travertine precipitation in the paleoproterozoic kuetsjarvi sedimentary formation pechenga greenstone belt ne fennoscandian shield abstract precambrian travertines tufas and speleothems either formed rarely or they have not been identified in previous studies in the absence of high pco2 soils in paleoproterozoic karst solution and speleothem formation occurred by processes distinct from those commonly found in present day low temperature karst environments however the high pco2 atmosphere could itself have encouraged karst formation the paleoproterozoic kuetsjarvi sedimentary formation of the pechenga greenstone belt nw russia includes abundant terrestrial carbonate precipitates these precipitates were sampled from a drillcore representing a complete section of the ca 120 m thick formation and were investigated for c and o isotopes acid soluble elemental contents and petrography the newly obtained results were used to constrain the origins of the precipitates and to illuminate different terrestrial carbonate types the investigated drillcore includes abundant small scale cavities and veins which are commonly filled with dolomite and quartz dolomite crusts are found both in the cavities and on bedding erosional surfaces dolomite cements coat uneven surfaces and surficial rock fragments the surficial dolomite crusts form distinct and discrete layers whereas the cements do not the cavity and vein fills are likely post depositional in origin whereas the surficial dolomite crusts and dolomite cements are likely syn depositional precipitates the investigated precipitates often show 13c values lower than those reported from their host rocks suggesting the influence of an external carbon source petrographic features and geochemical data suggest dissolution and precipitation of carbonate material originating from deep sourced co2 bearing fluids likely at high earth surface temperatures

multi proxy evidence of millennial climate variability from multiple bahamian speleothems abstract northern hemisphere tropical paleoclimate records support significant changes associated with dansgaard oeschger d o events and heinrich stadials 1 to 6 during the last 64 000 years however few absolutely dated terrestrial records from the western atlantic span the last six heinrich stadials here we present geochemical results from three new stalagmites collected from a cave in the bahamas which encompass heinrich stadials 1 to 6 we build on a previous study of the 13 c and 18 o values of the calcite and 18 o value of fluid inclusions from a single stalagmite from the same cave spanning the last three heinrich stadials absolute geochronometry using u th equilibrium series demonstrates that the stalagmites formed between 63 8 and 13 8 kyr bp the 13 c and 18 o values of the calcite show higher values associated with heinrich stadials 1 6 and lower values during the d o interstadial events the sr ca ratios of the calcite are shown to be relatively invariant while in two of the samples the mg ca ratios track the 13 c values increases in the 18 o values across heinrich stadials 1 6 are interpreted as being driven by lower temperatures the two deeper occurring stalagmites demonstrate increased mg ca ratios and 13 c values during heinrich stadials 1 and 2 which are interpreted as a signal of reduced flow rates in the epikarst and increased water rock interactions as a result of increased aridity which potentially occurred across all six heinrich stadials the observed reductions in mean annual temperature and amount of precipitation across heinrich stadials are proposed to be driven by a reduction in sea surface temperatures in the north atlantic and an expanded bermuda high during d o interstadials the bahamas cave records likely indicate warmer and or wetter climate however the isotopic shifts are not as significant as the isotopic excursions associated with heinrich stadials

investigation of young water inflow in karst aquifers using sf6 cfc 3h he 85kr 39ar and stable isotope components abstract karst aquifers are known for their wide distribution of water transfer velocities from this observation a multiple geochemical tracer approach seems to be particularly well suited to provide a significant assessment of groundwater flows but the choice of adapted tracers is essential in this study several common tracers in karst aquifers such as physicochemical parameters major ions stable isotopes and 13c to more specific tracers such as dating tracers 14c 3h 3h 3he cfc 12 sf6 and 85kr and 39ar were used in a fractured karstic carbonated aquifer located in burgundy france the information carried by each tracer and the best sampling strategy are compared on the basis of geochemical monitoring done during several recharge events and over longer time periods months to years this study s results demonstrate that at the seasonal and recharge event time scale the variability of concentrations is low for most tracers due to the broad spectrum of groundwater mixings the tracers used traditionally for the study of karst aquifers i e physicochemical parameters and major ions efficiently describe hydrological processes such as the direct and differed recharge but require being monitored at short time steps during recharge events to be maximized from stable isotopes tritium and cl contents the proportion of the fast direct recharge by the largest porosity was estimated using a binary mixing model the use of tracers such as cfc 12 sf6 and 85kr in karst aquifers provides additional information notably an estimation of apparent age but they require good preliminary knowledge of the karst system to interpret the results suitably the cfc 12 and sf6 methods efficiently determine the apparent age of baseflow but it is preferable to sample the groundwater during the recharge event furthermore these methods are based on different assumptions such as regional enrichment in atmospheric sf6 excess air and flow models among others 85kr and 39ar concentrations can potentially provide a more direct estimation of groundwater residence time conversely the 3h 3he method is inefficient in the karst aquifer for dating due to 3he degassing

carbon and oxygen isotope study of the active water carbonate system in a karstic mediterranean cave implications for paleoclimate research in semiarid regions abstract in a semiarid climatic zone such as the eastern mediterranean region annual rainfall variations and fractionation processes in the epikarst zone exert a profound influence on the isotopic compositions of waters seeping into a cave consequently the isotopic compositions of speleothems depositing from cave waters may show complex variations that need to be understood if they are to be exploited for paleoclimate studies this is confirmed by a four year study of the active carbonate water system in the soreq cave israel the 18o smow values of cave waters range from 6 3 to 3 5 the highest 18o values occur at the end of the dry season in waters dripping from stalactites and reflect evaporation processes in the epikarst zone whereas the lowest values occur in rapidly dripping fast drip waters at the peak of the rainy seasons however even fast drip waters are about 1 5 heavier than the rainfall above the cave which is taken to reflect the mixing of fresh with residual evaporated water in the epikarst zone 13c pdb values of dissolved inorganic carbon dic vary from 15 6 to 5 4 with fast drip waters having lower 13c values mostly 15 6 to 12 and higher dic concentrations relative to pool and stalactite drip water the low 13c values of fast drip waters and their supersaturation with respect to calcium carbonate indicates that the seepage waters have dissolved both soil co2 derived from overlying c3 type vegetation and marine dolomite host rock the 18o pdb values of various types of present day low magnesium calcite lmc speleothems range from 6 5 to 4 3 and 13c values from 13 to 5 5 and are not correlated with speleothem type an analysis of 18o values of present day calcite rafts and pool waters shows that they form in oxygen isotope equilibrium similarly the measured ranges of 13c and 18o values for all types of present day speleothems are consistent with equilibrium deposition at cave temperatures the 13c 18o range of contemporary lmc thus reflects the variations in temperatures and isotopic compositions of the presentday cave waters the 10 variation in the 13c values in waters can be modeled by a simple rayleigh calculation of the carbon isotope fractionation accompanying co2 degassing and carbonate precipitation these variations may obscure the differences in the carbon isotopic composition of speleothems that could arise when vegetation cover changes from c3 to c4 type plants this consideration emphasizes that it is necessary to characterize the full range of 13c values associated with contemporaneous speleothems in order to clarify the effects of degassing from those due to differing vegetation types isotopic studies of a number of different types of fossil lmc speleothems show many of them to exhibit isotopic trends that are similar to those of present day lmc but others show both higher and lower 18o ranges in particular the higher 18o range has been shown by independent age measurements to be associated with a period of drier conditions the results of the study thus indicate that it is necessary to work on a well calibrated cave system in semiarid climates and that the fossil speleothem record should be obtained from different types of contemporaneous deposit in order to fully characterize the 18o 13c range representative of any given climatic period

late quaternary paleoclimate in the eastern mediterranean region from stable isotope analysis of speleothems at soreq cave israel abstract the eastern mediterranean continental paleoclimate during the past 25 000 years was determined by a high resolution petrographic stable isotopic and age study of speleothems from soreq cave israel 18o 13c trends indicate that all speleothems older than 7000 yr formed under conditions that differ from those of today the period from 25 000 to 17 000 yr b p was characterized by the highest 18o and 13c values which indicate deposition at temperatures of 12 16 c annual rainfall of 300 450 mm and vegetation typical of a mixed c3 c4type from 17 000 to 10 000 yr b p deglaciation in northern europe 18o values dropped progressively correlative with warming 2 3 c and a gradual increase in precipitation a simultaneous decrease in 13c gives a range expected for c3 type vegetation this period also shows significant 18o and 13c spikes which are correlatable with global events e g heinrich events and the younger dryas stade the speleothems that grew between 10 000 and 7000 yr b p have a unique petrography showing irregular thin laminae of various colors and much detritus they have the lowest 18o corresponding to 1000 mm rain coupled with the highest 13c caused by flooding events which stripped the soil cover from 7000 to 1000 yr b p conditions became closer to those of today this study demonstrates that global events which were recognized in northern europe and north africa are also evident in the eastern mediterranean and are reflected principally by large changes in the rainfall rate

seasonal variations in sr mg and p in modern speleothems grotta di ernesto italy sub annual variations in trace element chemistry and luminescence have recently been demonstrated from speleothems and offer the potential of high resolution palaeoclimatic proxies however no studies have yet examined microscopic trace element variations in relation to modern cave conditions in this study the spatial variations in trace element sr mg and p concentrations in speleothems a stalagmite and a soda straw stalactite from the alpine ernesto cave temperature 6 6 0 1 c in a forested catchment in ne italy have been studied using secondary ion mass spectrometry sims and compared with environmental parameters and waters in the modern cave an annual lamination exists in the stalagmite and soda straw stalactite in the form of clear calcite with narrow visible layers which are uv fluorescent and interpreted to contain soil derived humic fulvic acids washed into the cave during autumn rains microanalyses were undertaken of seven annual laminae probably deposited during the 1960s in the stalagmite and seven laminae in the 1990s for the stalactite the analysis results show that sr consistently has a trough and p a peak centred on the inclusion rich layer mg shows mainly a negative covariation with sr in laminae formed in the 1990s but a positive covariation in the stalagmite formed in 1960s the spatial scale of the main geochemical variations is the same as that of annual laminae of inclusion poor and inclusion rich couplets mass balance arguments are used to show that the p is inorganic in form and presumably occurs as individual phosphate ions within the calcite most drip waters show limited chemical variations but a summer peak in trace elements in 1995 and a decrease in mg ca in the following winter are notable more pronounced covariations in mg ca and sr ca are shown by a site with highly variable drip rates where ratios increase at slow drip rates the strongest seasonal variations are found in pool waters where ratios increase reflecting significant ca removal from the water into the calcite during the winter in response to seasonal pco2 variations in cave air thus the cave waters compositions tend to reflect climate conditions such that mg ca and sr ca are tentatively interpreted to be higher when climate conditions are dry combining results from the speleothems and cave water along with the behaviour of each trace species mg ca variations in the speleothems are considered to reflect their variation in the cave waters whereas sr incorporation is also dependent on precipitation rate in this case mainly controlled by temporal variations in pco2 in the cave and conceivably also by inhibitors such as phosphate p adsorption a fraction of which is subsequently incorporated within calcite depends on aqueous phosphate concentration and water flux both of which should increase during the autumn therefore multiple trace element profiles in speleothems reflect multiple aspects of environment seasonality and conditions and hence a calibration against weather records is desirable to establish their palaeoclimatological meaning the strong annual variation of trace elements and particularly p can provide chronological markers for high resolution studies of other climate proxies such as stable isotopes

annual trace element variations in a holocene speleothem high resolution secondary ionization mass spectrometry sims analysis along the growth axis of a holocene speleothem from northern scotland reveals high frequency oscillations and longer term trends in mg ca sr ca and ba ca at the scale of the high frequency oscillations mg ca and sr ca display a well defined anticorrelation while sr ca and ba ca are positively correlated imaging of elemental ratios in two dimensions reveals that the high frequency signal is well preserved and laterally continuous across the sample tims 230th ages and annual ultraviolet luminescence banding provide chronological control and demonstrate that the high frequency cyclicity is annual trace element variations in speleothem calcite are a reflection of hydrochemical processes in the unsaturated zone overlying the cave supply effects and partitioning at the water calcite interface mg partitioning between water and calcite is temperature dependent calculations suggest that the annual mg ca oscillations may be caused by seasonal temperature changes however the longer timescale variations in mg ca are too great to be explained by this mechanism seasonal variations in water residence time in the unsaturated zone which reflect effective precipitation provide a more probable explanation for the observed annual oscillations and also explain the inverse relationship between mg ca and sr ca this record suggests that trace elements in speleothems have the potential to provide the high resolution insights into interannual palaeoclimatic variability required for assessment of general circulation models

the role of the subcutaneous zone in karst hydrology abstract the subcutaneous zone is the upper weathered layer of rock beneath the soil but above the permanently saturated phreatic zone it is of particular hydrological importance in karst because of its high secondary permeability arising from the considerable chemical solution in this zone however corrosional enlargement of fissures diminishes with depth thus permeability decreases in the same direction with the result that percolation is inhibited except down widened master joints and faults storage of water consequently occurs in this zone particularly after storms the upper surface of this suspended saturated layer in the subcutaneous zone is defined by a perched water table which slopes towards points of rapid vertical percolation the potential induces lateral water movement converging on the most permeable areas such as beneath dolines leakage from the subcutaneous store sustains slow percolation in the vadose zone cross correlation of rainfall with percolation rates in caves in new mexico u s a and new zealand reveal response lags of 2 14 weeks with no apparent relationship to depth below the surface other percolation sites show no correlation with rainfall interpreted as being a consequence of considerable friction in tight fissure networks the recognition of storage and rapid as well as very slow percolation from the subcutaneous zone requires re interpretation of the components of hydrographs from karst springs and of some conceptual models of karst aquifers the importance of subcutaneous storage in sustaining baseflow discharge at some sites must be recognised as must the contribution of subcutaneous water to flood hydrographs methods of estimating the volumes of subcutaneous and phreatic components of karst spring flood hydrographs are presented the paper concludes with a discussion of the significance of subcutaneous hydrologic processes for an understanding of karst geomorphology the desirability of explaining karst landform evolution in terms of hydrologic processes is stressed

major ion chemistry of the ganga brahmaputra river system weathering processes and fluxes to the bay of bengal the ganga brahmaputra one of the world s largest river systems is first in terms of sediment transport and fourth in terms of water discharge a detailed and systematic study of the major ion chemistry of these rivers and their tributaries as well as the clay mineral composition of the bed sediments has been conducted the chemistry of the highland rivers upper reaches of the ganga the yamuna the brahmaputra the gandak and the ghaghra are all dominated by carbonate weathering ca mg and hco3 account for about 80 of the cations and anions in the lowland rivers the chambal the betwa and the ken hco3 excess over ca mg and a relatively high contribution of na k to the total cations indicate that silicate weathering and or contributions from alkaline saline soils and groundwaters could be important sources of major ions to these waters the chemistry of the ganga and the yamuna in the lower reaches is by and large dictated by the chemistry of their tributaries and their mixing proportions illite is the dominant clay mineral about 80 in the bedload sediments of the highland rivers kaolinite and chlorite together constitute the remaining 20 of the clays in the chambal betwa and ken smectite accounts for about 80 of the clays this difference in the clay mineral composition of the bed sediments is a reflection of the differences in the geology of their drainage basins the highland rivers weather acidic rocks whereas the others flow initially through basic effusives the ganga brahmaputra river system transports about 130 million tons of dissolved salts to the bay of bengal which is nearly 3 of the global river flux to the oceans the chemical denudation rates for the ganga and the brahmaputra basins are about 72 and 105 tons km yr 1 respectively which are factors of 2 to 3 higher than the global average the high denudation rate particularly in the brahmaputra is attributable to high relief and heavy rainfall

late holocene drought responsible for the collapse of old world civilizations is recorded in an italian cave flowstone a severe drought in parts of low latitude northeastern africa and southwestern asia 4200 yr ago caused major disruption to ancient civilizations stable isotope trace element and organic fluorescence data from a calcite flowstone collected from the well watered alpi apuane karst of central western italy indicate that the climatic event responsible for this drought was also recorded in mid latitude europe although the timing of this event coincides with an episode of increased ice rafted debris to the subpolar north atlantic the regional ocean atmosphere response seems atypical of similar holocene ice rafting events furthermore comparison of the flowstone data with other regional proxies suggests that the most extreme part of the dry spell occurred toward the end of a longer term climate anomaly

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 13c values are linked to low 13c 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 13c 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

quaternary climatic instability in south east australia from a multi proxy speleothem record milankovitch scale quaternary climatic oscillations within south east australia are known to be characterized by relatively arid glacial and wet interglacial stages however terrestrial proxy records of environmental change are scarce based largely on river terraces dune sediments and pollen sequences here we present a speleothem based palaeoclimate record from yarrangobilly caves south east australia the oxygen isotopic composition of calcite 18ocalcite is taken to represent rainfall amount and used as an aridity index high resolution trace element profiles and uv fluorescence support interpretations based on 18ocalcite allowing further designation of key phases of speleothem growth into periods of relative aridity and moisture excess a hiatus of approximately 37 ka duration divides the record into two key phases of growth which can be mapped onto marine isotope stages 5c a and 3 respectively increasing aridity in the latter half of mis 5 led to cessation of speleothem growth for the duration of mis 4 growth recommences during mis 3 associated with greater moisture availability enhanced vegetation and augmented biogeochemical cycling this speleothem record provides a unique context of terrestrial environmental change and depicts hydrological conditions which fluctuate markedly over the 70 ka period covering the time of megafauna extinction and human arrival on the continent

late holocene annual growth in three alpine stalagmites records the influence of solar activity and the north atlantic oscillation on winter climate 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

magnetic fingerprint of southern portuguese speleothems and implications for paleomagnetism and environmental magnetism environmental magnetism of speleothems is still in its early stage of development here we report on our investigation of the environmental and paleomagnetic information that has been recorded in speleothems and what are the factors that control its preservation and reliability to address these issues we used a multidisciplinary approach including rock magnetism petrography scanning electron microscopy stable carbon and oxygen isotope compositions and major and trace element concentrations we applied this to a set of samples from different stages of speleothem evolution present day dripwater glass plates a weathered stalactite a fresh stalagmite cave sediments and terra rossa soils these samples come from the penico and excentricas caves located in two distinct aquifers of the algarve region south portugal our results show that the main magnetic carriers of the speleothems under study are primary detrital and consist of maghemite and magnetite similarities in coercivity and temperature dependence of the studied set of samples suggest that iron oxides are inherited from the terra rossa soils that cap the cave and were transported to the speleothems by dripwater hence they represent a regional environmental signature interestingly a stable and probably detrital remanent magnetization could be isolated in the fresh stalagmite whereas the weathered stalactite yielded chaotic magnetic directions and very low remanent intensities we propose that these low intensities can be the result from i different remanence acquisition mechanisms between stalagmite and stalactite and or ii iron dissolution by fungal activity we also suggest that magnetic properties and color and the content in detrital elements in the fresh speleothem inform about environmental processes acting on the interface of rock soil atmosphere while oxygen isotope composition and alkaline earth element concentrations inform about calcite water interaction processes these results provide a better understanding of how environmental information is recorded in speleothems and what the factors are that control the reliability of the paleomagnetic and paleo environmental signal

aeolian contribution to strontium and strontium isotope variations in a tasmanian speleothem abstract a speleothem from south central tasmania shows marked secular variations in its strontium content the element exhibits a striking bimodal distribution pattern with abrupt changes between two modal groups that is believed to be due to rapid changes in the direction of the dominant strong winds strontium isotope compositions in the speleothem range from 0 70865 to 0 70898 indicating derivation of sr from at least two distinct sources the first a persistent one from the overlying limestone the second a higher 87 sr 86 sr component probably representing input from terrestrial dust the speleothem record is unusual because it indicates a greater input of radiogenic sr dust flux during interstadial times than under full glacial conditions if an aeolian origin of some of the strontium contained in speleothems at other inland cave sites around the world can be confirmed variations in strontium isotope composition will provide high resolution records of how terrestrial dust flux has varied during the quaternary in near coastal sites significant amounts of strontium may be derived from seasalt and in those areas temporal variation of the element in speleothems may reflect at least in part changing distance from the coast due to changes in sealevel

controls on trace element sr mg compositions of carbonate cave waters implications for speleothem climatic records abstract at two caves clamouse s france and ernesto ne italy cave drip and pool waters were collected and sampled at intervals over a 2 3 year period mg ca and sr ca concentration ratios corrected for marine aerosols are compared with those of bedrocks and in some cases aqueous leachates of soils and weathered bedrocks cave waters do not lie along mixing lines between calcite and dolomite of bedrock carbonate but typically show enhanced and covarying mg ca and sr ca four factors are considered as controlling processes 1 the much faster dissolution rate of calcite than dolomite allows for the possibility of increase of mg ca if water rock contact times are increased during drier conditions a theoretical model is shown to be comparable to experimental leachates 2 prior calcite precipitation along a flow path is a powerful mechanism for generating enhanced and covarying mg ca and sr ca ratios this mechanism requires the solution to lose co 2 into pores or caverns 3 incongruent dolomite dissolution has only limited potential and is best regarded as two separate processes of dolomite dissolution and calcite precipitation 4 selective leaching of mg and sr with respect to ca is shown to be important in leachates from ernesto where it appears to be a phenomenon of calcite dissolution in general selective leaching can occur whenever ca is sequestered into precipitates due to freezing or drying of soils or if there is derivation of excess sr and mg from non carbonate species the ernesto cave has abundant water supply which in the main chamber is derived from a reservoir with year round constant p co 2 of around 10 2 4 and no evidence of calcite precipitation in the karst above the cave two distinct but overlying trends of enhanced and covarying mg ca and sr ca away from the locus of bedrock compositions are due to calcite precipitation within the cave and at a variable drip site due to enhanced selective leaching at slow drip rates mg enhancement in the first chamber is due to a more dolomitic bedrock and longer residence times the clamouse site has a less abundant water supply and presents geochemical evidence of prior calcite precipitation both in the cave and in overlying porous dolomite dedolomitized limestone bedrock initial p co 2 values as high as 10 1 are inferred experimental incubations of clamouse soils which generated enhanced p co 2 and precipitated caco 3 had compositions similar to the karst waters calcite precipitation is inferred to be enhanced in drier conditions hydrological controls on cave water chemistry imply that the trace element chemistry of speleothems may be interpretable in palaeohydrological terms drier conditions tends to promote not only longer mean residence times enhancing dolomite dissolution and hence mg ca but also enhances degassing and calcite precipitation leading to increased mg ca and sr ca

hydrogeochemical and climatic interpretations of isotopic signals from precipitation to drip waters in liangfeng cave guizhou province china oxygen isotope is a commonly used proxy for paleoclimatic studies on stalagmites in order to understand the transmission of isotopic signals from precipitation to stalagmites meteorological indexes of exterior and interior cave and hydrogeochemical proxies of drip waters in liangfeng cave have been monitored from april 2011 to april 2013 samples of rain and drip waters from three drip sites designated as 1 5 and 6 are collected for hydrogen and oxygen isotopes testing results show that the amount weighted mean 18o value of rain in the first year may 9 2011 to may 1 2012 is lighter than that in the second may 30 2012 to may 2 2013 this may result from different proportions of the pacific indian ocean source moistures the arithmetic mean 18o values of 1 5 and 6 are similar to the multi year amount weighted mean 18o value of precipitation hydrogeochemical analyses of drip waters reveal that the discharge rates increase in the order of 6 1 5 and that water rock reaction fresh old water mixing and co2 degassing exert dominant controls on seepage waters in aquifers hard infiltration of rain during dry season with heavier 18o value due to its small amount may cause lower mean drip water 18o values e g 1 evaporation during the dripping and exuding processes in dry season may result in heavier mean drip water 18o values e g 6 considering calcite depositing mostly during dry season we compare the mean 18o values of drip waters during dry season between the first and second years differences exist and share the same trend with rain the results indicate that drip waters can inherit oxygen isotopic signals of rain but it is critical to have a replication test on 18o records of stalagmites from the same cave for paleoclimatic studies what s more 18o values in stalagmites feeding by drip waters that have no little annual 18o variations may be useful to paleotemperature reconstructions

basement cover relationships and their along strike changes in the linking zone iberian range spain a combined structural and gravimetric study this study has been supported by the instituto para la reestructuracion de la mineria del carbon y el desarrollo alternativo de las comarcas mineras ministry of energy and industry spain additional support has also come from the dr3am and saltcres projects cgl2014 54118 from the science national plan of spain mineco the authors also acknowledge midland valley exploration for providing move software academic licenses the contribution of jose maria llorente agustin gonzalez and israel perez was essential for the acquisition of the geophysical data and the density measurements the financial support of the aragonian goberment is also acknowledged applied geology group geoap e01 17r the data used in this work can be found in the manuscript itself or in previous works listed in the references elevation reference data from the instituto geografico nacional http www ign es ign main index do were used in the gravity processing as well as digital terrain models from the spanish army geographical survey http www ejercito mde es unidades madrid ceget geological maps are available at the igme website http info igme es cartografiadigital whereas well data from the water authority che are accessible at the iber website http iber chebro es sitebro sitebro aspx hydrogeoebro

carbonate geochemistry and the concentrations of aqueous mg2 sr2 and ca2 western north coast of the yucatan mexico abstract we have measured concentrations of major cations sr 2 and alkalinity in groundwater pore water and surface water samples collected from the western north coast of the yucatan peninsula mexico thermodynamic calculations indicate that almost all water samples from the study area are supersaturated with respect to calcite aragonite high mg calcite hmc and dolomite analysis of the data suggests that the geochemical processes controlling mg 2 sr 2 and ca 2 concentrations differ in different environments mass balance modeling has been used to calculate the amount of dissolution and or precipitation of aragonite low mg calcite lmc and hmc and or dolomite required to produce waters with the observed mg 2 sr 2 and ca 2 concentrations mass balance calculations indicate that hmc and aragonite are dissolving whereas lmc is precipitating from most groundwater and inland surface waters the chemistry of surface waters from an extensive saline coastal swamp suggests that lmc and aragonite in surficial swamp sediments are converted to hmc or dolomite while swamp pore water chemistry suggests that hmc is dissolving and lmc and aragonite are precipitating in deeper swamp sediments the chemistry of pore waters suggests that they are derived from saline surface waters and that fresh to brackish groundwater from the shallow confined aquifer does not flow into swamp sediments

a stalagmite record of changes in atmospheric circulation and soil processes in the brazilian subtropics during the late pleistocene we present a high resolution 116 000 year carbon stable isotope record from a stalagmite from southern brazil which has been precisely dated using the u series method evaluation of carbon and oxygen isotope ratios together with the speleothem growth history suggest that the carbon isotopic composition of the speleothem is primarily controlled by biogenic co2 supply from the soil which is in turn affected by temperature and secondarily rainfall amount thus the speleothem provides evidence of paleoenvironmental change in southern brazil during the last glacial period predominantly high d 13 c values and low stalagmite growth rates reflect persistent cool conditions during most of the glacial period in subtropical brazil this cooling is probably related to an intensified extratropical circulation with more frequent and intense cold surges reaching a maximum at approximately 19 ky b p this cooling tendency is interrupted during periods of high obliquity values within the full glacial period at 93 85 and 47 40 ky b p and after 19 ky b p when a dramatic decrease in d 13 c marks the deglaciation time in the continent unlike d 18 o the d 13 c record does not exhibit a strong response to precessional forcing instead it shows a strong 40 ky obliquity signal here we propose that local temperature and thus the biological processes in the soil are primarily steered by the gradients of temperature between low and mid high latitudes which influence the meridional heat transport these gradient changes in turn are paced by obliquity r 2006 published by elsevier ltd

δ18o δ13c elemental content and depositional features of a stalagmite from yelang cave reflecting climate and vegetation changes since late pleistocene in central guizhou china abstract a 13 5 cm long stalagmite from yelang cave in central guizhou provides another example of ams 14 c dating on stalagmites which are not suitable for 230 th u dating due to very low u content and low 230 th 232 th ratio this record duplicates the published stalagmite record of 20120824 13 from the same cave zhao et al 2015 not only on 18 o and 13 c records but also on major growth hiatuses facilitating speleothem 18 o and 13 c as climate and vegetation proxies respectively based on the two stalagmite records climate and vegetation conditions can be deciphered as follow relatively cool and dry climates with c4 dominated plants during 33 4 36 ka very cold and dry climates with poor vegetation coverage during the last glacial maximum cold and dry climates with poor vegetation during younger dryas warming and very wet climates with the best vegetation mainly c3 plants coverage during 9 11 5 ka bp corresponding to a maximum insolation drying climate and decreased vegetation intensity from 9 ka to 8 ka relatively good vegetation coverage during 5 6 ka the summer monsoon strength decreased from 5 ka to 1 5 ka bp but increased during the medieval warm period to produce wet climates and abundant vegetation and strongly decadal variations in moisture budget and strong deforestation due to human impact during the past 600 years high fe mn and al contents from detritus caused dark bands near the hiatuses strong positive correlation of mg and sr with high mg sr values 23 in this study reflects source control on the mg and sr variations so that mg sr is not a function of cave temperature in such a case for pure calcite without detrital influence mg sr may register changes in cave temperature with higher mg sr indicating warmer temperature this study calls for the attention to find out climatic conditions in central guizhou during the bolling allerod warming and the middle holocene 6 8 ka intervals because of lacking deposition during these intervals in yelang cave using stalagmite 18 o alone to decipher climatic conditions on decadal to millennial scales needs to consider multiple factors such as amount source and temperature effects on the 18 o

soil and karst aquifer hydrological controls on the geochemical evolution of speleothem forming drip waters crag cave southwest ireland abstract in recent years there has been increased interest in cave speleothems as archives of palaeoclimate monitoring of rainfall and soil and karst water chemistries was performed at crag cave castleisland co kerry southwest ireland in august 1997 and january 1998 in order to understand temporal and spatial variations in karst water hydrology and chemistry and their implications for interpreting the potential palaeohydrological signal preserved by speleothems at this site temporal variations in karst water drip rates and geochemistry allow drips to be classified by hydrological response to rainfall and the associated processes of dilution piston flow source change and prior calcite precipitation during aquifer throughflow evolution from soil matrix and preferential flow solutions has also been determined to exert an important control on karst water chemistries as a result of these findings we present hydrogeochemical models and plumbing diagrams that delineate the controls on karst water evolution at a number of sampling locations within the cave at this site we propose that a palaeohydrological signal may be recorded by crag cave speleothems that may be interpreted via the study of mg ca ratios in speleothems linked to monitoring of modern drip water chemistry

caribbean hydroclimate and vegetation history across the last glacial period abstract we present a new speleothem trace element and stable isotope record which extends previous paleoclimate evidence from cuban speleothems to the last 96 ka multiple proxies were used to reconstruct caribbean hydroclimate and vegetation variability on orbital to millennial timescales in particular our proxies indicate a shift to more abundant c4 compared to c3 vegetation and or reduced soil activity during the last glacial maximum our results confirm the close link of caribbean precipitation to north atlantic climate variability insolation and the strength of the amoc the associated variations in caribbean ssts and the shift of the itcz led to substantial changes of the hydrological cycle during heinrich stadials and the younger dryas climatic conditions in cuba were comparably cool and or dry in contrast warm dansgaard oeschger cycles were accompanied by wetter conditions this is in agreement with previous evidence for the holocene when north atlantic cold warm events coincided with drier wetter conditions in cuba however our record suggests that this connection was less dominant during mis 4 to 2 displayed by a weaker response of cuban precipitation proxies to north atlantic climatic shifts than during mis 5 in particular we hypothesize that this weaker connection was mediated by the southerly shifted itcz inducing a weakening of the northern branch of the caribbean low level jet which usually transports moisture into the northern caribbean this is strikingly evident during the deglacial when driest and or coolest conditions prevailed in western cuba from hs 1 into the younger dryas including the bolling allerod interstadial

the sahara east mediterranean dust and climate connection revealed by strontium and uranium isotopes in a jerusalem speleothem this paper explores the potential of sr and u isotope systems in speleothems as tracers of eolian dust transport and hydrological conditions the study focuses on a speleothem from jerusalem spanning the past 220 kyr this speleothem provides a precisely dated record of dust flux from the sahara to the east mediterranean enhanced dust flux and terra rossa soil development are reflected by elevated 87sr 86sr ratios in the speleothem 0 7082 0 7086 while lower 87sr 86sr ratios 0 7078 indicate higher contribution of the local bedrock due to low dust flux and low soil accumulation the strontium isotope system in the speleothem is a robust monitor of the sahara monsoon modulated climate since dust uptake is related to development or reduction in vegetation cover of sahara soil the 234u 238u activity ratios in the speleothem range between 1 12 and 1 0 the high activity values may indicate selective removal of 234u from the soil while the low values converge to the bedrock the migration of 234u to the cave reflects mainly the regional hydrological conditions that are modulated by the north atlantic mediterranean climate system thus the speleothem provides a combined record of the monsoon north atlantic climatic systems long term stability in glacial 87sr 86sr ratios 0 7083 0 0001 over the past 220 kyr suggests an overall similarity in eolian dust sources and uniformity in the synoptic conditions that dominate the dust storm tracks during glacial periods

controls over the strontium isotope composition of river water abstract strontium concentrations and isotope ratios have been measured in river and ground waters from the ganges orinoco and amazon river basins when compared with major element concentrations the data set has allowed a detailed examination of the controls over the strontium isotope systematics of riverine input to the oceans in the following environments 1 1 typical drainage basins containing limestones evaporites shales and alumino silicate metamorphic and igneous rocks 2 2 shield terrains containing no chemical or biogenic sediments and 3 3 the floodplains that constitute the largest areas of many large rivers the strontium concentration and isotope composition of river waters are largely defined by mixing of strontium derived from limestones and evaporites with strontium derived from silicate rocks the strontium isotope composition of the limestone endmember generally lies within the phanerozoic seawater range which buffers the 87 sr 86 sr ratios of major rivers a major exception is provided by the rivers draining the himalayas where widescale regional metamorphism appears to have led to an enrichment in limestones of radiogenic strontium derived from coexisting silicate rocks the strontium isotope systematics of rivers draining shield areas are controlled by the intense transportlimited nature of the weathering reactions and thereby limits variations in the strontium flux from these terrains floodplains are only a minor source of dissolved strontium to river waters and precipitation of soil salts in some floodplains can reduce the riverine flux of dissolved strontium to the oceans the most effective mechanisms for altering the isotope ratio and flux of riverine strontium to the oceans are increased glaciation and large scale regional metamorphism of the type produced during continental collision both mechanisms provide a means for increasing the 87 sr 86 sr ratio of the global riverine flux

continuous early last glacial palaeoenvironmental record from a tasmanian speleothem based on stable isotope and minor element variations a columnar stalagmite from a limestone cave in the florentine valley tasmania has been dated by three 230th 234u age determinations continuous profiles of 170 18o and 13c values as well as magnesium and strontium concentrations are presented 18o values indicate temperatures lower than today with a gradual temperature decline in the basal part of the profile punctuated by two short cooling events and culminating in a double temperature minimum between 70 and 60 ka the profile shows marked similarities with the gisp ice core record from greenland which shows two short intense stadials centred on 74 and 70 ka preceding the last glacial temperature minimum they have been correlated with heinrich events in north atlantic marine cores which in turn have been attributed to periodic massive discharges of icebergs into the north atlantic the tasmanian speleothem record suggests that these events may also have affected climates in the southern hemisphere the 13c variations also appear to indicate periodic environmental change minor element variations were found to be significantly correlated with isotopic changes strontium concentrations show a bimodal distribution indicating control by a switching mechanism tentatively attributed to variations in calcitic dust supply to the ground surface above the site

controls on the spatial and temporal variability of vadose dripwater geochemistry edwards aquifer central texas abstract a 4 yr study of spatial and temporal variability in the geochemistry of vadose groundwaters from caves within the edwards aquifer region of central texas offers new insights into controls on vadose groundwater evolution the relationship between vadose and phreatic groundwaters and the fundamental influence of soil composition on groundwater geochemistry variations in sr isotopes and trace elements mg ca and sr ca ratios of dripwaters and soils from different caves as well as phreatic groundwaters provide the potential to distinguish between local variability and regional processes controlling fluid geochemistry and a framework for understanding the links between climatic and hydrologic processes the sr isotope compositions of vadose cave dripwaters mean 87sr 86sr 0 7087 and phreatic groundwaters mean 87sr 86sr 0 7079 generally fall between values for host carbonates mean 87sr 86sr 0 7076 and exchangeable sr in overlying soils mean 87sr 86sr 0 7088 dripwaters have lower mg ca and sr ca ratios and higher 87sr 86sr values than phreatic groundwaters dripwater 87sr 86sr values also inversely correlate with both mg ca and sr ca ratios mass balance modeling combined with these geochemical relationships suggest that variations in fluid compositions are predominantly controlled by groundwater residence times and water rock interaction with overlying soils and host aquifer carbonate rocks consistent differences in dripwater geochemistry i e 87sr 86sr mg ca and sr ca between individual caves are similar to compositional differences in soils above the caves while these differences appear to exert significant control on local fluid evolution geochemical and isotopic variations suggest that the controlling processes are regionally extensive temporal variations in 87sr 86sr values and mg ca ratios of dripwaters from some sites over the 4 yr interval correspond with changes in both aquifer and climatic parameters these results have important implications for the interpretation of trace element and isotopic variations in speleothems as paleoclimate records as well as the understanding of controls on water chemistry for both present day and ancient carbonate aquifers

a stepwise screening system to select storm sensitive stalagmites taking a targeted approach to speleothem sampling methodology a stepwise stalagmite sample screening process was applied in order to select a stalagmite as a sensitive recorder of recent tropical cyclone rainfall events near belize field and laboratory criteria were combined in series to screen out candidate stalagmites whose characteristics indicated lower sensitivity to stormwater infiltration the approach described here was designed to increase the likelihood that selected stalagmites would increase the signal noise ratio of the target phenomenon in the resulting proxy records this four stage method for sample selection may be an important methodological consideration for researchers attempting to use speleothems for stable isotope paleotempestology hallmarks of this approach include 1 establishing a priori scientific targets 2 applying sample criteria in the form of contra indicators and 3 organizing the sample screening protocol into a series of practical stages the overall approach to stalagmite selection presented here supports cave conservation and can be adapted readily by others in support of different scientific goals it is hoped that other investigators will also publish field and laboratory sample selection schemes as increased transparency will provide new information invaluable to replication efforts and to advancing the field of speleothem paleo environmental studies

comparison of high resolution sub annual records of trace elements in a modern 1911 1992 speleothem with instrumental climate data from southwest australia high spatial resolution measurements of mg p u sr ba and na using 193 nm excimer laser ablation inductively coupled plasma mass spectrometry has revealed clearly resolvable annual cycles in a modern speleothem from southwestern australia the age of this stalagmite is established by the dates of emplacement and removal of the boardwalk where it grew 1911 1992 this chronological constraint allows for the first confident comparison between the instrumental climate record and speleothem trace element content eleven laser ablation transects across a 0 5 mm wide section of the speleothem growth axis were measured cycles that could be matched between adjacent transects were stacked into a master record to minimise variability between tracks and permit greater confidence in comparing the trace elements to the instrumental climate record p and u positively and mg inversely mimic the sudden 20 decrease in annual rainfall experienced by this region since 1965 we argue that p from seasonal vegetation decay is transported to the speleothem before it is mineralised in the soil owing to the low p retention capacity of southwest australian soils both vegetation activity and the transport of vegetation derived hpo42 are sensitive to rainfall groundwater p concentration may also influence the transport of u through the strong affinity between phosphate and uranyl ions mg appears to be sensitive to groundwater residence time as this affects drip water mg ca composition by preferential loss of ca during drier episodes when calcite precipitates before reaching the stalagmite the effects of groundwater residence time may also be important for sr on inter annual scales however the behaviour of sr on the annual cycle is opposite to mg but compatible with ba and na which are shown to depend on speleothem growth rate

mg sr and sr isotope geochemistry of a belgian holocene speleothem implications for paleoclimate reconstructions in this study variations in mg ca sr ca and 87sr 86sr ratios in a holocene belgian speleothem cave secondary carbonate deposit are interpreted in terms of changes in water residence time and changes in weathering processes possibly induced by changes in west european climate a stalagmite from the pere noel cave belgium was dated with the tims u th method and was deposited between 13 and 2 ka bp the 1000 mg ca ratio varies between 4 9 and 26 and displays short term changes but no significant long term trend the 1000 sr ca ratio varies between 0 09 and 0 31 and displays both short term changes and a long term decreasing trend from 12 9 to 3 5 ka in parallel the sr isotopic composition of the speleothem decreases from 0 7090 at 12 9 ka to 0 7088 at 3 5 ka the sr isotope ratio is higher than expected from the overlying limestone 87sr 86sr 0 7081 which implies an external source of radiogenic sr most probably from a silicate phase short term and long term changes in mg ca sr ca as well as long term changes of 87sr 86sr ratios can be explained by changes in the dissolution and precipitation processes of the host limestone these processes are controlled by changes in water residence times linked to changes in the water excess precipitation minus evapo transpiration c 2000 elsevier science b v all rights reserved

climate influence on geochemistry parameters of waters from santana perolas cave system brazil abstract a four year study of water geochemistry and hydrology was performed in a relatively deep cave system overlying bedrock thickness varies from 100 to 300 m as part of two monitoring programs from june 1990 to february 1992 and from march 2000 to march 2002 the ph saturation index for calcite ca and so 4 concentrations and elemental ratios of mg ca and sr ca were measured in surface well and drip waters throughout the system despite local hydrological and geological differences among sampling sites the monitoring revealed significant synchronous intersite variations in these parameters that are related to seasonal changes in rainfall recharge suggesting that element ratios of speleothems formed in deep caves are capable of recording short term climate variations groundwater residence time appears to be the main factor affecting the water composition in the epikarst epikarstic waters are always undersaturated with respect to calcite but both saturation index s i and dissolved solids content increase substantially during drier periods because of longer residence times and longer interaction between meteoric water and limestone by contrast results from cave drips and rimstone pools indicate constant supersaturation for calcite and demonstrate that a major control on trace element ratios of waters in the deep vadose zone is the degree of prior calcite precipitation this mechanism is more effective during drier periods when higher mg ca and sr ca values are observed in all drip and pool sites however variations do occur independently of the general trend of drip discharge which suggest non linear features in cave seepage water geochemistry in addition synchronous variations in so 4 and cl concentration indicate high connectivity between different water flow pathways characterized by similar response to interseasonal changes in vadose water level fluctuations in trace element ratios of cave streams appear to reflect increased contribution of waters flushed from the vadose fissure aquifer during very wet periods by a piston flow mechanism flushing episodes are also responsible for maintaining more positive saturation indices in streams even during periods of high river discharge our results suggest that trace elements are a potential proxy for past rainfall changes but they also reveal different scenarios for interpreting trace elements ratios of speleothems and freshwater tufa deposited in a deep cave systems located in tropical humid areas

subsidence induced by urbanisation in the city of rome detected by advanced insar technique and geotechnical investigations abstract we applied the interferometric point target analysis ipta technique to study the city of rome italy aiming to detect and measure the surface movements of buildings and urban structures the available sar dataset has been delivered by esa cat1 3258 and ranges the period 1992 2005 in particular ers1 ers2 data processed covers 1995 2000 while envisat asar 2002 2005 the point target velocity map shows a general stability except for some very local areas affected by subsidence rate larger than 10 mm year the analysis of the time series compared to a detailed geological and geotechnical investigation of the lithostratigraphy of the alluvial sediments of the tiber river and combined with a temporal reconstruction of the expansion of the city over the alluvial valleys allowed us to depict the main factors controlling the observed subsidence these are the in situ effective stress conditions the related compressibility and viscous characteristics of the loaded soils the thickness of the compressible stratum the time since loading instant and the entity of loading furthermore the observed subsidence is time dependent even at a long time scale with respect to the age of the buildings being most of the buildings constructed since the 50s still affected by slow subsidence we mainly focused on the grottaperfetta stream valley that is characterized by an anomalous high and time lasting subsidence original data on the lithostratigraphic setting of this alluvial valley indicate that the high subsidence rate measured up to 2005 is caused by a still active primary consolidation process

east asian hydroclimate modulated by the position of the westerlies during termination i speleothem oxygen isotope records have revolutionized our understanding of the paleo east asian monsoon yet there is fundamental disagreement on what they represent in terms of the hydroclimate changes we report a multiproxy speleothem record of monsoon evolution during the last deglaciation from the middle yangtze region which indicates a wetter central eastern china during north atlantic cooling episodes despite the oxygen isotopic record suggesting a weaker monsoon we show that this apparent contradiction can be resolved if the changes are interpreted as a lengthening of the meiyu rains and shortened post meiyu stage in accordance with a recent hypothesis model simulations support this interpretation and further reveal the role of the westerlies in communicating the north atlantic influence to the east asian climate

stalagmite carbon isotopes and dead carbon proportion dcp in a near closed system situation an interplay between sulphuric and carbonic acid dissolution 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 13c most likely reflects post glacial soil recovery above the cave with a progressive increase of soil co2 contribution to the total dissolved inorganic carbon dic pronounced millennial scale shifts in dcp and relatively small coeval but antipathetic changes in 13c 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

modeling speleothem δ13c variability in a central sierra nevada cave using 14c and 87sr 86sr abstract 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 13c 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 13c increases in stalagmite dcp between 16 5 and 8 8 ka are coincident with decreased 13c 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 13c 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 13c values and degassing calculations suggest that some degree of prior calcite precipitation is necessary at all time intervals to explain measured stalagmite 13c values even during relatively wet intervals these results illustrate the importance of constraining degassing and prior calcite precipitation in the interpretation of speleothem 13c records particularly those from caves that formed in seasonal semi arid to arid environments

hydrochemistry of carbonate terrains in alpine glacial settings nearly 200 analyses of meltwaters ice and snow from three alpine glacial sites in carbonate terrain are summarized and discussed in terms of sources of solutes and kinetic controls on the progress of weathering reactions most data derive from the swiss glacier de tsanfleuron which is based on cretaceous and tertiary pure and impure limestones two other sites marmolada italian dolomites and the saskatchewan glacier alberta are based on a mixed calcitic dolomitic substrate most solutes originate from carbonate dissolution moreover where pyrite is present its oxidation supplies significant sulphate and forces more dissolution of carbonate the ratios sr2 ca2 and mg2 ca2 are much higher in tsanfleuron melt waters than local bedrock a phenomenon that can be reproduced in the laboratory at small percentages of dissolution these anomalous ratios are attributed to incongruent dissolution of traces of the metastable carbonates mg calcite and aragonite these phases also provide na to solution k is argued to originate mainly by ion exchange on clays with solute ca2 quartz and very minor feldspar dissolution are also inferred locally enhanced input from atmospheric sources is recognized by high cl and associated na the progress of weathering reactions has been evaluated by the trends in the data computer modelling and some simple laboratory experiments the most dilute samples show a trend towards removal of co2 to low partial pressures c 10 5 5 atmospheres reflecting initially rapid carbonate dissolution and relatively slow dissolution of gaseous co2 later addition of atmospheric co2 or acid from pyrite oxidation allows further carbonate dissolution but solutions show a wide range of saturations and co2 pressures as high as 10 2 2 where pyrite oxidation is important in a carbonate terrain measurement of electroconductivity corrected to 25 c and alkalinity in the field allows the following preliminary deductions where meq stands for milliequivalents formula presented where s is the minimum meq ca2 mg2 produced by simple dissolution of carbonate unconnected with pyrite oxidation as with any proxy method these deductions do not remove the need for chemical analysis of waters in a given study area copyright 1994 john wiley sons ltd

the origin of erratic calcite speleothems in the dangcheomul cave lava tube cave jeju island korea abstract dangcheomul cave in jeju island korea is a lava tube about 110 m long the cave is located only a few meters below the surface under alkali basalt and contains numerous and various calcite speleothems such as soda straws stalactites stalagmites columns cave corals curtains flowstones rimstones carbonate powders and shelfstones carbonate sand dunes overlying the lava tube are responsible for the formation of calcite speleothems the sand dunes were formed from the carbonate sediments transported from adjacent shallow seas and beaches and are composed of mollusks echinoderms coralline algae benthic foraminifers bryozoans etc oxygen isotopic compositions of some speleothems and cave water indicate that the spelothems have grown mostly by evaporation of cave water also carbon isotopic compositions suggest that the majority of carbon was derived from overlying carbonates with a minor contribution of organic carbon from the overlying soil most speleothems in dangcheomul cave do not show typical morphology as can be commonly seen in limestone caves these erratic forms imply a different mode of speleothem formation high density of soda straws stalactites and columns as well as erratic morphology may also provide the evidence that the plant roots are responsible for their growth

the nature of annual lamination in carbonate flowstones from non karstic fractures vinschgau northern italy abstract the vinschgau is an inneralpine valley in the southern alps whose steep flanks are composed of strongly sheared gneisses and schists affected by deep seated gravitational slope deformations fractures generated by these movements host a groundwater system characterised by high amounts of dissolved solids which reflect long residence times and water rock interactions driven by sulphide oxidation this in combination with high air and soil temperatures on the south facing slope sonnenberg of the valley favoured the deposition of calcite and aragonite flowstone in shallow parts of this fractured non karstic aquifer about 5 of these speleothems exhibit well developed regular lamination whose annual origin was confirmed by radiometric dating a stable isotope petrographic and trace element study combined with u th dating was undertaken to disentangle the processes controlling lamina formation a succession of darker and lighter laminae forms distinct macroscopic couplets 0 2 2 mm wide in three of the samples while one sample comprises alternating white and translucent laminae microscopically the darker and white laminae show a higher abundance of opaque particles whose organic origin is confirmed by their strong epifluorescence the crystal fabric is dominated by the fascicular optic type the calcite shows regular 18 o oscillations with an amplitude of up to 1 2 with the exception of one sample 13 c lacks such a regular pattern and only shows smaller variations which do not correlate with 18 o in a consistent way all samples exhibit regular low amplitude mg sr ba and u cycles in three samples mg shows oscillations similar to the 18 o cycles in their frequency but opposite in phasing 18 o and mg oscillations are primarily attributed to surface temperature variations that are transmitted to the shallow subsurface by thermal conduction low amplitude trace element cycles mg sr ba and u are most probably driven by intra annual variations in the degree of prior aragonite precipitation in the seepage path which relates to seasonal changes in evaporation

stalagmite records of hydroclimate in central california during termination 1 abstract the last deglaciation is marked by large and abrupt hydroclimatic changes in the great basin and the american southwest however comparatively little is known about how hydroclimate varied on the western side of the sierra nevada we present new evidence for abrupt changes in precipitation amount in the central sierra nevada during the last deglaciation our new record from mclean s cave overlaps with a previously published record from nearby moaning cave oster et al 2009 and extends the record of hydroclimatic change in the region through heinrich stadial 1 mclean s cave speleothem 18o 13c mg ca and sr ca indicate a shift to drier conditions at the beginning of heinrich stadial 1 from 16 1 to 17 5 ka followed by wetter conditions at the end of heinrich stadial 1 when the majority of great basin lakes reached their deglacial highstands during the last deglaciation coincident shifts in the moaning and mclean s cave proxy records indicate drier conditions in the western sierra nevada during millennial scale intervals of warming at high latitudes such as the bolling and allerod and wetter conditions during cooler intervals such as the older and younger dryas thus the sierra nevada speleothem records are consistent with other regional records that document increased winter rainfall during millennial scale cold periods of the last deglaciation however regional differences exist in the hydroclimatic response to the younger dryas with central californian and interior southwestern sites indicating an increase in winter storms that is not apparent in southern california dynamic simulations of atmospheric circulation indicate that wetter conditions during the younger dryas relative to the bolling at mclean s cave may have resulted from a stronger storm track in the north pacific at the latitude of northern california

point recharge of limestone aquifers a model from new zealand karst abstract closed depressions of moderate dimensions solution dolines sinkholes cockpits are a widely described feature of limestone terrains but very little attention has been paid to their contemporary hydrological function in many areas the depressions act as funnels concentrating near surface waters and forming important point sources of recharge to limestone aquifers in this paper the mechanisms by which flow is concentrated and then transmitted to the underlying aquifer are examined and a model of depression hydrology is proposed the model is shown to be useful in explaining the recharge mechanisms of conduit flow dominated aquifers which drain polygonal karst terrain in the waitomo district new zealand

uranium series chronology and environmental applications of speleothems an increasing number of scientists recognize the value of speleothems1 as often extremely well preserved archives of information about past climate vegetation hydrology sea level nuclide migration water rock interaction landscape evolution tectonics and human action well constrained data are required to document past changes reconstruct past patterns and predict future responses of the earth system at a wide range of spatial and temporal scales speleothems are particularly useful in this regard because they can be found in many locations of the globe sampled at high resolution and reliably dated using high precision uranium series techniques speleothems are bodies of mineral material formed in caves as the result of chemical precipitation from groundwater flowing or dripping in a cave most speleothems are composed of calcite formed by slow degassing of co2 from supersaturated groundwater but aragonite and gypsum forms are also common particularly near cave entrances where evaporative effects are important a host of different speleothem types decorate the walls ceilings and floors of caves and their mineralogy and morphology is a function of fluid flow and chemistry of waters feeding a particular location as well as the ambient conditions temperature chemistry light in the air or water filled void subaerial forms include the familiar stalagmites stalactites draperies flowstones subaqueous forms include rimstone pools rafts mammillary calcite wall coatings and dog tooth spar for an extensive review of the types of speleothem that have been observed see hill and forti 1997 speleothems are used in a multitude of ways to explore past environmental conditions perhaps the most fundamental of which is their very presence or absence deposition of speleothems relies on sufficient water supply and soil co2 to enable dissolution and transport of reactants in the vadose zone to underlying caves in arid or glacial times conditions may not have been favorable for speleothem formation

the eastern mediterranean paleoclimate as a reflection of regional events soreq cave israel the climate of the eastern mediterranean region of the last 60 ky was determined by a high resolution study of the oxygen and carbon isotopic composition 1500 measurement pairs of speleothems from the soreq cave israel with chronology provided by 53 precise 230 th 234 u tims ages the high precision of the speleothem tims ages permits us to determine the timing of regional climatic events in the eastern mediterranean region and to see if they correlate with global events during the period from 60 to 17 ky the 18 o and 13 c values were generally 2 2 5 higher than during the period from 17 ky to present this is consistent with the climatic transition from glacial to interglacial within the 60 to 17 ky period the soreq cave stable isotope profile includes four cold peaks at 46 35 25 and 19 ky and 2 warm peaks at 54 and 36 ky in addition the period 17 ky has two more cold peaks at 16 5 and from 13 2 to 11 4 ky the ages of four of the six cold peaks correlate well with the ages of three heinrich events h1 h2 h5 and with the age of the younger dryas however the other two heinrich events are not reflected in the soreq cave record several other isotope peaks which appear during the last 7 ky are contemporaneous with regional climatic events in the middle east and north africa in addition to the drop in 18 o and 13 c observed between the last glacial and the holocene sharp simultaneous drops in 234 u 238 u 0 ratios sr concentrations and in 87 sr 86 sr are also observed suggesting that the latter are climate related these variations are interpreted in terms of major changes in the temperature the mean annual rainfall and its isotopic composition the isotopic composition of the mediterranean vapor source the soil moisture conditions and in the mixing proportions of sources with different 87 sr 86 sr ratios sea spray dust particles and dolomitic host rock

multi proxy stalagmite records from northern california reveal dynamic patterns of regional hydroclimate over the last glacial cycle abstract despite its importance for california s water resources little is known about how precipitation has varied in far northern california beyond the historical record we present a new multi proxy paleoclimate record derived from two coeval stalagmites from lake shasta caverns lsc california that covers the end of marine isotope stage 3 through heinrich stadial 1 35 000 to 14 000 years bp at 40 8 n lsc is situated within the transition zone between regions in the northwestern and southwestern united states that demonstrate different precipitation responses to both modern and paleoclimatic drivers stable isotope and trace element proxies from lsc stalagmites indicate the region experienced wet conditions during interstadials warm periods associated with dansgaard oeschger cycles similar to proxy records from southern oregon and the northern great basin but in contrast to records from the desert southwest similar to the northern cascades and rocky mountains lsc was drier during the last glacial maximum however proxies indicate increased rainfall throughout heinrich stadial 1 similar to the great basin and southwest thus the lsc record demonstrates the non stationarity of the transition zone location and illustrates a complex pattern of precipitation response to global climate change in the western united states covariation of speleothem 18o an indicator of moisture source with 13c and trace elements indicators of moisture amount suggest a higher proportion of central pacific precipitation during the last glacial maximum despite the enhanced aridity in contrast periods characterized by increased precipitation amounts such as early heinrich 1 are associated with enhanced moisture from the northern pacific

hydrologic and climatic implications of stable isotope and minor element analyses of authigenic calcite silts and gastropod shells from a mid pleistocene pluvial lake western desert egypt abstract authigenic calcite silts at wadi midauwara in kharga oasis egypt indicate the prolonged presence of surface water during the marine isotope stage 5e pluvial phase recognized across north africa exposed over an area of 4 25 km 2 these silts record the ponding of water derived from springs along the libyan plateau escarpment and from surface drainage the 18 o values of these lacustrine carbonates 11 3 to 8 0 pdb are too high to reflect equilibrium precipitation with nubian aquifer water or water of an exclusively atlantic origin mg ca and sr ca of the silts have a modest negative covariance with silt 18 o values suggesting that the water may have experienced the shortest residence time in local aquifers when the water 18 o values were highest furthermore intra shell 18 o sr ca and ba ca analyses of the freshwater gastropod melanoides tuberculata are consistent with a perennially fresh water source suggesting that strong evaporative effects expected in a monsoonal climate did not occur or that dry season spring flow was of sufficient magnitude to mute the effects of evaporation the input of a second isotopically heavier water source to aquifers possibly indian ocean monsoonal rain could explain the observed trends in 18 o and minor element ratios

the 2002 2003 el nino recorded in australian cave drip waters implications for reconstructing rainfall histories using stalagmites 1 a 30 month study of drip hydrochemistry from kooringa cave eastern australia revealed a clear geochemical response to the 2002 2003 el nino through the drought drip discharge fell to base flow drip ca2 concentrations fell by half and drip mg ca and sr ca increased in a co varying pattern calcite mg ca and sr ca predicted from drip waters displayed a marked increase through and just beyond the period of greatest moisture deficit the results suggest that stalagmites from shallow caves in drought sensitive eastern australia potentially preserve a valuable record of el nino la nina history

palaeoclimate determination from cave calcite deposits calcite deposits formed in limestone caves have been found to be an excellent repository of palaeoclimatic data for terrestrial environments the very presence of a relict deposit indicates non glacial conditions at the time of formation and both 14c and uranium series methods can be used to date the deposit and hence the age of these climatic conditions variations in 13c and 18o content of the calcite in 2h and 18o content of fluid inclusions in trace element concentrations and more recently in pollen assemblages trapped in the calcite are all potentially available as synchronous palaeoclimatic indicators previous work has tended to concentrate mainly on abundance of deposits as a palaeoclimatic indicator for the last 300 000 years this literature is briefly reviewed here together with the theory and methods of analysis of the u series and stable isotopic techniques the combined use of u series ages and 13c and 18o variations in cave calcites illustrates the potential for palaeoclimate determination previously unpublished results of stable isotopic variations in dated calcites from caves in northern england indicate the level of detail of stable isotopic variations and time resolution that can be obtained and the complexity of interpretation that may arise tentative palaeoclimatic signals for the periods 90 125 ka and 170 300 ka are presented more comprehensive studies are needed in future work especially in view of the difficulty in obtaining suitable deposits and the ethics of cave deposits conservation

trace element partition coefficients in the calcite water system and their paleoclimatic significance in cave studies abstract speleothems stalactites stalagmites formed in limestone caves have been found to contain much information on the timing and intensity of past climates from analysis of their u th 13c and 18o contents because the incorporation of certain trace elements e g mg mn and zn in calcite is known to be temperature dependent it may be possible to use variations in trace metal content of fossil speleothems as an alternative paleotem perature indicator using specially developed ion exchange sampling techniques analysis of trace metal content of seepage water and associated fresh calcite deposits in caves in vancouver island and jamaica shows that mg is distributed between phases in a consistent manner within the temperature regimes of the caves 7 and 23 c respectively average values of the distribution coefficient for mg are respectively 0 017 and 0 045 at these temperatures these results indicate that the mg content of calcite varies directly with temperature and in a sufficiently pronounced manner that a 1 c rise in depositional temperature of a speleothem containing 500 ppm mg at 10 c would be seen as an increase of 35ppm mg a readily determinable shift other factors affecting mg content of a speleothem are considered

chemical models of solute acquisition in glacial melt waters chemical models for the evolution of bulk melt waters can be constructed by assuming that rock mineral weathering and solute acquisition are controlled by carbonate equilibria different open and closed system models are defined by variations in the rates of weathering relative to the rate of hydrogen ion supply by the dissolution and dissociation of co2 and can be recognized by characteristic ph and relationships the observed and inferred compositions of englacial and subglacial melt suggest that mixing is unlikely to be conservative and that closed system conditions result where post mixing weathering reactions occur the final composition of bulk melt waters is determined by the mixing ratio between englacial and subglacial melt the extent of post mixing evolution and opportunity for mixing with ground waters or re equilibration with the atmosphere