modification and preservation of environmental signals in speleothems speleothems are primarily studied in order to generate archives of climatic change and results have led to significant advances in identifying and dating major shifts in the climate system however the climatological meaning of many speleothem records cannot be interpreted unequivocally this is particularly so for more subtle shifts and shorter time periods but the use of multiple proxies and improving understanding of formation mechanisms offers a clear way forward

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

holocene climatic conditions in the eastern adriatic recorded in stalagmites from strasna pec cave croatia abstract in the study we present results of stable isotope analysis 18o 13c of two stalagmites spd 1 and spd 2 from strasna pec cave situated on dugi otok island in the central adriatic region the growth interval of the speleothems based on u th dating covers the period from 4 4 ka to 1 5 ka both speleothems show frequent 18o and 13c fluctuations with similar average values 18o value of 4 for both speleothems and average value of 13c 8 5 and 8 8 respectively in order to reconstruct the holocene climatic conditions in the eastern adriatic the speleothem isotopic record is discussed and compared with other holocene records they reveal periods of drought which occurred at 4 3 4 ka and around 3 5 ka with relatively wet phases between from 3 ka there is a general trend towards dryness as evidentiated by the relatively high 18o values of 3 5 to 2 5 recorded in speleothem spd 1 there is distinct trend of drying during the roman warm period and further toward the dark age cold period dacp with shorter periods of wetter conditions these changes coincide well with the other records thus revealing regional events along the eastern adriatic

climate caving in to new chronologies speleothems formed in caves such as stalagmites can be dated precisely and are increasingly providing detailed and accurate records of past climates

climatic and local effects on stalagmite δ13c values at lianhua cave china abstract carbon isotopes in speleothems may serve as indicators of vegetative change climatic conditions and karst processes in many recent studies of chinese stalagmites however carbon isotopes have often been neglected or underutilized in interpreting paleoenvironments here we present a continuous decadal scale 13 c record 819 measurements of the mid to late holocene from a precisely dated 10 230 th dates aragonite stalagmite from lianhua cave hunan province china compared to coeval stalagmites from other chinese caves the average 13 c value 3 6 of stalagmite a1 is higher by 2 7 variations in the 13 c values 0 1 to 6 0 reflect changes in both vegetative productivity and inorganic processes which respond to climatic processes the 13 c record of stalagmite a1 can be subdivided into three intervals 1 warm humid stage 6 6 to 3 8 ka 2 transitional stage 3 8 to 1 6 ka and 3 cool arid stage 1 6 ka to present comparisons with other stalagmite and paleoclimatic records demonstrate that these intervals are generally consistent with changes in regional vegetation and climatic conditions

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

calcite fabrics growth mechanisms and environments of formation in speleothems from the italian alps and southwestern ireland five fabrics were identified in alpine and irish caves on the basis of morphological and microstructural characteristics and re lated to growth mechanisms and growth environment columnar and fibrous fabrics grow when speleothems are continuously wet and from fluids at near equilibrium conditions low supersaturation sicc 0 35 through the screw dislocation mechanism the highly defective microcrystalline fabrics form at the same supersaturation range as co lumnar fabric but under variable discharge and the presence of growth inhibitors dendritic fabrics which have the highest density of crystal defects develop in disequilibrium conditions high supersaturation un der periodic very low flow regime periods that result in prolonged out gassing cave calcareous tufa forms in disequilibrium conditions only the calcite crystals of fabrics formed at low supersaturation seem to precipitate near isotopic equilibrium conditions

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

coniacian santonian deep ocean anoxia euxinia inferred from molecular and inorganic markers results from the demerara rise odp leg 207 abstract we investigated coniacian to early santonian sediments from odp site 1261 demerara rise using organic inorganic and molecular methods to reconstruct the development of ocean water anoxia euxinia high lycopane n c 31 values of up to 4 5 suggest oxygen depleted conditions in the water column for most of the time lower values 1 across the early to mid coniacian transition probably mark a period of stronger oxygenation in two higher resolution intervals we observe strong enrichment in zn concurrent with an increase in the lycopane n c 31 ratio marking the onset of euxinic bottom waters whereas decreases in lycopane n c 31 values and decreases in ni enrichment characterize the termination of sulfidic conditions photic zone euxinia appears to be restricted to the early coniacian interval as isorenieratene derivatives were exclusively detected in this part of the section the combination of biomarker and inorganic geochemical proxies suggests a general decoupling of surface and mid water oxygenation from deep water oxygenation from the mid coniacian onwards this process might be related to the successive opening of the equatorial atlantic gateway allowing a migration of surface and intermediate water masses before the establishment of a deep water connection

microclimatic characterization of a karstic cave human impact on microenvironmental parameters of a prehistoric rock art cave candamo cave northern spain the candamo cave contains an impor tant group of paleolithic paintings which have been seriously deteriorated due to mass tourism in this work an analysis was carried out of different cli matic parameters co2 temperature humidity 222 rn during annual cycles with the cave closed to the public and during an experimental period of controlled visits the effect of visits on the geo chemical characteristics of karstic water was also analyzed together with the cave ventilation the natural variations in the cave air co2 were above 3000 ppm the increase produced through visits was only 100 110 ppm and since the humidi ty is almost permanently at saturation point the critical parameter which limits the visitor capacity becomes air temperature the temperature changes during the annual cycle are of the order of 1 7c in the external part and less than 0 5 7c in the internal part of the cave and a maximum increase of 0 13 7c was observed during the period of the visits the 222 rn and co2 concentration minimums in the summer period july october show that this is the most propitious time for visits since the greatest ventilation is produced in the cave at this time and therefore the greatest capacity for recovery the geochemistry of the water on the other hand indi cated that this is the period of the year in which processes of wall corrosion can be most easily in troduced although this would be of limited magni tude the visitor capacity calculated was 29 visi tors day

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

climatic and hydrological variations during the last 117 166 years in the south of the iberian peninsula from spectral and correlation analyses and continuous wavelet analyses the most complete historical series of instrumental data available spanning more than a century on rainfall temperature and outflow of a karst spring obtained from gauging stations in the south of the iberian peninsula were analysed by means of spectral and correlation analyses and continuous wavelet analyses annual periodicity of the rainfall and temperature distributions was constant over more than 100 years although weaker 6 month periodicities have also been observed as well as rainfall and temperature periodicities of 5 and 2 5 years which have also been recorded in other areas of europe these multiannual scale components can be explained by climatic variations or effects described in the literature in connection with the north atlantic oscillation nao and are likely to be the same as the climate variability at decadal to annual scale detected in several proxy data from geological records no long term trends in the distribution of precipitation and temperature were detected

nanoscale effects of strontium on calcite growth an in situ afm study in the absence of vital effects abstract this experimental study presents in situ measurements of step migration rates for layer growth of calcite at various levels of superaturation and fluid sr concentrations our results show that sr has complex behavior as an impurity at low concentrations sr promotes faster growth this effect may be associated with slight shifts in calcite solubility when sr is incorporated or may be due to as yet uncharacterized kinetic effects at higher concentrations sr stops step advancement by pinning kink sites or step edges the threshold concentration of sr needed to halt growth is positively correlated with supersaturation addition of sr to the calcite growth system leads to significant changes in hillock morphology hillocks become elongate perpendicular to the projection of the c glide plane in contrast to the changes previously reported for mg step edges also become scalloped and the boundary between the obtuse stepped flanks disappears and is replaced by a new step direction with edges parallel to 010 incorporation of sr was measured at two supersaturation levels and identical fluid sr the results indicate a strong positive correlation between fluid supersaturation and crystal sr content further sr is strongly fractionated between obtuse and acute stepped flanks by a factor of approximately two the sensitivity of sr uptake to supersaturation may explain apparently contradictory results in the literature regarding whether sr uptake in the calcite produced by one celled marine organisms is controlled by temperature in addition sr contents of natural calcite samples may be good indicators of the levels of supersaturation at which the crystals grew results of this investigation demonstrate the importance of understanding impurity specific interactions with calcite growth surfaces at the microscopic scale despite similar chemical behavior in some systems mg and sr clearly have very different effects on calcite growth if sr and other impurities are to be used as robust indicators of growth conditions in natural calcite samples well grounded understanding of the mechanisms of recording trace element signatures in calcite is an essential step toward correctly deciphering paleoenvironmental signals from fossil calcite compositions

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

seasonal trace element and stable isotope variations in a chinese speleothem the potential for high resolution paleomonsoon reconstruction abstract we report the presence of clear annual cycles in trace element mg ca sr ca ba ca and u ca and stable isotope 18o and 13c composition in an annually banded stalagmite from heshang cave hubei province china 30 44 n 110 42 e through a combination of micromilling and in situ analysis la mc icpms we measured geochemical variations across 16 annual growth bands to assess their potential as seasonal resolution paleomonsoon proxies to facilitate comparison with modern climatic and environmental data we created composite annual cycles for each proxy by stacking 6 well defined years speleothem 18o variations 10 8 to 8 5 are controlled by seasonal variations in temperature and drip water 18o which lead to maximum values during may around the time of summer monsoon onset this provides a chronological marker which can be used to constrain the timing of the other geochemical cycles the composite cycles reveal a strong positive correlation between mg ca sr ca ba ca and 13c values in the micromilled section r2 0 65 0 98 with minimum values occurring around may maximum u ca values occur at the same time we present simple models which show that these correlations as well as the observed ranges of mg ca 14 1 to 22 4 mmol mol sr ca 0 2 to 0 4 mmol mol and 13c 12 5 to 10 7 may be fully explained by progressive co2 degassing and calcite precipitation from an initially saturated solution using realistic initial conditions for heshang cave t 18 c mg casolution 0 84 mol mol sr casolution 0 69 mmol mol 13ctdic 16 75 we find that the observed relationships can be produced by using dmg 0 016 and dsr 0 30 within the range of expected values the model suggests that the fraction of ca removed from the solution ranges from 0 to 30 to produce the observed seasonal cycles this variation may be due to two related processes which occur during drier periods 1 increased prior precipitation of calcite in the epikarst or on the cave ceiling and or 2 a greater degree of co2 degassing and calcite precipitation on stalagmite surfaces when drip rates are lower both mechanisms would have the effect of enriching speleothem mg ca sr ca ba ca and 13c values during drier periods past variations in heshang carbonate chemistry may therefore be useful as seasonal resolution proxies for past rainfall

a tale of two extinctions converging end permian and end triassic scenarios the end permian c 252 ma and end triassic c 201 ma mass extinction events are commonly linked to the emplacement of the large igneous provinces of the siberia traps and central atlantic magmatic province respectively accordingly scenarios for both extinctions are increasingly convergent and cross fertilization of ideas has become important here we present a synthesis of extinction scenarios based on a critical assessment of the available palaeontological sedimentological geochemical and geophysical evidence how similar were the extinction events what gaps exist in our understanding and how can a comparison of the events enhance our understanding of each event individually our focus is on the most important proximate kill mechanisms including climate change and atmospheric pollution increased soil erosion weathering and runoff forest dieback and the spread of pathogens and ocean temperature changes anoxia and acidification there is substantial evidence to suggest that very similar kill mechanisms acted upon late permian as well as late triassic ecosystems strengthening the hypothesis that the ultimate causes of the mass extinction events were similar

radiocarbon evidence for decomposition of aged organic matter in the vadose zone as the main source of speleothem carbon 2015 elsevier ltd several recent studies have used records of the radiocarbon 14c bomb peak in speleothems to inversely model the soil a 14co 2 and the age distribution of soil organic material som above caves in part to investigate the potential of speleothems as sensitive records of past som dynamics the results of these modeling studies have suggested that soil co 2 at karst sites is derived primarily from the decomposition of som with turnover times on the order of decades to centuries this result is in stark contrast with observations of soil a 14co 2 at non karst sites which indicate that soil co 2 is derived primarily from root respiration and decomposition of som with much shorter turnover times this discrepancy suggests that som in karst settings may have a very different age distribution than sites that have been studied previously and or that soil co 2 is not the main source of speleothem carbon to help resolve this discrepancy we present an improved inverse model which we use to estimate the age of co 2 above several caves we also present results from a detailed case study of soil carbon dynamics at heshang cave china this work demonstrates that som in karst sites may be much older than som in non karst soils that have been studied previously but that co 2 produced in the shallow soil zone is unlikely to be the main source of speleothem carbon a review of the literature suggests that the most likely explanation for the aforementioned discrepancy is that decomposition of down washed som in the vadose zone is the dominant source of speleothem carbon

trace element variation in speleothem aragonite potential for palaeoenvironmental reconstruction trace element variation in annually laminated stalagmites has the potential to record long term high resolution palaeoclimatic data provided both 1 the relationship between trace element content in the carbonate and the climate and 2 the mechanism of stalagmite growth are understood here we report a secondary ion mass spectrometry sims study of an aragonitic speleothem t7 from cold air cave southern africa which achieves small m spatial resolution and ppm precision t7 has a series of fine visible laminae believed to be annual to subannual this article establishes 1 the usefulness of sims in analyzing speleothem aragonite at the spatial resolution and precision relevant to climatic studies 2 the distribution of trace elements in aragonite on micron scales and their relationship to models for speleothem growth and 3 the potential of aragonite speleothems to encode climatic data at subannual resolution complex reproducible oscillations in sr ca and ba ca are observed parallel to the growth direction of the speleothem however in addition to this variability we observe trace element oscillations perpendicular to the growth direction and infer that aragonite crystallites in the speleothem are laterally as well as vertically zoned stepscans parallel to the growth direction demonstrate complex zoning patterns from which simple climatic data are difficult to extract due to small scale lateral heterogeneity in the aragonite however time series analysis of the whole data set reveals regular cycles in sr ca and ba ca at a scale that matches the magnitude of the visible laminae on this basis it appears that within the complex geochemical variability there resides a regular environmental control possibly variation in water throughput hence rainfall

a 53 year seasonally resolved oxygen and carbon isotope record from a modern gibraltar speleothem reconstructed drip water and relationship to local precipitation abstract the response of a climate proxy against measured temperature rainfall and atmospheric circulation patterns at sub annual resolution is the ultimate test of proxy fidelity but very few data exist showing the level of correspondence between speleothem climate proxies and the instrumental climate record cave sites on the gibraltar peninsula provide a unique opportunity to calibrate speleothem climate proxies with the longest known available precipitation isotopes and instrumental records an actively growing speleothem sampled from new st michaels cave in 2004 is composed of paired laminae consisting of light columnar calcite and a darker microsparitic calcite stable isotope analysis of samples micromilled in 100 m steps at the equivalent of bi monthly intervals reveals fabric correlated annual cycles in carbon isotopes oxygen isotopes and trace elements responding to seasonal changes in cave microclimate hydrology and ventilation patterns calcite 13 c values reach a minimum in the light columnar fabric and evidence from trace element behaviour and cave monitoring indicates that this grows under cave winter conditions of highest p co 2 whereas the dark microsparitic calcite characterised by elevated 13 c and 18 o values grows under low summer p co 2 conditions drip water 13 c dic reaches a minimum in march april at which time the attenuated 18 o signal becomes most representative of winter precipitation an age model based on cycle counting and the position of the 14 c bomb carbon spike yields a precisely dated winter oxygen isotope proxy of cave seepage water for comparison with the gnip and instrumental climate record for gibraltar the 18 o characteristics of calcite deposited from drip water representing winter precipitation for each year can be derived from the seasonally resolved record and allows reconstruction of the 18 o drip water representing winter precipitation for each year from 1951 2004 these data show an encouraging level of correspondence r 2 0 47 with the 18 o of rainfall falling each year between october and march and on a decadal scale the 18 o of reconstructed winter drip water mirrors secular change in mean winter temperatures

rainfall recharge relationships within a karstic terrain in the eastern mediterranean semi arid region israel δ 18o and δd characteristics annual rainfall variations and processes in the upper vadose zone exert a profound influence on the chemical and isotopic compositions of waters of carbonate aquifers in semi arid climatic zones in order to define these processes we have studied the surface temperatures during rainfall events the isotopic composition of rain infiltrating and groundwaters this study was carried out within a karstic terrain soreq cave israel located in cenomanian dolomitic rocks approximately 40 km inland of the mediterranean sea and 400 m above sea level the climate is typical of the eastern mediterranean semi arid conditions with a rainy winter and dry summer and the average annual rainfall in the area is 500 mm close monitoring indicates that the d and 18o values of individual rainstorm events decrease with increasing rainfall annual average isotopic values of years with rainfall of 500 600 mm do not vary systematically years with extreme rainfall values define a negative covariation between the 18o and rainfall the d 18o relationship of all rain events of more than 20 mm fall on the mediterranean meteoric water line mmwl with a slope of 8 and d excesses of 20 30 these rain events occur when mid winter surface temperatures are 5 to 10 c rainfall events of less than 20 mm mainly occurring at above 10 c have slopes of less than 8 and smaller d excess as a consequence of evaporation processes beneath the clouds two main water types infiltrating into the cave are recognized slow and fast drip slow drip occurs from the tips of stalactites and takes place throughout the year these waters represent seepage water that remains in the upper vadose zone for up to several decades fast drip emanates from fissures in the cave roof during the winter seasons these waters represent vadose flow with a short residence time of less than 1 year the infiltration of the fast drip water into the cave depends on the fracture system of the rock cover and on the intensity of the rainstorms in the inner parts of the cave where the rock cover is thick fast drip starts only after several massive 20 mm rainstorms whereas below a thin roof the response time of fast drip is a few hours to a few days after intensive rainstorms both fast and slow drip water fall on the mmwl indicating that they are derived mainly from the relatively intensive rainstorms that compose about 23 of the annual rainfall although fast dri water represents massive rainstorms their 18o and d values are nonetheless higher by 1 and 10 respectively relative to the average rainwater compisition this indicates that the fast drip water consists predominantly of water derived from intensive rainstorms admixed with a minor component of isotopically 18o and d enriched water which is represented by the slow drip waters the fast drip waters are derived mainly from massive rain events at surface temperatures of 5 to 10 c which thermally equilibrate with the host rock and upon reaching the cave they have already acquired the mean temperature 20 c of the cave

palaeo climate reconstruction from stable isotope variations in speleothems a review abstract speleothems are now regarded as valuable archives of climatic conditions on the continents offering a number of advantages relative to other continental climate proxy recorders such as lake sediments and peat cores they are ideal materials for precise u series dating yielding ages in calendar years thereby circumventing the radiocarbon calibration problems associated with most other continental records stable isotope studies in speleothems have shifted away from attempting to provide palaeo temperature reconstructions to the attainable goal of providing precise estimates for the timing and duration of major o isotope defined climatic events characterised by high signal to noise ratios e g glacial interglacial transitions dansgaard oeschger oscillations the 8200 year event unlike the marine records speleothem data sets are not tuned and their independent chronology offers opportunities to critically assess leads and lags in the climate system that in turn can provide important insights into forcing and feedback mechanisms improved procedures for the extraction and measurement of stable isotope ratios in fluid inclusions trapped in speleothems are likely to provide in the near future a much enhanced basis for the quantitative interpretation of o isotope ratios in speleothem calcite the latter developments open up once again the tantalising prospect of palaeo temperature estimates but more importantly perhaps provide a direct test for a new generation of general circulation models whose hydrological cycles will incorporate the water isotopes the literature is reviewed briefly to provide for the reader a sense of the current state of the art and to provide some pointers for future research directions

neotectonics and shoreline history of the rock of gibraltar southern iberia abstract several sets of staircased quaternary marine deposits can be observed along the gibraltar coast ranging from 1 to 210 m above the present mean sea level geomorphological mapping establishes from the relationship between shore scree and dune sedimentary formations five main morphotectonic steps on the rock marine terraces between 1 and 25 m 30 60 m 80 130 m 180 210 m and above each terrace level and its slope aeolian linked sediments is backed by a steep relict sea cliff margin so forming a composite cliff the most recent coastal landforms and sediments are associated with the last 250 ka linked to oxygen isotope stages ois 1 3 5 and 7 these landforms determine a morphosedimentary highstand lowstand sequence with several staircased and offlapped episodes comprising a major morphotectonic step a well developed palaeocliff usually separates the highstand marine terraces of ois 9 from those of ois 7 the gibraltar mean tectonic uplift value of 0 05 0 01 mm yr is maintained from 200 ka to the present before this at least to 250 ka the mean uplift rate was higher 0 33 0 05 mm yr possibly compatible with major tectonic events in response to a nnw sse compressive stress field between africa and iberia

influence of rainfall quantity on the isotopic composition 18o and 2h of water in mountainous areas application for groundwater research in the yunquera nieves karst aquifers s spain abstract the isotopic composition 18 o and 2 h of rainwater and groundwater was determined in the yunquera nieves hydrogeological unit a karstic massif in s spain with complex orography and hydrogeology the aims were to identify 1 the source of the water 2 the main factors determining the isotopic content 3 the catchment area of the springs and 4 the aquifer behaviour the isotopic content of the sampled waters is of mixed atlantic mediterranean origin and is opposite to the quantity of rainwater distribution both in space and time spatially water is isotopically less depleted toward the eastern sector where rainwater quantity is lower which is locally affected by the orography thus it is possible to differentiate the catchment areas of the main springs aquifer recharge is produced by winter precipitation when rainfall water is isotopically more negative and evaporation is lower the decrease in rainfall quantity during the study period provoked an increase in 18 o and 2 h values both in rainwater and in groundwater the recorded variations of the isotopic content of the rainfall are rapidly evident in the spring waters which demonstrates a well developed karst network inside the carbonate aquifers and thus the existence of conduit flow systems

controls on dissolved inorganic carbon and δ13c in cave waters from desoto caverns implications for speleothem δ13c assessments abstract unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time series 13c records of speleothems here we report the results of a 3 year study of total dissolved inorganic carbon dic and 13cdic from cave waters at desoto caverns southeastern usa that offer valuable insight on carbon transport and the accompanied isotope fractionations from end member sources to speleothems dic and 13cdic values of cave waters range from 0 2 to 6 0 mm and 2 7 to 12 9 vpdb respectively dic and 13cdic of seasonal drips show seasonal albeit noisy variability and are inversely related 13cdic 2 49 dic 0 64 r2 0 84 a shallow pool fed by multiple drips shows a bimodal 13cdic distribution with an isotopically heavier mode during winter 4 to 5 vpdb relative to summer months 9 to 10 vpdb a multi year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry coupled cave air winter ventilation summer stagnation and varying co2 fluxes through the soil horizon and epikarst exert the strongest influence on seasonal dic and 13cdic variability measured values of high dic and low 13cdic from cave waters collected during the summer early fall closely approximate isotopic equilibrium conditions conversely low dic and high 13cdic values during winter early months indicate kinetically enhanced isotopic fractionations within the cave waters the kinetically enhanced isotopic fractionation of hco 3 partitioned between degassed co2 and precipitated caco3 1000 ln co 2 hco 3 caco 3 ar hco 3 2 is greater by about a factor of two 6 7 0 3 relative to the same isotopic fractionation under equilibrium conditions 3 1 on the basis of 14c mass balance and paired 14c u th measurements we estimate that on average about 23 of c delivered annually by the drips to the aragonite stalagmites is derived from 14c dead dolomite cap while the remainder of 77 is derived from 14c live biomass 13c measurements of aragonite n 12 sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite 13c values calculated using the shallow pool summer early fall data thus confirming the 13c seasonality in both drips and coeval aragonite 13c values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of 7 1 1 2 n 81 and a mode of 7 to 8 that are statistically indistinguishable from the annual mean and mode of all dripwaters thus secular time series 13c records of stalagmites at desoto caverns with resolving power 10 1 year will likely carry the imprints of drip annual means that record climate driven 13c seasonal biases

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

an isotopic and modelling study of flow paths and storage in quaternary calcarenite sw australia implications for speleothem paleoclimate records abstract we investigated the distinctive shallow sub surface hydrology of the southwest western australia swwa dune calcarenite using observed rainfall and rainfall 18 o soil moisture cave drip rate and dripwater 18 o over a six year period august 2005 march 2012 a lumped parameter hydrological model is developed to describe water fluxes and drip 18 o comparison of observed data and model output allow us to assess the critical non climatic karst hydrological processes that modify the precipitation 18 o signal and discuss the implications for speleothem paleoclimate records from this cave and those with a similar karst setting our findings include evidence of multiple reservoirs characterised by distinct 18 o values and recharge responses low and high flow sites dripwaters exhibit 18 o variations in wet versus dry years at low flow sites receiving diffuse seepage from the epikarst with an attenuated isotopic composition that approximates mean rainfall recharge from high magnitude rain events is stored in a secondary reservoir which is associated with high flow dripwater that is 1 lower than our monitored low flow sites 18 o one drip site is characterised by mixed flow behaviour and exhibits a non linear threshold response after the cessation of drainage from a secondary reservoir following a record dry year 2006 additionally our results yield a better understanding of the vadose zone hydrology and dripwater characteristics in quaternary age dune limestones we show that flow to our monitored sites is dominated by diffuse flow with inferred transit times of less than one year diffuse flow appears to follow vertical preferential paths through the limestone reflecting differences in permeability and deep recharge into the host rock

centennial scale holocene climate variability revealed by a high resolution speleothem δ18o record from sw ireland evaluating the significance of holocene submillennial 18 o variability in the greenland ice cores is crucial for understanding how natural climate oscillations may modulate future anthropogenic warming a high resolution oxygen isotope record from a speleothem in southwestern ireland provides evidence for centennial scale 18 o variations that correlate with subtle 18 o changes in the greenland ice cores indicating regionally coherent variability in the early holocene evidence for previously undetected early holocene cooling events is presented but mid to late holocene ice rafting in the north atlantic appears to have had little impact on 18 o at this ocean margin site

stable isotope microsampling of speleothems for palaeoenvironmental studies a comparison of microdrill micromill and laser ablation techniques three different techniques are currently in use to microsample speleothem and tufa specimens at moderate to high spatial resolution manual microdrilling using a dentist drill semi automated micromilling and laser ablation while a separate handling step is involved in the first two techniques transferring the sample powder to an on line carbonate preparation system linked to an isotope ratio mass spectrometer the laser is directly interfaced with the mass spectrometer via a gas preparation device in this study we compare stable c and o isotope results obtained by these three preparation techniques using continuous he flow mass spectrometry on the same speleothem samples the overall consistency of the results is satisfactorily high in particular between the micromill and the laser data although the precision of the laser data is slightly lower than analyses obtained by the other two methods in particular with respect to 18o the speed of acquisition renders laser ablation a useful reconnaissance technique for rapidly analyzing long sections of speleothems micromilling is the method of choice to obtain highly spatially resolved isotope data of high analytical precision while microdrilling is still an low cost alternative for sampling at comparably low resolution e g of fast growing stalagmites

annually laminated sequences in the internal structure of some belgian stalagmites importance for paleoclimatology abstract fifteen stalagmites from four caves and one sealed tunnel in southern belgium are composed of alternations of annually deposited white porous and dark compact laminae this is demonstrated by comparing the number of laminae with the local history of the site for modern stalagmites and with radioisotopic ages for late glacial and holocene stalagmites annual cyclicity in the internal structure of these speleothems is explained by the highly seasonal variations of the water excess which influences underground water flow comparison between climatic data and modern stalagmites of a closed tunnel shows that growth laminae can record climatic variations 1 there is a good correlation r 0 84 between lamina thickness in a stalagmite and water excess 2 during years with a high water excess dark compact laminae are more developed which makes the speleothem darker vertical successions of several laminae represent microsequences that may have recorded climatic variations with a time resolution of 1 2 year in a late glacial stalagmite successive laminae microsequences form very regular cycles of 11 years separated by a thick darkcompact lamina it is supposed that as for modern stalagmites the thick dark compact lamina corresponds to a period of high water excess hence this 11 year cycle may reflect a climatic cycle

annual trace element cycles in calcite aragonite speleothems evidence of drought in the western mediterranean 1200 1100 yr bp each of two calcitic stalagmites from grotte de clamouse herault southern france displays a discrete aragonite layer dated at around 1100 yr bp the layer of fanning aragonite ray crystals is immediately preceded by calcite with mg and sr compositions that are uniquely high for the past 3 kyr trace element compositions close to the boundary between original aragonite and calcite are consistent with quasi equilibrium partitioning of trace elements between the phases study of modern dripwaters demonstrates that pronounced covariation of mg ca and sr ca ratios in dripwater occurs owing to large amounts of calcite precipitation upflow of the drips that fed the stalagmites trace element to ca ratios are enhanced during seasonally dry periods ion microprobe data demonstrate a pronounced covariation of trace elements including mg and sr in calcite and sr u and ba in aragonite the mean peak spacing is close to the long term mean of annual growth rates determined by differences in u series ages and so the trace element peaks are interpreted as annual the trace element chemistry of the stalagmites on annual to inter annual scales thus directly reflects the amounts of prior calcite precipitation interpreted as an index of aridity the longer term context is a multi decadal period of aridity 1200 1100 yr bp possibly correlated with an analogous episode in central america the arid period culminated in the nucleation of aragonite but within a decade was followed by a return to precursor conditions copyright 2005 john wiley sons ltd

annual to sub annual resolution of multiple trace element trends in speleothems this study aims to establish evidence for the widespread existence of preserved high resolution trace element variations in speleothems that may have climatic significance ion microprobe analysis of speleothems reveals that annual to sub annual variations in element chemistry exist at five shallow western european cave sites crag cave county kerry and ballynamintra county waterford ireland uamh an tartair sutherland scotland grotte pere noel belgium grotta di ernesto ne italy with widely varying climatic geomorphic and geological settings the variations are not restricted to species mg sr and ba known to substitute directly for ca in the calcite lattice but include h f na and p phosphorus as phosphate displays the greatest variability and may have the most significance as a proxy for the seasonal temperature cycle because of its role as a nutrient element the technique allows estimation of growth rate of speleothems at any interval of interest which is one of several possible uses in palaeoclimatology

cave air control on dripwater geochemistry obir caves austria implications for speleothem deposition in dynamically ventilated caves there are very few process studies that demonstrate the annual variation in cave environments depositing speleothems accordingly we initiated a monitoring program at the obir caves an austrian dripstone cave system characterized by a seasonally changing air flow that results in a predictable pattern of high pco2 during summer and low pco2 in winter although similar seasonal changes in soil pco2 occur they are not directly connected with the changes in the subsurface since the dripwaters are fed from a well mixed source showing little seasonal variation cold season flushing by relatively co2 poor air enhances degassing of co2 in the cave and leads to a high degree of supersaturation of dripwater with regard to calcite forced calcite deposition during the cold season also gives rise to a pronounced pattern of synchronous seasonal variations in electrical conductivity alkalinity ph ca and 13cdic which parallel variations recorded in 13ccave air chemical components unaffected by calcite precipitation e g d 18o sio2 so4 lack a seasonal signal attesting to a long residence in the karst aquifer modeling shows that degassing of co2 from seepage waters results in kinetically enhanced c isotopic fractionation which contrasts with the equilibrium degassing shown from the soreq cave in israel the obir caves may serve as a case example of a dripstone cave whose seepage waters and speleothems show intra annual geochemical variability that is primarily due to chemical modification of the groundwater by a dynamic bidirectional subsurface air circulation

climatic and environmental controls on speleothem oxygen isotope values variations in speleothem oxygen isotope values d 18 o result from a complicated interplay of environmental controls and processes in the ocean atmosphere soil zone epikarst and cave system as such the controls on speleothem d 18 o values are extremely complex an understanding of the processes that control equilibrium and kinetic fractionation of oxygen isotopes in water and carbonate species is essential for the proper interpretation of speleothem d 18 o as paleoclimate and paleoenvironmental proxies and is best complemented by study of site specific cave processes such as infiltration flow routing drip seasonality and saturation state and cave microclimate among others this review is a process based summary of the multiple controls on d 18 o in the atmosphere soil epikarst and speleothem calcite illustrated with case studies primary controls of d 18 o in the atmosphere include temperature and relative humidity through their role in the multiple isotope effects variability and modifications of water d 18 o values in the soil and epikarst zones are dominated by evaporation mixing and infiltration of source waters the isotopically effective recharge into a cave system consists of those waters that participate in precipitation of caco3 resulting in calcite deposition rates which may be biased to time periods with optimal dripwater saturation state recent modeling experimental and observational data yield insight into the significance of kinetic fractionation between dissolved carbonate phases and solid caco3 and have implications for the hendy test to assist interpretation of speleothem d 18 o time series quantitative and semi quantitative d 18 o climate calibrations are discussed with an emphasis on some of the difficulties inherent in using modern spatial and temporal isotope gradients to interpret speleothems as paleoclimate proxy records finally several case studies of globally significant speleothem paleoclimate records are discussed that show the utility of d 18 o to reconstruct past climate

stable isotope variations in modern tropical speleothems evaluating equilibrium vs kinetic isotope effects applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information the present study of harrison s cave barbados uses the analysis of the modern climatology and groundwater system to evaluate controls on the c and o isotopic composition of modern speleothems this new approach directly compares the 18 o and 13 c values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation if modern speleothems can be demonstrated to precipitate in isotopic equilibrium then ancient speleothems suitable for paleoclimatic studies from the same cave environment may also have been precipitated in isotopic equilib rium if modern speleothems are precipitated out of isotopic equilibrium then the magnitude and direction of the c and o isotopic offsets may allow specific kinetic and or equilibrium isotopic fractionation mechanisms to be identified carbon isotope values for the majority of modern speleothem samples from harrison s cave fall within the range of equilibrium values predicted from the combined use of 1 calcite water fractionation factors from the literature 2 measured temperatures and 3 measured 13 c values of the dissolved inorganic carbon of drip waters calcite samples range from 0 8 higher to 1 1 lower than predicted values the 13 c depletions are likely caused by kinetically driven departures in the fractionation between hco3 aq and caco3 from equilibrium conditions caused by rapid calcite growth 13 c enrichments can be accounted for by rayleigh distillation of the hco3 aq reservoir during degassing of 13 c depleted co2 modern speleothems from harrison s cave are not in o isotopic equilibrium with their corresponding drip waters and are 0 2 to 2 3 enriched in 18 o relative to equilibrium values 18 o variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between hco3 aq and caco3 from equilibrium conditions to nonequilibrium conditions consistent with rapid calcite growth in contrast to 13 c 18 o values of modern calcite may not be affected by rayleigh distillation during degassing because co2 hydration and hydroxylation reactions will buffer the o isotopic composition of the hco3 aq reservoir if the effects of rayleigh distillation manifest themselves in the o isotopic system they will result in 18 o enrichment in the hco3

timing duration and transitions of the last interglacial asian monsoon thorium 230 ages and oxygen isotope ratios of stalagmites from dongge cave china characterize the asian monsoon and low latitude precipitation over the past 160 000 years numerous abrupt changes in 18o 16o values result from changes in tropical and subtropical precipitation driven by insolation and millennial scale circulation shifts the last interglacial monsoon lasted 9 7 1 1 thousand years beginning with an abrupt less than 200 years drop in 18o 16o values 129 3 0 9 thousand years ago and ending with an abrupt less than 300 years rise in 18o 16o values 119 6 0 6 thousand years ago the start coincides with insolation rise and measures of full interglacial conditions indicating that insolation triggered the final rise to full interglacial conditions

in situ measurement of seasonal δ18o variations and analysis of isotopic trends in a modern speleothem from southwest australia we present a record of seasonal and inter annual oxygen o and carbon c isotope ratios from an 81 year old stalagmite from moondyne cave southwest australia the growth history of stalagmite mnd s1 is known since it grew on a cave boardwalk that was installed in 1911 and removed in 1992 this stalagmite provides an excellent test of speleothem climate proxies because the regional climate is strongly seasonal wet winter dry summer and has experienced a 200 mm 20 reduction of mean rainfall since the mid 1960s and a 0 8 c temperature rise since 1953 seasonal variations in calcite o were measured in situ by high spatial resolution ion microprobe whilst inter annual variations of o and c were measured by conventional gas source mass spectrometry comparison of the speleothem stable isotopes and instrumental temperature records reveals that o variations are too large to be driven by temperature alone and are in the opposite sense however daily rainfall o measurements show that the mean seasonal range in o of rainfall in southwest australia is large 2 and inversely correlated with rainfall amount a rainfall driver for the speleothem o is confirmed by the detection of seasonal shifts of 0 7 1 5 in speleothem that track rainfall o smoothed by storage in the overlying limestone the seasonal range in speleothem o is larger than any inter annual and decadal variation observed in the record the prominent annual cycles in speleothem o revealed by ion microprobe analysis indicate that subtle changes in the frequency of intense winter rainfall events or possibly also moisture sources could produce significant changes in mean speleothem o the ion microprobe results also raise the possibility that the masses of speleothem calcite deposited in winter and summer could vary as a function of the seasonal drip rate and carbonate saturation state of these waters if this is the case then small changes in the relative masses of calcite deposited in winter and summer could produce significant shifts in mean o and c that have a complex relation to climate this finding should be generally applicable to the interpretation of long term trends in speleothem geochemical records for shallow cave sites where seasonal variations in geochemical tracers are relatively large including most of the sub tropical monsoon belts and mid to high latitudes with distinct rainfall seasons

stable isotope study of cave percolation waters in subtropical brazil implications for paleoclimate inferences from speleothems we analyze the interannual monthly variability of oxygen isotope ratios in data from iaea stations along the atlantic coast of south america between 238 and 348 s to evaluate the influence of parameters such as temperature rainfall amount and moisture source contribution on meteoric water recharging two karst systems in subtropical brazil in addition a 2 year monitoring program performed on soil and cave drip and rimstone pool waters from sampling sites with contrasting discharge values and located at 100 and 300 m below the surface in the santana cave system 24831v s 48843v w is used to test the influence of hydrologic and geologic features on the temporal variations of seepage water d 18 o interannual monthly variations in d 18 o of rainfall reflect primarily regional changes in moisture source contribution related to seasonal shifts in atmospheric circulation from a more monsoonal regime in summer negative values of d 18 o to a more extratropical regime in winter positive values of d 18 o variations in groundwater d 18 o indicate that the climatic signal of recent rainfall events is rapidly transmitted through the relatively deep karst aquifer to the cave drip waters regardless of location of collection in the cave in addition the data also suggest that water replenishment in the system is triggered by the increase in hydraulic head during periods when recharge exceeds the storage capacity of the soil and epikarst reservoirs significant perturbations in the groundwater composition characterized by more positive values of d 18 o are probably connected to an increased atlantic moisture contribution associated with extratropical precipitation this implies that the d 18 o of speleothems from caves in this region may be a suitable proxy for studying