Dr Andrea Borsato

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.

The genesis of calcite coralloid speleothems from Lamalunga cave (Southern Italy) is here investigated from a purely petrographic perspective, which constitutes the basis for any subsequent chemical investigation. Lamalunga cave coralloids formed on bones and debris on the floor of the cave. They consist of elongated columnar crystals whose elongation progressively increases from the flanks to the tips of the coralloid, forming a succession of lens-shaped layers, which may be separated by micrite or impurity-rich layers. Organic molecules are preferentially concentrated toward the centre of convex lenses as highlighted by epifluorescence. Their occurrence on cave floor, lens-shaped morphology and concentration of impurities toward the apex of the convex lenses supports the hypothesis that their water supply was hydroaerosol, generated by the fragmentation of cave drips. Evaporation and degassing preferentially occurred on tips, enhancing the digitated morphology and trapping the organic molecules and impurities, carried by the hydroaerosol, between the growing crystals which became more elongated. Micrite layers, that cap some coralloid lenses, likely identify periods when decreasing in hydroaerosol resulted in stronger evaporation and higher supersaturation with respect to calcite of the parent film of fluid. This interpretation of coralloid formation implies that these speleothems can be used to extract hydroclimate information.

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 (Zinf) ranging from 355 to 2400 m a.s.l., corresponding to infiltration mean annual temperatures (MATinf) between 12 and 0 °C. Since all the caves developed in pure carbonate rocks, soil pCO2 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 (SICC) are directly correlated with the MATinf, which influences the vegetation zones and eventually the production of CO2 in the soil. SICC linearly depends on MATinf (SICC = 0.09 MATinf - 0.4) and SICC = 0 is reached at Zinf = 1.66 km a.s.l., corresponding to a MATinf = 4.4 °C. This point identifies the "speleothem limit" defined here as the elevation (or corresponding MATinf) above which no sparitic speleothem precipitation usually occurs. We demonstrate that due to temperature-forced changes in the soil and vegetation and subsequently SICC, 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 SiO2/Ca and SO4/Ca ratios in cave waters to complement Mg/Ca and Sr/Ca ratios as markers of PCP. SO4 and SiO2 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, SiO2/Ca and SO4/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.

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.

Sulphate concentrations in speleothems identify major volcanic eruptions, provide useful information on soil and aquifer dynamics and, in similar fashion to the ¹⁴C 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<inf>4</inf> concentration from a high of 7.5±0.8mg/l in 1993-1994 to a low of 2.2±0.2mg/l in 2013-2014, and replicates with a delay of ~15 years the decline in the atmospheric SO<inf>2</inf> 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.

Terrestrial records of past climatic conditions, such as lake sediments and speleothems, provide data of great importance for understanding environmental changes. However, unlike marine and ice core records, terrestrial palaeodata are often not available in databases or in a format that is easily accessible to the non-specialist. As a consequence, many excellent terrestrial records are unknown to the broader palaeoclimate community and are not included in compilations, comparisons, or modelling exercises. Here we present a compilation of Western European terrestrial palaeo-records covering, entirely or partially, the 60-8-ka INTIMATE time period. The compilation contains 56 natural archives, including lake records, speleothems, ice cores, and terrestrial proxies in marine records. The compilation is limited to include records of high temporal resolution and/or records that provide climate proxies or quantitative reconstructions of environmental parameters, such as temperature or precipitation, and that are of relevance and interest to a broader community. We briefly review the different types of terrestrial archives, their respective proxies, their interpretation and their application for palaeoclimatic reconstructions. We also discuss the importance of independent chronologies and the issue of record synchronization. The aim of this exercise is to provide the wider palaeo-community with a consistent compilation of high-quality terrestrial records, to facilitate model-data comparisons, and to identify key areas of interest for future investigations. We use the compilation to investigate Western European latitudinal climate gradients during the deglacial period and, despite of poorly constrained chronologies for the older records, we summarize the main results obtained from NW and SW European terrestrial records before the LGM.

Mounting evidence exists that variations in sulphur content in stalagmites are closely linked to changes in volcanic or anthropogenic atmospheric sulphur. The strong dependency of sulphur on soil pH and ecosystem storage, however, can result in a delay of several years to decades in the registration of volcanic eruptions and anthropogenic emissions by stalagmites. Here we present synchrotron-radiation based trace element analysis performed on a precisely-dated section of a stalagmite from Sofular Cave in Northern Turkey. As this section covers the time interval of the intensively studied Minoan volcanic eruption between 1600 and 1650 BC, we can test whether this vigorous eruption can be traced in a stalagmite. Of all measured trace elements, only bromine shows a clear short-lived peak at 1621 ± 25 BC, whereas sulphur and molybdenum show peaks later at 1617 ± 25 and 1589 ± 25 respectively. We suggest that all trace element peaks are related to the Minoan eruption, whereas the observed phasing of bromine, molybdenum and sulphur is related to differences in their retention rates in the soil above Sofular Cave. For the first time, we can show that bromine appears to be an ideal volcanic tracer in stalagmites, as it is a prominent volatile component in volcanic eruptions, can be easily leached in soils and rapidly transferred from the atmosphere through the soil and bedrock into the cave and stalagmite respectively. Highly resolved oxygen and carbon isotope profiles indicate that the Minoan eruption had no detectable climatic and environmental impact in Northern Turkey. © 2014 Elsevier B.V.

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. © 2014 by The Society for Freshwater Science.

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±15ka to 130.1±1.9ka. Thus, the skeleton from Altamura represents the most ancient Neanderthal from which endogenous DNA has ever been extracted.

In the past decade a new approach to cartography and mapping of Quaternary continental deposits allowed the abandonment of the now obsolete "classical model" by Penck & Brückner (1909), which was based on four major glaciations. The new approach utilizes stratigraphic units, which are bounded by discontinuities and defined by following glacial and/or hydrographic basins, framed within a relative chronological scale (Allostratigraphic Units and Unconformity-bounded stratigraphic units). The present paper, which synthesizes different approaches to Quaternary continental stratigraphy, proposes a definition of the terminology used in the Alpine area, in order to make clear the significance of each term, and assess its proper use. The terms Last Glacial Maximum (LGM), post-glacial, and Pre-LGM are here discussed in detail. The term LGM indicates the last local glacial maximum, without any reference to stratigraphic and chronostratigraphic units. The term post-glacial is used to indicate the events which followed the last local glacial expansion. The term Pre-LGM indicates the events that preceded the last local glacial maximum. Furthermore, we here discuss some of the problems of classification that arise following the use of the new terminology, and suggest possible cartographic solutions.

We present the multifractal analysis of several signals recorded at the valclusian karstic spring of Prese val, located in the Dolomities area NW of Trento (Italy). The data analysed include water discharge, temperature and electric conductivity. Both electric conductivity and temperature, which mimic the spatial variability of hydraulic conductivity, show the signature of multifractality with increments distributed as a Lévy stable probability distribution. This is not the case for the water discharge. We conclude that accurately recorded signals of electric conductivity and temperature of spring water can be used for characterization of karst systems.

Calcite moonmilk, which is a cave deposit formed of calcite crystals and water, is found in many caves in the Italian Alps. These modern and ancient deposits are formed of fiber calcite crystals, 50-500 nm wide and 1 to > 10 µm long, and polycrystalline chains that have few crystal defects. Radiocarbon dating indicates that most moonmilk deposits in these caves are fossil and that for most precipitation ceased ~ 6400 cal years BP, at the end of the mid-Holocene Hypsithermal. In the caves of the Italian Alps, the optimal conditions for formation of calcite moonmilk are: (1) a temperature range of 3.5-5.5°C, (2) low discharge volumes of seepage waters that are slightly supersaturated (SICAL = 0.0 to ~ 0.2), and (3) relative humidity that is at or close to 100%. Microbial activity apparently did not play an active role in the formation of the calcite moonmilk. Conditions for moonmilk formation are typically found in caves that are located beneath land surfaces, which are soil covered and support a conifer forest. Precipitation of the fiber calcite crystals apparently involved very slow flow of slightly supersaturated fluids. The fact that moonmilk appears to form under a narrow range of environmental conditions means that this cave deposit has potential as a paleoclimatic indicator in high alpine karst areas. Copyright © 2000, SEPM (Society for Sedimentary Geology).

Calcite moonmilk, which is a cave deposit formed of calcite crystals and water, is found in many caves in the Italian Alps. These modern and ancient deposits are formed of fiber calcite crystals, 50-500 nm wide and 1 to > 10 µm long, and polycrystalline chains that have few crystal defects. Radiocarbon dating indicates that most moonmilk deposits in these caves are fossil and that for most precipitation ceased ~ 6400 cal years BP, at the end of the mid-Holocene Hypsithermal. In the caves of the Italian Alps, the optimal conditions for formation of calcite moonmilk are: (1) a temperature range of 3.5-5.5°C, (2) low discharge volumes of seepage waters that are slightly supersaturated (SICAL= 0.0 to ~ 0.2), and (3) relative humidity that is at or close to 100%. Microbial activity apparently did not play an active role in the formation of the calcite moonmilk. Conditions for moonmilk formation are typically found in caves that are located beneath land surfaces, which are soil covered and support a conifer forest. Precipitation of the fiber calcite crystals apparently involved very slow flow of slightly supersaturated fluids. The fact that moonmilk appears to form under a narrow range of environmental conditions means that this cave deposit has potential as a paleoclimatic indicator in high alpine karst areas. Copyright © 2000, SEPM (Society for Sedimentary Geology).

The present work has been performed in the framework of the research project AQUAPAST. The main focus of AQUAPAST is the reconstruction of past climate changes in the atmospheric circulation and in particular in the water vapour transport mechanism over the Mediterranean area starting from the analysis of the isotopic content of cave speleothemes in the Trentino Province (North-East of Italy). A Lagrangian methodology for the reconstruction and the analysis of the airstreams which govern the transport of water vapour has been applied to recent events. The average monthly isotopic signal of the precipitation water sampled in stations located in key geographic settings in the Province of Trento is used as tracer to infer the origin of the precipitating water and to validate Lagrangian analysis. A comparison between the isotopic signal of November 2002 and November 2003 is here presented, as most of the yearly precipitation falls in November over the Eastern Alps. Hypotheses are proposed about the meteorological factors (e.g. monthly averaged sea surface temperature atmospheric circulation, etc.) determining different isotopic signal in the two years.