal lineage. [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]

In 1993, a fossil hominin skeleton was discovered in the karst caves of Lamalunga, near Altamura, in southern Italy. Despite the fact that this specimen represents one of the most extraordinary hominin specimens ever found in Europe, for the last two decades our knowledge of it has been based purely on the documented on-site observations. Recently, the retrieval from the cave of a fragment of bone (part of the right scapula) allowed the first dating of the individual, the quantitative analysis of a diagnostic morphological feature, and a preliminary paleogenetic characterization of this hominin skeleton from Altamura. Overall, the results concur in indicating that it belongs to the hypodigm of Homo neanderthalensis , with some phenetic peculiarities that appear consistent with a chronology ranging from 172 ± 15 ka to 130.1 ± 1.9 ka. Thus, the skeleton from Altamura represents the most ancient Neanderthal from which endogenous DNA has ever been extracted. [ABSTRACT FROM AUTHOR]

Time series of hydrological and geochemical signals at two karst springs, located in the Dolomiti del Brenta region, near Trento, Italy, are used to infer how karst catchments work internally to generate runoff. The data analyzed include precipitation, spring flow and electric conductivity of the spring water. All the signals show the signature of multifractality but with different intermittency and non-stationarity. In particular, precipitation and spring flow are shown to have nearly the same degree of non-stationarity and intermittency, while electric conductivity, which mimics the travel time distribution of water in the karst system, is less intermittent and smoother than both spring flow and precipitations. We found that spring flow can be obtained from precipitation through fractional convolution with a power law transfer function. An important result of our study is that the probability distribution of travel times is inconsistent with the advection dispersion equation, while it supports the anomalous transport model. This result is in line with what was observed by Painter et al. [Geophys. Res. Lett. 29 (2002) 21.1] for transport in fractured rocks. [Copyright &y& Elsevier]

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]

The spatiotemporal variability of the Asian Monsoon (AM) over the last two millennia has been attributed to a combination of external solar and volcanic forcing and/or internal coupled atmosphere-ocean dynamics, but the relative importance of these mechanisms remains unresolved. The present knowledge of multidecadal to centennial-scale AM variability over Mainland Southeast Asia is not well-constrained, despite substantial progress in understanding seasonal to decadal variability from tree ring records. Here we present the first high-resolution stable isotope (δ 13 C and δ 18 O) speleothem record from northern Laos spanning the Common Era (∼50 BCE to 1880 CE). The δ 13 C record reveals substantial centennial-scale fluctuations primarily driven by local water balance. Notably, the driest period at our site occurred from ∼1280 to 1430 CE, during the time of the Angkor droughts, supporting previous findings that this megadrought likely impacted much of Mainland Southeast Asia. In contrast, variations in stalagmite δ 18 O reflect changes in rainfall upstream from our study site. Interestingly, the δ 18 O record exhibits a positive correlation with solar activity that persists after 1200 CE, contrary to the findings in previous studies. Solar-forced climate model simulations reveal that these δ 18 O variations may be driven by solar-forced changes in upstream rainout over the tropical Indian Ocean, which modify the δ 18 O of moisture transported to our study site without necessarily affecting local rainfall amount. We conclude that future rainfall changes in Mainland Southeast Asia are likely to be superimposed on multidecadal to centennial-scale variations in background climate driven primarily by internal climate variability, whereas solar forcing may impact upstream rainout over the Indian Ocean. • New high-resolution speleothem record from northern Laos spanning ∼50 BCE to 1880 CE. • δ 13 C reflects local water balance and records centennial-length dry periods during the Little Ice Age. • δ 18 O reflects upstream rainout over the Indian Ocean and may be influenced by solar forcing. [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]

Organic phosphorus incorporated in calcite during laboratory precipitation experiments and in natural cave deposits was investigated by solid-state NMR spectroscopy. For calcite precipitated in the presence of organic phosphoesters of varying size and functionality, solid-state 31 P{ 1 H} CP/MAS NMR shows that the phosphoesters were incorporated intact into the solid. Systematic changes in the 31 P NMR chemical shift of the phosphate group were observed between the solid phosphoester and that incorporated in the solid precipitate, yielding 31 P NMR chemical shifts of the coprecipitates in the range of +1.8 to −2.2 ppm. These chemical shifts are distinct from that of similarly prepared calcite coprecipitated with inorganic phosphate, 3.5 ppm. Only minor changes were noted in the phosphoester 31 P chemical shift anisotropy (CSA) which suggests no significant change in the local structure of the phosphate group, which is dominated by C–O–P bonding. Close spatial proximity of the organic phosphate group to calcite structural components was revealed by 31 P/ 13 C rotational echo double resonance (REDOR) experiments for coprecipitates prepared with 13 C-labeled carbonate. All coprecipitates showed significant 31 P dephasing effects upon 13 C-irradiation, signaling atomic-scale proximity to carbonate carbon. The dephasing rate for smaller organophosphate molecules is similar to that observed for inorganic phosphate, whereas much slower dephasing was observed for larger molecules having long and/or bulky side-chains. This result suggests that small organic molecules can be tightly enclosed within the calcite structure, whereas significant structural disruption required to accommodate the larger organic molecules leads to longer phosphate–carbonate distances. Comparison of 31 P NMR spectroscopic data from the synthetic coprecipitates with those from calcite moonmilk speleothems indicates that phosphorus occurs mainly as inorganic orthophosphate in the natural deposits, although small signals occur with characteristics consistent with phosphate monoesters. The results of this study indicate that trace- to minor concentrations of dissolved organic molecules can be effectively taken up during calcite precipitation and incorporated in the structure, leaving a resilient record of materials present during crystallization. [ABSTRACT FROM AUTHOR]

Lake Tovel is an oligotrophic, meromictic, mountain lake of the Dolomites that undergoes marked seasonal water-level fluctuations (WLFs). We used neo- and paleolimnological data collected since 1999 to test the utility of algal and cyanobacterial pigments and diatom and chironomid biodiversity as proxies for WLF and to highlight the contribution of benthic algae to the sediment record. We found that detailed knowledge of presentday spatiotemporal patterns of WLF is essential for a complete and correct interpretation of paleolimnological data. Scytonemin, a cyanobacteria-specific photoprotective pigment, was produced by epilithic cyanobacteria in the depth zone affected by WLF and should be considered a proxy for the extent of WLF. The phytobenthos was as important as phytoplankton as a source of sedimentary pigments. We used information gained on the detailed distribution of diatoms at different depths and on different substrata in the 2 basins to show the probable location in the lake from which taxa in sediment cores originated to aid in interpretation of the sediment archive (including identification of periods of active hydrology). We sampled present-day chironomids in springs and streams feeding the lake and along a depth transect in the main basin. The taxa found were all rheophilic, crenophilous, or typical of the littoral zone of oligotrophic lakes. We interpreted sections of the cores containing large numbers of Orthocladiinae and Diamesinae head capsules as indicative of periods of active hydrology (including sudden and marked WLF) because the littoral taxa found in the cores must have been derived from the littoral zone by sediment focusing or slumps. Thus, we identified useful proxies of WLF in mountain, carbonate lakes. [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]

There is a shortage of archives of sulfur that can be used to investigate industrial or volcanic pollution in terrestrial catchments, but the role of S as a nutrient, coupled with sparse published evidence, suggests that trees are promising targets. We focused on two conifer species (Picea abies (L) Karst and Abies alba Miller) from an Alpine site in NE Italy. Bulk analyses of Abies demonstrate that S concentrations were higher in the second half of the 20th century but with some high outliers possibly reflecting particulate impurities. X-ray synchrotron analyses confirmed the observed time trend, which is similar to that of a nearby stalagmite, and reflects an atmospheric pollution record mediated by storage in the soil and ecosystem. S and P were found to be localized in the inner cell wall (ca. 2μm wide), local thickenings of which probably account for some outlying high values of S in synchrotron studies. S occurs as a mixture of oxidation states (0 to +0.5, +2, +5, and +6) which are consistent in space and time. The results indicate that wood older than a few years contains archive-quality S but that robust conclusions require multiple replicate analyses. [ABSTRACT FROM AUTHOR]

The magnitude of recent warming, and the variability of climate on centennial-millennial time scales are compromised by questions concerning the ability of tree rings to capture low-frequency climate fluctuations. Annually laminated stalagmite records can potentially provide a low-frequency climate archive through variations in annual growth rate. Presented here is an initial attempt to demonstrate the applicability of annually laminated stalagmite series to a large-scale climate reconstruction, by producing a 500-year Northern Hemisphere temperature reconstruction. The reconstruction shows an overall warming trend with a magnitude of 0.65 K and several other low-frequency characteristics consistent with other independent Northern Hemisphere archives. The result is sufficiently encouraging to warrant significant future effort in characterising annual growth rate records from laminated speleothems. Copyright © 2006 Royal Meteorological Society. [ABSTRACT FROM AUTHOR]

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]