Speleothem preservation and diagenesis in South African hominin sites implications for paleoenvironments and geochronology

Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ¹³C values of the primary and secondary calcites range from +6 to −9‰ and δ¹⁸O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ¹³C and relatively invariant δ¹⁸O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO₂ during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C₃ and C₄ vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.     

Identifying low-temperature hydrothermal karst and palaeowaters using stable isotopes: a case study from an alpine cave,Entrische Kirche,Austria

The area south of the prominent east–west trending Salzach Valley at the northern rim of the Central Alps of Austria has long been known to host anomalously warm springs emerging from a highly deformed calcite marble (Klammkalk). This unit also hosts cavities whose shapes suggest a hydrothermal karst origin and which are lined by calcite spar. We report here petrographic and isotopic evidence suggesting that dissolution by ascending low-temperature thermal waters also played an important role in the origin of a large cave in this region, Entrische Kirche. A paleo cave wall, preserved behind a thick flowstone in the interior of this cave, revealed a brownish bleaching zone which contrasts to the medium grey colour of the unaltered marble beneath. Across this zone the C and O isotope values gradually decrease by 3 and 11‰, respectively. These compositions are very different from those of the speleothem above but are similar to phreatic calcite spar from hydrothermal karst cavities in other outcrops in the area, where the absence of two-phase fluid inclusions suggests a low-temperature (less than ca. 50°C) hydrothermal origin. U/Th dating of the flowstone capping the alteration zone yielded a minimum age of the thermal water invasion in Entrische Kirche of ca. 240 kyr. There is no evidence in Entrische Kirche that these palaeowaters reached the point of calcite precipitation, but it is physically conceivable that higher and as yet unexplored parts of this deep (ca. 900 m) cave contain cavities lined by phreatic cave spar.     

Origin and palaeoenvironmental significance of lamination in stalagmites from Katerloch Cave,Austria

The origin and environmental dependencies of lamination in stalagmites from Katerloch, common in speleothems from other cave sites, are examined in detail. Petrographic observations and chemical analyses (including isotopes) of stalagmites and modern calcite were combined with multi‐annual cave monitoring. All investigated stalagmites are composed of low‐Mg calcite and show white, porous laminae and typically thinner, translucent dense laminae. The binary lamination pattern results from changes in the calcite fabric: white, porous laminae are characterized by a high porosity and abundant fluid inclusions and also by enhanced vertical growth and thinning towards the flanks. Translucent, dense laminae exhibit a compact fabric and constant thickness of individual growth layers. U‐Th dating supports an annual origin of the lamination and the seasonally changing intensity of cave ventilation provides a robust explanation for the observed relationships between lamination, stable C isotopic compositions and trace elements (Mg, Sr and Ba). The seasonally variable air exchange, driven by temperature contrasts between the cave interior and outside atmosphere, modulates the rate and amount of CO₂ degassing from the drip water and affects the hydrochemistry and consequently the fabric of the precipitating calcite. Although cave air composition and drip rate are both major variables in controlling CO₂ degassing from the drip water, the seasonally changing ventilation in Katerloch exerts the primary control and the results suggest a secondary (amplifying/attenuating) influence of the drip rate. Drip rate, however, might be the controlling parameter for lamina development at cave sites experiencing only small seasonal cave air exchange. Importantly, the seasonally variable composition of drip water does not reflect the seasonal cycle of processes in the soil zone, but results from exchange with the cave atmosphere. The alternating porous and dense calcite fabric is the expression of a variable degree of lateral coalescence of smaller crystallites forming large columnar crystals. The white, porous laminae represent partial coalescence and form during the warm season: low calcite δ¹³C values are linked to low δ¹³C values of cave air and drip water during that time. This observation corresponds to times of reduced cave ventilation, high pCO₂ of cave air, low drip water pH, lower calcite supersaturation and typically high drip rates. In contrast, the translucent, dense laminae represent more or less complete lateral coalescence (inclusion‐free) during the cold season (high calcite, drip water and cave air δ¹³C values), i.e. times of enhanced cave ventilation, low cave air pCO₂, increased drip water pH, relatively high calcite supersaturation and typically low drip rates. In essence, the relative development of the two lamina types reflects changes in the seasonality of external air temperature and precipitation, with a strong control of the winter air temperature on the intensity of cave‐air exchange. Thick translucent, dense laminae are favoured by long, cold and wet winters and such conditions may be related closely to the North Atlantic Oscillation mode (weak westerlies) and enhanced Mediterranean cyclone activity during the cold season. Studies of speleothem lamination can thus help to better understand (and quantify) the role of seasonality changes, for example, during rapid climate events.     

Pleistocene speleothems of Mallorca: implications for palaeoclimate and carbonate diagenesis in mixing zones

The Pleistocene speleothems of Sa Bassa Blanca cave, Mallorca, are excellent indicators of palaeoclimate variations, and are samples that allow evaluation of the products and processes of mixing‐zone diagenesis in an open‐water cave system. Integrated stratigraphic, petrographic and geochemical data from a horizontal core of speleothem identified two main origins for speleothem precipitates: meteoric‐marine mixing zone and meteoric‐vadose zone. Mixing‐zone precipitates formed at and just below the water–air interface of cave pools during interglacial times, when the cave was flooded as a result of highstand sea‐level. Mixing‐zone precipitates include bladed and dendritic high‐Mg calcite, microporous‐bladed calcite with variable Mg content, and acicular aragonite; their presence suggests that calcium‐carbonate cementation is significant in the studied mixing‐zone system. Fluid inclusion salinities, δ¹³C and δ¹⁸O compositions of the mixing‐zone precipitates suggest that mixing ratio was not the primary control on whether precipitation or dissolution occurred, rather, the proximity to the water table and degassing of CO₂ at the interface, were the major controls on precipitation. Thus, simple two‐end‐member mixing models may apply only in mixing zones well below the water table. Meteoric‐vadose speleothems include calcite and high‐Mg calcite with columnar and bladed morphologies. Vadose speleothems precipitated during glacial stages when sea level was lower than present. Progressive increase in δ¹³C and δ¹⁸O of the vadose speleothems resulted from cooling temperatures and more positive seawater δ¹⁸O associated with glacial buildup. Such covariation could be considered as a valid alternative to models predicting invariant δ¹⁸O and highly variable δ¹³C in meteoric calcite. Glacio‐eustatic oscillations of sea‐level are recorded as alternating vadose and mixing‐zone speleothems. Short‐term climatic variations are recorded as alternating aragonite and calcite speleothems precipitated in the mixing zone. Fluid‐inclusion and stable‐isotope data suggest that aragonite, as opposed to calcite, precipitated during times of reduced meteoric recharge.     

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

Meteoric sphaerosiderite lines (MSLs), defined by invariant δ¹⁸O and variable δ¹³C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO₃ nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO₃) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca²⁺, Mg²⁺ and Mn²⁺ for Fe²⁺. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ¹⁸O and δ¹³C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ¹⁸O and δ¹³C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ¹⁸O vs. δ¹³C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ¹⁸O and δ¹³C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.     

Effective precipitation in southern Spain ( 266 to 46 ka) based on a speleothem stable carbon isotope record

We present the longest-duration directly dated terrestrial palaeoclimate record from the western Mediterranean region: a flowstone speleothem from Gitana Cave, southeast Spain. The main phase of growth was 274 to 58 ka, dated by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) U-series methods. Effective precipitation, which we consider primarily responsible for flowstone calcite δ¹³C variations, measured at 300 μm resolution, was higher during interglacials associated with marine oxygen isotope stages (MIS) 7 and 5, and lower during glacial MIS 6. There is a close correspondence between speleothem δ¹³C and sea surface temperature (SST) estimates from adjacent Atlantic Ocean cores during MIS 6, which implies that oceanic conditions are critical in controlling the western Mediterranean terrestrial moisture balance during glacial periods. Other features of our record, such as the sequence of termination II warming/moistening between approximately 133 and 127 ka, including a “pause” around 130–128 ka, and the lagged termination of MIS 5 warm intervals (5e, 5c and 5a) are similar to other terrestrial records within the Mediterranean basin, indicating climate synchroneity along the northern Mediterranean coast. The Gitana cave region also may have been a refugium for temperate species during short-lived cold/arid periods during MIS 5.     

Modeling speleothem δC variability in a central Sierra Nevada cave using C and Sr/Sr

Carbon isotopes in speleothems can vary in response to a number of complex processes active in cave systems that are both directly and indirectly related to climate. Progressing downward from the soil zone overlying the cave, these processes include soil respiration, fluid-rock interaction in the host limestone, degassing of CO₂ and precipitation of calcite upflow from the speleothem drip site, and calcite precipitation at the drip site. Here we develop a new approach to independently constrain the roles of water-rock interaction and soil processes in controlling stalagmite δ¹³C. This approach uses the dead carbon proportion (dcp) estimated from coupled ¹⁴C and ²³⁰Th/U measurements, in conjunction with Sr isotope analyses on stalagmite calcite from a central Sierra Nevada foothills cave in California, a region characterized by a highly seasonal Mediterranean-type climate, to determine the roles of water-rock interaction and soil processes in determining stalagmite δ¹³C. Increases in stalagmite dcp between 16.5 and 8.8 ka are coincident with decreased δ¹³C, indicating a varying yet substantial contribution from the soil organic matter (SOM) reservoir, likely due to significantly increased average age of SOM in the soil veneer above the cave during wet climatic intervals.We use geochemical and isotope mixing models to estimate the host-carbonate contribution throughout the δ¹³C time series and determine the degree of degassing and calcite precipitation that occurred prior to precipitation of stalagmite calcite. The degree of degassing and prior calcite precipitation we calculate varies systematically with other climate indicators, with less degassing and prior calcite precipitation occurring during wetter climatic intervals and more during drier intervals. Modeled δ¹³C values and degassing calculations suggest that some degree of prior calcite precipitation is necessary at all time intervals to explain measured stalagmite δ¹³C values, even during relatively wet intervals. These results illustrate the importance of constraining degassing and prior calcite precipitation in the interpretation of speleothem δ¹³C records, particularly those from caves that formed in seasonal semi-arid to arid environments.     

The significance of chemical,isotopic, and detrital components in three coeval stalagmites from the superhumid southernmost Andes (53°S) as high-resolution palaeo-climate proxies

Stalagmites are important palaeo-climatic archives since their chemical and isotopic signatures have the potential to record high-resolution changes in temperature and precipitation over thousands of years. We present three U/Th-dated records of stalagmites (MA1–MA3) in the superhumid southern Andes, Chile (53°S). They grew simultaneously during the last five thousand years (ka BP) in a cave that developed in schist and granodiorite. Major and trace elements as well as the C and O isotope compositions of the stalagmites were analysed at high spatial and temporal resolution as proxies for palaeo-temperature and palaeo-precipitation. Calibrations are based on data from five years of monitoring the climate and hydrology inside and outside the cave and on data from 100 years of regional weather station records.Water-insoluble elements such as Y and HREE in the stalagmites indicate the amount of incorporated siliciclastic detritus. Monitoring shows that the quantity of detritus is controlled by the drip water rate once a threshold level has been exceeded. In general, drip rate variations of the stalagmites depend on the amount of rainfall. However, different drip-water pathways above each drip location gave rise to individual drip rate levels. Only one of the three stalagmites (MA1) had sufficiently high drip rates to record detrital proxies over its complete length. Carbonate-compatible element contents (e.g. U, Sr, Mg), which were measured up to sub-annual resolution, document changes in meteoric precipitation and related drip-water dilution. In addition, these soluble elements are controlled by leaching during weathering of the host rock and soils depending on the pH of acidic pore waters in the peaty soils of the cave’s catchment area. In general, higher rainfall resulted in a lower concentration of these elements and vice versa. The Mg/Ca record of stalagmite MA1 was calibrated against meteoric precipitation records for the last 100 years from two regional weather stations. Carbonate-compatible soluble elements show similar patterns in the three stalagmites with generally high values when drip rates and detrital tracers were low and vice versa. δ¹³C and δ¹⁸O values are highly correlated in each stalagmite suggesting a predominantly drip rate dependent kinetic control by evaporation and/or outgassing. Only C and O isotopes from stalagmite MA1 that received the highest drip rates show a good correlation between detrital proxy elements and carbonate-compatible elements. A temperature-related change in rainwater isotope values modified the MA1 record during the Little Ice Age (～0.7–0.1 ka BP) that was ～1.5 °C colder than today. The isotopic composition of the stalagmites MA2 and MA3 that formed at lower drip rates shows a poor correlation with stalagmite MA1 and all other chemical proxies of MA1. ‘Hendy tests’ indicate that the degassing-controlled isotope fractionation of MA2 and MA3 had already started at the cave roof, especially when drip rates were low. Changing pathways and residence times of the seepage water caused a non-climatically controlled isotope fractionation, which may be generally important in ventilated caves during phases of low drip rates. Our proxies indicate that the Neoglacial cold phases from ～3.5 to 2.5 and from ～0.7 to 0.1 ka BP were characterised by 30% lower precipitation compared with the Medieval Warm Period from 1.2 to 0.8 ka BP, which was extremely humid in this region.     

Speleothems from the earliest Quaternary: Snapshots of paleoclimate and landscape evolution at the northern rim of the Alps

Ancient cave systems in the Northern Calcareous Alps, today located well above the timberline at altitudes of 2400–2500 m, host U-rich speleothems that preserved growth layers on the microscopic scale of presumably annual origin. Two flowstone samples were dated to 2.019 + 0.037/?0.069 Ma and 1.730 + 0.032/?0.068 Ma, respectively, using U–Pb isochron techniques. These ages are corroborated by the Late Pliocene to Early Pleistocene pollen spectrum extracted from one of the samples. We use a multiproxy approach and exploit laminated speleothem sequences to tie high-resolution stable isotope data to a floating lamina-counted chronology. O isotope values of growth intervals when calcite deposition was close to isotopic equilibrium are low compared to modern and Holocene speleothems from other alpine caves and are inconsistent with the current altitudinal setting of the caves. A vegetated but geomorphologically stable alpine catchment (i.e. ～2000 m asl., no (peri)glacial processes) combined with a deep-seated cave (the thickness of the vadose zone might have exceeded 1000 m) is required in order to reconcile the isotopic data with the pollen record and the petrographic evidence. Furthermore, the data can be used to constrain the rate for Quaternary rock-uplift to ≤0.8 mm/annum for this frontal part of the European Alps. Collectively, the data suggest that these speleothems formed both during interglacials (MIS 59 or 61) and interglacial–glacial transitions (MIS 75/74 or 77/76), but the seasonal precipitation pattern was arguably markedly different from today's. Provided that the highly regular microscopic laminae are indeed annual, lamina counts suggest a minimum length of ca 6 ka for interglacials during the earliest Pleistocene.     

Intra‐annual variation of the calcite deposition rate of drip water in Shihua Cave,Beijing, China and its implications for palaeoclimatic reconstructions

Cai, B., Zhu, J., Ban, F. & Tan, M. 2011: Intra‐annual variation of the calcite deposition rate of drip water in Shihua Cave, Beijing, China and its implications for palaeoclimatic reconstructions. Boreas, Vol. 40, pp. 525–535. 10.1111/j.1502‐3885.2010.00201.x. ISSN 0300‐9483. Monthly in situ monitoring of the calcite deposition rate, drip‐water chemistry and surrounding cave environment was carried out at Shihua Cave, Beijing, China, through two hydrological years (from January 2006 to February 2008) to determine the seasonal variability and mechanisms of stalagmite growth in Shihua Cave. Calcite deposition rates exhibit significant intra‐annual variation, with the lowest values during the summer monsoonal rainy season (July–August) and peak values from autumn to spring. The temporal change in the calcite deposition rate is negatively correlated with the drip rate, cave‐air PCO₂ (CO₂ partial pressure) and Ca concentration, and positively correlated with the pH of the feeding drip water. The seasonal recharge regime of drip water is likely to be the primary control on the drip‐water quality and quantity, which, in turn, control the calcite deposition rate in Shihua Cave. During the summer rainy season, periodic and intense rainstorms increase the drip rate and cave‐air PCO₂, leading to drip water with a lower pH and saturation index of calcite, thereby reducing the calcite precipitation. It seems that the high cave‐air PCO₂ is the dominant control on the calcite deposition rate during the rainy season. Our previous study on the dissolved organic carbon of drip water concluded that the thin luminescent bands in stalagmite laminae from Shihua Cave form during the rainy season. The lower calcite deposition rate during the rainy season further supports this suggestion. The significant intra‐seasonal variability of the calcite deposition rate implies that the seasonal bias of δ¹⁸O of stalagmites should be considered when stalagmite δ¹⁸O is used as a high‐resolution palaeoclimatic archive.     

CO clumping in speleothems: Observations from natural caves and precipitation experiments

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ¹⁸O. Interpreting speleothem δ¹⁸O records in terms of absolute paleotemperatures and δ¹⁸O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ₄₇ (a geochemical variable reflecting the statistical overabundance of ¹³C¹⁸O bonds in CO₂ evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ₄₇ value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation.Here we report Δ₄₇ values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ₄₇ and heavier δ¹⁸O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ₄₇ disequilibrium and that of δ¹⁸O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ¹⁸O and Δ₄₇ values, probably inherited from prior degassing within the cave system.In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ₄₇ in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ₄₇ in inorganic carbonates.     

Speleothem record of the last 180 ka in Villars cave (SW France): Investigation of a large δ18O shift between MIS6 and MIS5

The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U–Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ¹⁸O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ¹⁸O variations in speleothem calcite.Oxygen isotope analyses of fluid inclusions indicate that drip water δ¹⁸O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ¹⁸O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ¹⁸O.Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ¹⁸O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ¹⁸O yield unreasonably high estimates of ～20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site.Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ¹⁸O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records.     

Environmental responses to Lateglacial climatic fluctuations recorded in the sediments of pre‐Alpine Lake Mondsee (northeastern Alps)

Investigation of the sedimentary record of pre‐Alpine Lake Mondsee (Upper Austria) focused on the environmental reaction to rapid Lateglacial climatic changes. Results of this study reveal complex proxy responses that are variable in time and influenced by the long‐term evolution of the lake and its catchment. A new field sampling approach facilitated continuous and precisely controlled parallel sampling at decadal to sub‐annual resolution for µ‐XRF element scanning, carbon geochemistry, stable isotope measurements on ostracods, pollen analyses and large‐scale thin sections for microfacies analysis. The Holocene chronology is established through microscopic varve counting and supported by accelerator mass spectrometry ¹⁴C dating of terrestrial plant macrofossils, whereas the Lateglacial age model is based on δ¹⁸O wiggle matching with the Greenland NGRIP record, using the GICC05 chronology. Microfacies analysis enables the detection of subtle sedimentological changes, proving that depositional processes even in rather large lake systems are highly sensitive to climate forcing. Comparing periods of major warming at the onset of the Lateglacial and Holocene and of major cooling at the onset of the Younger Dryas reveals differences in proxy responses, reflecting threshold effects and ecosystem inertia. Temperature increase, vegetation recovery, decrease of detrital flux and intensification of biochemical calcite precipitation at the onset of the Holocene took place with only decadal leads and lags over a ca. 100 a period, whereas the spread of woodlands and the reduction of detrital flux lagged the warming at the onset of the Lateglacial Interstadial by ca. 500–750 a. Cooling at the onset of the Younger Dryas is reflected by the simultaneous reaction of δ¹⁸O and vegetation, but sedimentological changes (reduction of endogenic calcite content, increase in detrital flux) were delayed by about 150–300 a. Three short‐term Lateglacial cold intervals, corresponding to Greenland isotope substages GI‐1d, GI‐1c2 and GI‐1b, also show complex proxy responses that vary in time. Copyright © 2011 John Wiley & Sons, Ltd.     

A late Holocene climate record in stalagmites from Modrič Cave (Croatia)

Few terrestrial Holocene climate records exist from south‐eastern Europe despite its important geographical position as a transitional climatic zone between the Mediterranean and mainland continental Europe. Here we present new petrographic and stable isotope data for two Holocene speleothems from Modri? Cave, Croatia (44°15′N, 15°32′E), a coastal Adriatic site (120 m inland). Modern meteorological and cave conditions have been monitored for 2 years to understand the links between climate variability and stable isotope time‐series records in speleothems. Typical of a Mediterranean‐type climate, a negative water balance exists between April and September, so that recharge of the aquifer is restricted to the winter months. The weighted mean δ¹⁸O of the rainfall is ?5.96‰ (2σ = 2.83), and the weighted mean D/H rainfall value is ?36.83‰ (2σ = 19.95), slightly above the Global Meteoric Water Line, but well below the Mediterranean Meteoric Water Line. Modern calcite from the tops of each stalagmite exhibits δ¹⁸O values that are close to isotopic equilibrium with their respective drip water values. Unfortunately, the relatively young ages and low uranium contents (ca. 50 p.p.b.) of both stalagmites hamper the use of U‐series dating. Radiocarbon dates have been used instead to constrain their chronology using a dead carbon correction. Apart from some Isotope Stage 3 material (ca. 55 ka), both stalagmites were deposited during the late Holocene. Climatic conditions during the late Holocene are inferred to have been sufficiently wet to maintain stalagmite growth and any hiatuses appear to be relatively short lived. Inferred changes in the stalagmite diameters during deposition are linked to δ¹³C and δ¹⁸O variations, indicating alternating periods of drier and wetter conditions. Drier conditions are inferred for the late Roman Ages warm period and the mid‐Medieval Warm Period. Wetter conditions are associated with the Little Ice Age. Copyright © 2012 John Wiley & Sons, Ltd.     

Carbonate stromatolites from a Messinian hypersaline setting in the Caltanissetta Basin, Sicily: petrographic evidence of microbial activity and related stable isotope and rare earth element signatures

Lower Messinian stromatolites of the Calcare di Base Formation at Sutera in Sicily record periods of low sea‐level, strong evaporation and elevated salinity, thought to be associated with the onset of the Messinian Salinity Crisis. Overlying aragonitic limestones were precipitated in normal to slightly evaporative conditions, occasionally influenced by an influx of meteoric water. Evidence of bacterial involvement in carbonate formation is recorded in three dolomite‐rich stromatolite beds in the lower portion of the section that contain low domes with irregular crinkly millimetre‐scale lamination and small fenestrae. The dominant microfabrics are: (i) peloidal and clotted dolomicrite with calcite‐filled fenestrae; (ii) dolomicrite with bacterium‐like filaments and pores partially filled by calcite or black amorphous matter; and (iii) micrite in which fenestrae alternate with dark thin wispy micrite. The filaments resemble Beggiatoa‐like sulphur bacteria. Under scanning electron microscopy, the filaments consist of spherical aggregates of dolomite, interpreted to result from calcification of bacterial microcolonies. The dolomite crystals are commonly arranged as rounded grains that appear to be incorporated or absorbed into developing crystal faces. Biofilm‐like remains occur in voids between the filaments. The dolomite consistently shows negative δ¹³C values (down to ?11·3‰) and very positive δ¹⁸O (mean value 7·9‰) that suggest formation as primary precipitate with a substantial contribution of organic CO₂. Very negative δ¹³C values (down to ?31·6‰) of early diagenetic calcite associated with the dolomite suggest contribution of CO₂ originating by anaerobic methane oxidation. The shale‐normalized rare earth element patterns of Sutera stromatolites show features similar to those in present‐day microbial mats with enrichment in light rare earth elements, and M‐type tetrad effects (enrichment around Pr coupled to a decline around Nd and a peak around Sm and Eu). Taken together, the petrography and geochemistry of the Sutera stromatolites provide diverse and compelling evidence for microbial influence on carbonate precipitation.     

Seasonal records of climatic change in annually laminated tufas: short review and future prospects

Many Recent and fossil freshwater tufa stromatolites contain millimetre‐scale, alternating laminae of dense micrite and more porous or sparry crystalline calcites. These alternating laminae have been interpreted to represent seasonally controlled differences in the biotic activity of microbes, and/or seasonally controlled changes in the rate of calcification. Either way, couplets of these microbially mediated alternating calcified laminae are generally agreed to represent annual seasonality. Combined stable isotope (δ¹⁸O and δ¹³C) and trace element (Mg, Sr, Ba) geochemistry from Recent tufa stromatolites show that seasonal climatic information is available from these calcites. Variability in δ¹⁸O (and in one case Mg concentration) has been shown to be controlled primarily by stream temperature change, usually driven by solar insolation. In arid climates, seasonal evaporation can also cause δ¹⁸O enrichment by at least 1‰. Variability in δ¹³C results potentially from: (1) seasonal change in plant uptake of ¹²C‐enriched CO₂; (2) seasonal change in degassing of ¹²C‐enriched CO₂ in the aquifer system; and (3) precipitation of calcite along the aquifer or river flow path, a process that increases δ¹³C of dissolved inorganic carbon (DIC) in the remaining water. Mechanisms 2 and 3 are linked because calcite precipitates in aquifers where degassing occurs, e.g. air pockets. The latter mechanism for δ¹³C enrichment has also been shown to cause sympathetic variation between trace element/Ca ratios and δ¹³C because trace elements with partition coefficients much greater than 1 (e.g. Sr, Ba) remain preferentially in solution. Since degassing in air pockets will be enhanced during decreased recharge when water saturation of the aquifer is lowest, sympathetic variation in trace element/Ca ratios and δ¹³C is a possible index of recharge and therefore precipitation intensity. High‐resolution geochemical data from well‐dated tufa stromatolites have great potential for Quaternary palaeoclimate reconstructions, possibly allowing recovery of annual seasonal climatic information including water temperature variation and change in rainfall intensity. However, careful consideration of diagenetic effects, particularly aggrading neomorphism, needs to be the next step. Copyright © 2005 John Wiley & Sons, Ltd.     

A continuous stable isotope record from the penultimate glacial maximum to the Last Interglacial (159–121 ka) from Tana Che Urla Cave (Apuan Alps,central Italy)

Relatively few radiometrically dated records are available for the central Mediterranean spanning the marine oxygen isotope stage 6–5 (MIS 6–5) transition and the first part of the Last Interglacial. Two flowstone cores from Tana che Urla Cave (TCU, central Italy), constrained by 19 U/Th ages, preserve an interval of continuous speleothem deposition between ca. 159 and 121 ka. A multiproxy record (δ¹⁸O, δ¹³C, growth rate and petrographic changes) obtained from this flowstone preserves significant regional-scale hydrological changes through the glacial/interglacial transition and multi-centennial variability (interpreted as alternations between wetter and drier periods) within both glacial and interglacial stages. The glacial stage shows a wetter period between ca. 154 and 152 ka, while the early to middle Last Interglacial period shows several drying events at ca. 129, 126 and 122 ka, which can be placed in the wider context of climatic instability emerging from North Atlantic marine and NW European terrestrial records. The TCU record also provides important insights into the evolution of local environmental conditions (i.e. soil development) in response to regional and global-scale climate events.     

Sub‐millennial climate shifts in the western Mediterranean during the last glacial period recorded in a speleothem from Mallorca,Spain

Very few high‐resolution and directly dated terrestrial archives of the last glacial period exist for the western Mediterranean region, yet this is a key locality for recording sub‐millennial North Atlantic and Mediterranean climate change. Here, we present evidence of effective precipitation changes based on growth history and δ¹³C of calcite in a Mallorcan stalagmite that grew between 112 and 48 ka. Effective precipitation in Mallorca appears to have been sensitive to proximal sea surface temperature variations and at certain times, ca. 76 ka for example, changed rapidly from moist to arid conditions in only a few centuries. A sea‐level highstand during Marine Isotope Stage (MIS) 5a interrupted growth. Regrowth started promptly after this, but effective precipitation decreased markedly for much of the later part of MIS 5a, and also for shorter periods correlative with Heinrich events H8 (ca. 90 ka) and H6 (ca. 65 ka), with growth ceasing during H5 (ca. 48 ka). Arid episodes in Mallorca appear to be expressions of extremely cold periods recorded further north in Europe and occur contemporaneously with rapid decreases in Greenland temperature. Copyright © 2008 John Wiley & Sons, Ltd.     

Manifestations of Quaternary syn-eruptive fluid circulations on carbonate veins,Central Anatolian Volcanic Province

In this study, we investigate the geochronological, geochemical and isotopic characteristics of two travertine sites surrounded by Quaternary eruption centres in central Anatolia with ample palaeo-eruption records. High-resolution carbonate precipitation records, revealed by U-Th dating, are clustered around 5–35, 60–100 and 120–170 ka and are well correlated with the dataset on eruptions as well as the position of fractures related to the volcanic centres. Syn-eruptive carbonate precipitation seems to occur due to the circulation of CO₂-rich fluids along the extensional fracture systems aligned tangentially to the related volcanic conduit and, therefore, the study of this system could be an alternative technique for the reconstruction of palaeo-eruptions. δ¹⁸O values of the studied travertines are within the range of meteogene fluids. Oxygen isotope compositions at around 130 ka match well with Glacial Termination II that is also recorded by climate proxies in various cave and benthic deposits throughout the world. It is likely that the studied carbonates were precipitated under similar fluid circulation conditions which are represented by a high rate of dilatation followed by a meteoric water influx into the extensional fractures.     

桂林地区近150年来的气候变化——基于 210Pb计年的洞穴碳酸盐沉积物记录

采用 ²¹⁰Pb定年和碳、氧稳定同位素分析方法对盘龙洞内的洞穴次生碳酸盐沉积物进行了系统研究,重建桂林地区近150年来的气候变化。本文采用的次生碳酸盐沉积物是采自桂林盘龙洞中的P001石笋和P007流石,分别获得9个和12个 ²¹⁰Pb测年数据; 以及41个和46个碳、氧同位素数据。P001石笋碳、氧同位素记录年代跨度为公元 1869～2002年,  δ¹⁸O  平均值为－6.28‰, δ¹³O  平均值为－7.59‰; P007流石碳、氧同位素记录跨度为公元 1854～2004年,  δ¹⁸O  平均值为－5.27‰, δ¹³O  平均值为－6.68‰。P001石笋和P007流石碳、氧同位素记录的低频信号显示出一致的变化趋势,而且二者的 δ13C 曲线相对  δ¹⁸O  曲线一致性更强,说明它们受同样环境条件所制约,同时也说明了其 ²¹⁰Pb年代系列的建立是可靠的。盘龙洞石笋和流石的  δ¹⁸O 和  δ¹³O 记录在公元 1930～1965年都出现一个低谷,表明该时段植被生产力相对减弱,亦即降水相对减少。通过P001石笋和P007流石的碳、氧同位素记录与现代降雨记录的比较可知,在年际至10年际尺度上,氧同位素反映的为降水或者季风的强弱。由此,公元1854年到2005年的151年内,盘龙洞碳酸盐沉积物氧同位素所反映的气候变化信息为3个阶段： 1)1854年至1900年的相对较强季风期,降水量较丰, δ18O 平均值为－6.3‰; 2)1900年至1960年的较弱季风期,降水量较少, δ¹⁸O 平均值为－5.1‰; 3)1960年至2005年的较强季风期,降水量较丰富,δ¹⁸O 平均值为－6.1‰。