geochemical and textural evidence for early shallow diagenetic growth of stratigraphically confined carbonate concretions upper devonian rhinestreet black shale western new york laterally persistent carbonate concretionary horizons are conspicuous to the upper devonian frasnian rhinestreet black shale of the western new york state appalachian plateau field observations including randomly tilted concretions and differential compaction of host sediment laminae around concretions are consistent with early diagenetic growth in unconsolidated sediment further estimates of pre cementation host sediment porosity based on the volume percentage of caco3 cement 74 93 and perhaps most importantly the preservation of a cardhouse clay fabric in mudstones collected from concretion pressure shadow regions suggest that concretionary growth occurred rapidly within perhaps a meter of the seafloor petrographic examination sem of matrix carbonate samples collected from six concretions reveals a relatively porous 4 7 framework of calcite micrite and microsparite euhedral pyrite most abundant near concretion rims disseminated pyrite framboids and randomly oriented detrital clay platelets and domains c isotopic compositions of rhinestreet concretion matrix carbonate range from 13 9 to 1 7 pdb suggesting derivation of c from a mixed source that included depleted and isotopically heavy c slightly to moderately depleted o isotopic compositions 3 8 to 6 8 pdb do not corroborate the shallow depth of concretion growth suggested by field and textural observations the vertically confined nature of most rhinestreet concretions their large size oblate ellipsoidal shape variable c isotope compositions and absence of any evidence that concretions were sited at local concentrations of organic matter suggest an origin by anaerobic ch4 oxidation early pre concretion sulfate reduction and associated pyrite framboid formation that occurred throughout the host sediment was renewed in thin shallow zones of uncompacted sediment the concretionary horizons by ch4 and isotopically heavy dissolved carbonate diffusing upward from the zone of biogenic methanogenesis to the base of the sulfate reduction zone probably little more than a meter below the seabed local variations in the mix of isotopically light ch4 and heavier dissolved carbonate may have been responsible for the wide range of 13c isotopic compositions of rhinestreet concretions crucial to this mechanism is a pause in deposition that would have held the zone of carbonate precipitation at a fixed distance below the ocean floor long enough for the large concretions to grow evidence that sedimentation slowed or even stopped during concretion growth includes 1 laminae that can be traced through concretions with no observed systematic changes in thickness and 2 minimal concretion center to edge variations in estimated pre cementation porosity a resumption of sedimentation and related burial brought concretion growth in each horizon to an end the moderately depleted 18o values of rhinestreet concretions probably reflect the resetting of o isotopic compositions by warm fluids migrating through the permeable concretions during burial

chaos and irregularity in karst percolation 1 this paper focuses on analyzing chaos in cave percolation water drip rates which has implications for flow routing in fractured media and on the use of speleothems for paleoclimate reconstructions it has been shown that the physics of dripping faucets involve a set of non linear equations leading to chaotic drip rate meaning that for a given drip rate the interval between individual drops can vary greatly it can be expected that drip waters supplying stalagmites show similar properties and consequently the dependency between water flux and stalagmite growth rate or geochemistry could be more complicated than usually assumed we used high frequency monitoring of two contrasting drips in a cave in australia and identified chaos in cave drip rate our findings also indicate that the occurrence of chaos can give insights into flow routing in fractured media

intra and inter annual growth rate of modern stalagmites we measure the factors that determine growth rate temperature drip rate calcium ion concentration for 31 waters that feed stalagmites within six cave systems throughout europe water samples were collected at a frequency of at least 1 month to permit the modelling of both inter and intra annual growth rate variations utilising the theory of wolfgang dreybrodt chem geol 29 1980 89 105 chem geol 32 1981 237 245 dreybrodt w 1988 processes in karst systems springer verlag berlin 288 pp inter annual growth rates were measured using the stalagmites that were associated with the analysed water samples growth rate was determined from annual lamina counting specific time markers within the stalagmites and location of bomb 14c when compared to theoretically predicted values a good agreement between theoretical and measured stalagmite growth rates is observed r2 0 69 when compared to site climate and geochemical parameters a good correlation is observed between measured growth rate and mean annual temperature for five sites r2 0 63 and dripwater calcium content r2 0 61 but not drip rate r2 0 09 the good correlation with both calcium and temperature is due to soil co2 production being primarily determined by surface temperature and soil moisture however when we compare our data to that in the grotte de clamouse a site that has little soil cover we observe that the growth rate temperature relationship breaks down due to either the lack of soil co2 production or prior calcite precipitation intra annual data demonstrates that maximum growth rate occurs when calcium concentrations are high and that this occurs under different seasons depending on the hydrology of each site our results demonstrate a stronger dependence of intra annual stalagmite growth rate on dissolved calcium ion concentrations than drip rate for the range of drip rates investigated here 0 01 t 2drip s 1 but for lower drip rates this factor becomes important in controlling growth rate we suggest that for well monitored and understood sites stalagmite growth rate variations can provide useful information for palaeoclimate reconstruction

holocene climate variability in sicily from a discontinuous stalagmite record and the mesolithic to neolithic transition abstract fabric and stable isotopic composition of a holocene stalagmite cr1 from a cave in northern sicily record changes in paleorainfall in the early holocene high 13c stable isotope values in the calcite deposited from ca 8500 to ca 7500 yr ago are interpreted as reflecting periods of high rainfall the wet phase was interrupted by two periods of multi century duration characterized by relatively cool and dry winters centered at ca 8200 and ca 7500 yr ago highlighted by low 13c and 18o values a high variability of 13c values is recorded from ca 7500 to ca 6500 yr ago and indicates that the transition from a pluvial early holocene to the present day climate conditions was punctuated by decadal scale periods of relatively dry winters in northern sicily the traditional elements of the neolithic appear at ca 7700 yr ago it is possible that changes in rainfall influenced the passage from hunter gathering to farming and sheep herding economies

climate and vegetation history of the midcontinent from 75 to 25 ka a speleothem record from crevice cave missouri usa four missouri stalagmites yield consistent overlapping records of oxygen and carbon isotopic changes and provide a climate and vegetation history with submillennial resolution from 75 to 25 thousand years ago ka the thorium 230 dated records reveal that between 75 and 55 ka the midcontinental climate oscillated on millennial time scales between cold and warm and vegetation alternated among forest savanna and prairie temperatures were highest and prairie vegetation peaked between 59 and 55 ka climate cooled and forest replaced grassland at 55 ka when global ice sheets began to build during the early part of marine oxygen isotope stage 3

jointing within the outer arc of a forebulge at the onset of the alleghanian orogeny the oldest joint set in devonian rocks of western new york state has an atypical ns strike and predates regionally more abundant nw striking and ene striking joints driven by hydrocarbon related fluid decompression the ns joints originated in higher modulus diagenetic carbonate and were driven initially by a different mechanism either joint normal stretching and or thermoelastic contraction the origin of these joints in higher modulus carbonate concretions indicates the presence of a tensile stress produced by uniform regional extensional strain upper devonian shale hosting the ns joints crops out in that area of the appalachian basin where a morrowan erosional unconformity marks the region of maximum upward lithospheric flexure of an early alleghanian forebulge the ns strike of these early joints points to a forebulge stretching axis oriented approximately east west and associated in time and space with crustal loading that drove both the northfieldian orogeny and the underplating of the bronson hill anticlinorium in new england ultimately subsidence of the morrowan forebulge buried the upper devonian shale succession to the oil window during the latter part of the alleghanian tectonic cycle resulting in the propagation of fluid driven nw and ene trending joints in black shale

elevated and variable values of 13c in speleothems in a british cave system 13c isotope variations in speleothems have been investigated for samples from the british isles where plants which use the hatch slack or c4 photosynthetic pathway are not present the range of 13c expected in speleothem carbonate formed in isotopic equilibrium with soil co2 derived from the overlying c3 vegetation should thus fall in the range 12 to 6 forty one actively growing speleothem samples from low discharge sites were analysed from stump cross caverns yorkshire england ten percent have 13c greater than 6 in addition a large range of 13c was observed 8 06 1 38 a 1 variability of 17 with adjacent samples having 13c differing by a maximum of 4 74 similar findings were obtained from a review of analyses of late quaternary speleothem samples from the british isles with 75 of flowstone samples and 57 of high flow stalagmite samples exhibiting elevated 13c three possible processes are proposed as possible causes of elevated 13c in speleothems firstly fractionation may occur between the stalactite and stalagmite due to evaporation or degassing secondly degassing of the groundwaters may have occurred within the aquifer before reaching the cave void allowing release of some co2 from the water whilst remaining saturated in calcium finally the elevated 13c may be due to short water residence times in the soil such that equilibrium between soil water and soil co2 is not reached evidence presented here demonstrates that any one of these mechanisms may be important in the karst areas of the british isles caution is needed before interpreting the 13c signal within speleothems in terms of palaeovegetation

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

former carboniferous overburden in the northern appalachian basin a reconstruction based on vitrinite reflectance abstract elevated vitrinite reflectance values have been observed in the upper devonian west falls group of the northern new york appalachian basin in new york lopatin modeling suggests that the high thermal maturity of these and associated strata was caused by the presence of a devonian and carboniferous overburden that has subsequently been eroded from the northern appalachian basin devonian overburden reconstructed from extrapolation of stratigraphic data thickens from west 0 4 km to east 2 0 km across the field area in contrast carboniferous overburden reconstructed by lopatin modeling thins from west 2 0 3 4 km to east 0 7 1 2 km the inferred geometry of a northeasterly thinning wedge of sediment is compatible with the existing distribution of late paleozoic sediments in the appalachian basin and suggests the northern part of the basin experienced only moderate subsidence during carboniferous time

the role of near surface cavities in the carbon dioxide cycle of karst areas evidence from the carburangeli cave natural reserve italy hydrological chemical and meteorological data collected during the years 2006 2007 at carburangeli cave italy have provided new insights on the near surface cycle of carbon dioxide particularly concerning the role played by fractures and karst conduits carbon dioxide is trapped in the underground atmosphere essentially when its temperature is lower than the outer one by contrast convective air circulation disperses all the excess co2 in the external environment when the thermal differential is inverted the network of fractures and karst conduits then works in the vadose zone as a re circulator of co2 from the soil to the atmosphere the total amount of co2 fixed in the underground is controlled during the wet season by the amount of infiltrating waters which act as the main carrier of co2 in the subsoil by contrast during the dry season gravitational drainage is responsible for the accumulation of carbon dioxide in the underground voids the quantitative balance demonstrated that the degassed co2 amounts are one order of magnitude higher than the dissolved co2 in light of this if the near surface outgassing processes are not taken into account co2 budgets may be affected by significant errors

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

airborne pseudo dual doppler analysis of a dryline outflow boundary intersection abstract on 3 june 1995 as part of the verification of the origins of rotation in tornadoes experiment vortex the electra doppler radar eldora onboard the national center for atmospheric research ncar electra aircraft made possible a high resolution examination of clear air motions in the texas panhandle in and around the intersection of the dryline and a surface baroclinic boundary a location commonly referred to as the triple point the eldora observations as well as conclusions drawn from analyses of these data are presented and discussed a transverse secondary circulation associated with the dryline is visualized through analyses of the eldora data typical values of rising and sinking air are found to be 2 m s 1 and 2 3 m s 1 respectively these vertical velocities are approximately the same as those indicated by in situ data collected onboard the electra because the maximum in rising motion is found at the western edge of the dewpoint gradient and because the low level relative airfl

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

a new evaluation of palaeo heat flows and eroded thicknesses for the carboniferous ruhr basin western germany palaeo heat flows and thicknesses of eroded carboniferous overburden in the coal bearing ruhr basin western germany were estimated using one dimensional basin modelling techniques thermal and burial histories for 11 localities were calibrated by comparing measured and calculated vitrinite reflectance data based on the assumption of pre tectonic maturation in contrast to former studies the kinetic easy r0 approach applied for the calculation of vitrinite reflectance lopatin s tti algorithm was used in addition for one well in order to demonstrate the impact of the selection of the algorithm for vitrinite reflectance calculation on the simulation results simulated palaeo heat flows for the time of maximum burial most probably in the stephanian range from 64 to 83 mw m2 and decrease towards the south these heat flows are lower than values computed during earlier studies but are still relatively high in comparison to recent foreland basins the regional distribution of palaeo heat flows indicates that the crust beneath the ruhr basin was relatively thin and thickened towards the south at the end of the carboniferous after the stephanian 2200 3500 m of carboniferous overburden were eroded an observed southward increase in eroded thicknesses is caused by an uplift of the area studied which decreased towards the north at the end of the variscan folding large thicknesses of deposited and later eroded carboniferous sediments have to be postulated to explain the maturity data even along the present southern margin of the ruhr basin this indicates that the late carboniferous sediments originally extended far to the south geological arguments suggest that the deposition of carboniferous sediments in the entire ruhr basin continued until the stephanian

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

oxygen and hydrogen isotopes of rainfall and dripwater at desoto caverns alabama usa key to understanding past variability of moisture transport from the gulf of mexico abstract the southeast and the us gulf coast in particular are notably lacking isotope data in the water cycle despite the fact that moisture transport from the gulf of mexico gom has a considerable influence on both regional and continental rainfall patterns this study reports time series of oxygen and hydrogen isotopes acquired over a 3 year period 2005 2008 from gom derived rainfall cave dripwater and shallow groundwaters and offers valuable insights on the links between factors controlling regional rainfall and the ubiquitous karst hydrology amount weighted mean monthly rainwater 18o and d values in tuscaloosa alabama range from 1 5 to 8 3 and 1 2 to 49 5 respectively and show mean seasonal amplitudes of 4 18o and 25 d in comparison d excess values display large seasonal amplitudes of 10 20 resulting from differences in the degree of evaporation from falling raindrops between summer and winter months and correlate well with the coeval air temperature r2 0 59 p dripwater samples from nearby desoto caverns show weak 18o and d seasonal variations and record only 20 and 51 of the 18o and 2h enrichments respectively discerned in the rainwater 3 year time trends the seasonal and interannual amplitude attenuations in the dripwaters are attributed to a relatively thick overlying bedrock 30 40 m and a relatively large well mixed epikarst storage reservoir residence time of water in the cave s epikarst is estimated to be 1 3 months based on high resolution flow rate data our investigation suggests that global atmospheric circulation patterns enso and bermuda high likely govern the interannual 18o and d isotope trends discerned in the water cycle compartments but much longer time series are required to confirm our conjectures the results of this study form a solid basis for future acquisition and interpretation of climate proxy records from regional speleothems

aragonite calcite relationships in speleothems grotte de clamouse france environment fabrics and carbonate geochemistry abstract in grotte de clamouse france aragonite forms in a variety of crystal habits whose properties reflect the conditions of formation prolonged degassing and evaporation yield needle aragonite which is more enriched in 18o and 13c than aragonite ray crystals which form near isotopic equilibrium at present aragonite ray crystals form at the tops of stalagmites at very low discharge 0 00035 ml min and when fluid mg ca ratio is 1 1 temperature and evaporation do not seem to have a significant role in their formation the presence of aragonite in stalagmites should be indicative of a decrease in drip rate related to either dry climate conditions or local hydrology fossil aragonite was in part replaced by calcite in a time frame 13c signal and u content and preserved aragonite relicts up to 16 weight the isotope signal of different aragonite habits may reflect conditions of formation rather than climate parameters the real extent of aragonite to calcite transformation may be underestimated when replacement calcite inherits both textural and chemical properties of the precursor

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

time and temperature in petroleum formation application of lopatin s method to petroleum exploration n v lopatin in the soviet union has developed a method for taking both time and temperature into account as factors in thermal maturation of kerogen lopatin s time temperature index of maturity tti values correlate with the thermal regimes corresponding to generation and preservation of hydrocarbons because such information is potentially of great interest for oil exploration a calibration and evaluation have been made of lopatin s method within the limitations of the data presently available the following statements can be made 1 the rate of the chemical reactions involved in thermal maturation of organic material appears to double with every 10 c 18 f rise in temperature 2 threshold values of lopatin s time temperature index of maturity tti are 15 onset of oil generation 75 peak oil generation 160 end oil generation 500 40 oil preservation deadline 1 000 50 oil preservation deadline 1 500 wet gas preservation deadline 65 000 dry gas preservation deadline 3 tti values calculated from lopatin reconstructions consistently agree with other maturation parameters commonly used by petroleum geochemists potential applications of lopatin s method for oil exploration include timing of oil generation calculation of volume of hydrocarbons generated within a basin and determination of economic deadlines

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

carbon dioxide and dissolution rate dynamics within a karst underflow overflow system savoy experimental watershed arkansas usa abstract within numerical models of karst development geochemical and hydrological boundary conditions are typically assumed to be constant however rates of calcite dissolution in natural karst systems can vary substantially in time in particular variation in carbon dioxide co2 concentrations has been shown to produce time variability in dissolution rates in karst streams but controls on co2 variation within karst systems are relatively poorly quantified here we analyze hourly in situ measurements of dissolved co2 discharge and specific conductance at a pair of karst underflow overflow springs and examine potential drivers of variability in co2 and dissolution rates the springs display strong seasonal variability in co2 and saturation state as well as moderate variation during storm events though both springs have elevated co2 concentrations in the summer season the overflow spring experiences a substantial decrease in dissolved co2 below a critical discharge threshold we hypothesize that this decrease results from ventilation within the overflow portion of the system as segments of the flow path transition from full pipe to open channel flow the overflow spring experiences substantially lower average dissolution rates than the underflow spring despite larger discharge and chemical variability during high flow events at the overflow spring though open systems are frequently presumed to have higher dissolution rates because of their ability to replenish co2 that is consumed in the dissolution process these data suggest that dissolution rates within the closed portion of the system may in some cases be higher due to the inability of closed flow paths to ventilate excess co2 to the atmosphere such conditions are likely to occur in conduits where co2 concentrations are elevated above atmospheric levels and average flow through times are short compared to the time scale over which water reaches equilibrium with respect to calcite

distribution of maximum burial temperatures across northern appalachian basin and implications for carboniferous sedimentation patterns clay mineral diagenesis and apatite fission track age data indicate that the maximum burial temperatures to which the middle devonian tioga metabentonite was exposed rise abruptly from low values in western new york state to higher values in the east the highest temperatures which approach 175 sup 0 c were reached just west of syracuse neither the pattern nor the magnitude of burial temperatures can be explained solely by burial of the metabentonite beneath upper devonian sediments although spatial variations in the geothermal gradient could have produced the observed pattern of burial temperatures it is more likely that carboniferous sediments no longer preserved in the area were responsible for the indicated burial the inferred presence of thick carboniferous sequences in western new york state suggests that the allegheny orogeny had a stronger influence on sedimentation in the northern appalachian basin than has been previously recognized 25 references 2 figures 2 tables

present day kinematic behaviour of active faults in the eastern alps abstract the neogene to quaternary lateral extrusion of the eastern alps towards the pannonian basin is accommodated by a system of strike slip faults despite decades lasting gps observations no information on contemporary kinematic behaviour of these faults has been available therefore we had monitored subsidiary and or conjugated faults associated to these major fault systems in six caves throughout the eastern alps over a 1 5 2 5 year observation period by means of high resolution three dimensional moire extensometers tm71 we confirmed that the monitored faults revealed present day aseismic displacements at a micrometer level during several activity phases that usually also coincided with periods of increased local seismicity the annual displacement rates of the monitored faults were mostly about an order of magnitude smaller than the rates of the entire crustal wedges revealed from gnss the particular displacements consisted of a variety mechanisms and faulting regimes fault dilations and compressions were mostly associated with thermal volumetric variations normal dip slips and downward hanging wall displacements originated due to gravitational relaxation or mass movement displacements with the same mechanisms as the geologically documented fault systems or with an upward component were attributed to tectonic creep and strain built up during the interseismic period on the other hand the countervailing displacements opposite to the master fault kinematics were most probably caused by elastic rebound they were usually registered few days in advance to distinct local earthquakes that were simultaneously activated at locked segments within the same deformation band therefore the countervailing events could be considered an indicator of impending near earthquake within the rebound zone their better understanding and real time detecting could be a step forward to an effective earthquake early warning in similar geological settings

deep burial of coal bearing strata anthracite region pennsylvania sedimentation or tectonics recent studies of vitrinite reflectance sedimentary compaction and fluid inclusions indicate that coal bearing strata of the pennsylvania anthacite region were once buried at depths ranging from 6 to as much as 9 km vitrinite reflectance anisotropy suggests that anthracite rank was attained by normal geothermal heating largely prior to and during alleghanian folding paleomagnetic ages for the folding and paleobotanical ages of the youngest extant sediments delimit the maximum burial and deformation to a relatively short interval 285 to 270 ma in comparison with typical molasse sequences the implied thicknesses and rates of deposition are excessive suggesting that much of the former overburden was emplaced tectonically or by extremely rapid sedimentation the total implied thickness about 20 km of paleozoic strata in the region is abnormally large for an epicontinental basin an inferred body of mafic rock embedded in the precambrian basement evidenced by the scranton gravity high sgh may have influenced crustal subsidence especially during the allegheny orogeny and produced a large downwarp accounting for the high coal rank the fact that isorank contours paleozoic sediment isopach contours and a large structural sag all lie roughly parallel to the boundaries of the sgh oblique to the principal alleghanian fold trend lends support to this idea

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

the demise of the last interglacial recorded in isotopically dated speleothems from the alps abstract the transition from interglacial to glacial climate has attracted much attention in paleoclimatic research partly because orbital forcing dictates that such a return to a new ice age is inescapable albeit in the distant future only the detailed series of steps that leads to glacial inceptions remains poorly understood however and studies of past glacial inceptions are often compromised by incomplete records imprecise chronological control and or uncertainties associated with proxy transfer functions here we present results from u th dated speleothems from a cave in the austrian alps entrische kirche cave which grew continuously between ca 127 and 114 ka and intermittently also during subsequent stadials and interstadials the alpine setting of this cave is prone to periglacial and glacial processes as well as temperature and precipitation changes which are recorded in these cave deposits we use high resolution stable isotope data to constrain paleoenvironmental changes associated with the demise of the last interglacial unprecedented in detail for central europe peak interglacial conditions are characterized by high 18 o values and high growth rates from ca 127 to 124 ka a major drop in 18 o by 3 occurred at ca 118 ka which coincided with cold event c26 in the north atlantic this isotopic shift which occurred at or close to isotopic equilibrium cannot be explained by simple uniform cooling modelling suggests that enhanced seasonality dominated by significant changes in winter precipitation are required to reconcile the isotope data with the fact that calcite deposition continued across the mis 5e d transition i e no cave freezing this period of enhanced seasonality lasted for several millennia during which the catchment area of the cave remained geomorphologically stable and ice free eventually speleothem growth terminated at ca 114 ka which is in line with widespread ice rafting in the north atlantic cold event c24 and the onset of fully stadial conditions during mis 5d

variation of the asian summer monsoon since the last glacial interglacial recorded in a stalagmite from southwest china abstract a number of studies proposed a close link between the climate changes in the asian summer monsoon asm the southern hemisphere sh and high latitudes of the northern hemisphere nh but the mechanisms is still an open question although speleothems 18o records have displayed excellent values in the reconstruction of paleoclimate change at centennial millennial to orbital timescales the significance of speleothems 18o and 13c is still debatable here a high precise 230th dated stalagmite from southwestern china was used to reconstruct the changes of asm and regional hydrological conditions since the last interglacial 3 6 118 1 ka bp by the coupled 18o and 13c we found 1 the easm and ism are synchronous changing on the orbital timescale responding to the change of north hemisphere summer insolation nhsi and high latitude climate change there is a teleconnection between antarctic temperature change and asm through the mascarene high and the somali jet 2 during mis 5d the stalagmite 18o in yangzi cave is nearly 1 5 higher than that in mis 2 the maximum of last glacial this should be attributed to the different isotopic compositions in moisture source of ism and easm and the dynamic changes of monsoon circulations 3 from mis 3 to mis 2 the asm showed a stepped pattern in weakening consistent with the decreasing nhsi and increasing global ice volume 4 the changes in stalagmite 13c indicated the changes of local hydrological conditions and closely correlated with climate changes revealed by stalagmite 18o the effective humidity which determined by temperature evaporation and precipitation dominated the regional hydrological conditions the change of effective humidity recorded in stalagmite 13c by influencing surface biomass and soil co2 production

time temperature burial significance of devonian anthracite implies former great 6 5 km depth of burial of catskill mountains new york specimens of coalified plant debris in tully correlative strata of the gilboa formation uppermost middle devonian within the eastern catskill mountains of new york state have been converted to anthracite having a vitrinite reflectance of 2 5 this implies a level of organic metamorphism lom of 16 the specimens are about 350 m y old if 200 m y is taken as the duration of the time of exposure to the maximum geothermal temperature then the lom of 16 and other thermal indicators imply a maximum temperature of 190 sup 0 c using a geothermal gradient of 26 sup 0 c km sup 1 17 sup 0 f 1 000 ft sup 1 a former depth of burial of 6 5 km is implied such former deep burial is not usually inferred for the catskills but it is consistent with the idea that the thick about 6 4 km or 21 000 ft carboniferous strata of northeastern pennsylvania formerly extended northeast far enough to bury the catskills the lack of metamorphism of the paleozoic strata lying about 4 5 km beneath the tully correlative rocks and exposed in the adjacent hudson valley places low limits on the former geothermal gradient this supports the concept of great depth of former burial of the catskills for example 6 5 km of former burialmore and a geothermal gradient of 26 sup 0 c km sup 1 imply a temperature of 307 sup 0 c for the base of the paleozoic by contrast only 1 km of former burial requires a geothermal gradient of 170 sup 0 c km sup 1 which would have subjected the base of the paleozoic to a temperature of 955 sup 0 gamma which is far higher than the 600 to 650 sup 0 c recently inferred for the acadian age metamorphism of the taconic allochthon in southwestern massachusetts and adjoining areas less

loading and unloading of sedimentary basins the effect of rheological hysteresis 1 we present a model for the study of the effect of rheological hysteresis on compaction in sedimentary basins when surface loading and unloading occurs when compaction is slow sedimentation rate is large and or permeability is small the hysteresis has little effect on the basal compaction layer but in the more realistic case where compaction is fast i e sedimentation is slow and or permeability is large surface unloading leads to downward propagation of a decompaction front across which the vertical porosity gradient jumps while subsequent surface reloading leads to downward propagation of a discontinuity in porosity despite the fact that the porosity is governed by a diffusive equation of richards type

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

infiltration processes and flow rates in developed karst vadose zone using tracers in cave drips the purpose of this research was to identify groundwater recharge mechanisms and measure flow velocities through the epikarst and the vadose zone in a typical site of mediterranean carbonate karst in natural rain conditions by avoiding artificial flushing more realistic travel times could be measured and the effective resultant vadose flow velocity could be inferred additionally detailed monitoring enabled better description and quantification of infiltration and percolation processes nine different cave drips were monitored and sampled for three hydrological years in fractured karst lithology on mount carmel israel at three drips discharge was measured continuously by tipping buckets rainfall and soil water content were recorded above the cave an artificial tracer experiment was conducted using uranine placed in a joint and at the soil rock interface at soil pockets both 27 m above the cave four hydrological types of drips post storm seasonal perennial and overflow were identified each demonstrating different characteristics in terms of discharge and chemistry the maximum effective flow velocities uranine dye arrival times were 41 76 cm h tracer mass flux was computed from the uranine breakthrough curves and drip hydrographs the dominant flow velocities derived from the peak of tracer mass flux were 0 35 0 41 cm h from post storm drips and 22 24 cm h from the other drips pulse through intra event piston flow was indicated by the time lags between the increase in drip rate and the time of drop in salinity and appearance of the tracer in most of the measured drips chloride concentrations were used to distinguish between old matrix water and preferential flow water in the perennial drips demonstrating a two component mixing model in 2005 2006 preferential flow water reached up to 20 25 from annual discharge of these drips this study promoted a method to compute dominant effective flow rates in the vadose zone in natural rain conditions copyright 2010 john wiley sons ltd

calculation of organic maturation levels for offshore eastern canada implications for general application of lopatin s method recorded maximum bottom hole temperatures may vary significantly from true formation temperatures because of the effects of drilling fluid circulation a theoretical temperature correction technique was applied to log heading data to compute 191 static temperatures for 64 wells on the scotian shelf a linear regression performed on 140 computed temperatures produced an average geothermal gradient of 2 66 c 100 m correlation coefficient 0 97 a geothermal gradient map constructed from the corrected data shows that areas of thicker sediment accumulation are marked by high geothermal gradients e g abenaki sable subbasins whereas areas of shallow basement coincide with low gradients e g lahave platform canso ridge it is proposed that the major control on the distribution of scotian shelf geothermal gradients is the thermal conductivity of the sediments radiogenic heat production within the sediments and subsurface fluid movement probably contribute to a lesser extent within the basins higher

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

inter relationship and environmental significance of stalagmite δ13c and δ18o records from zhenzhu cave north china over the last 130 ka abstract there is a vigorous and ongoing debate about the interpretation of the stalagmite 18 o record from east china as an indicator of east asian summer monsoon easm intensity this is mainly because of the inconsistent spatial variation of precipitation amount in east china but the generally consistent variation of precipitation 18 o on various timescales however a direct comparison of a proxy record of precipitation amount with the 18 o record from the same stalagmite has rarely been reported especially in north china here we present precisely dated high resolution stalagmite 13 c and 18 o records for the past 130 ka 1 ka 1000 years from zhenzhu zz cave in north china on multi millennial to orbital timescales the 13 c and 18 o records exhibit a high degree of in phase co variation however there are differences in the trend and amplitude of change between various marine isotopic stages mis specifically mis5e mis5c mis5a mis3 and mis1 modern monitoring results of two years from zz cave together with a comparison of the 13 c record from the cave with a pedogenic carbonate 13 c record from the western chinese loess plateau clp demonstrate that the 13 c record is a sensitive and reliable indicator of easm rainfall amount considering that variations in both the amount and 18 o of precipitation can be modulated by the atmospheric circulation system we conclude that the amplitude and trend of the stalagmite 18 o variations from north china are not an absolute indicator of easm intensity but rather an indicator of changes in the phase of the easm we suggest that stalagmite 18 o records combined with other unambiguous proxy indicators from stalagmites can provide a more comprehensive history of changes of the easm

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

floating rafts of calcite crystals in cave pools central texas u s a crystal habit vs saturation state abstract calcite precipitation at the air water interface in cave pools in central texas u s a produces floating rafts of interconnected low mg calcite crystals with individual crystal habits that range from equant length to width 1 1 to prismatic 4 1 saturation state for the waters ranges from 0 19 to 1 35 sic log iap k equant crystals precipitate from waters with a lower saturation index sic and form rafts with a fused fabric whereas prismatic crystals precipitate from higher sic waters and form rafts with an interlaced fabric the pools contain low magnesium molal mg ca 0 6 calcium bicarbonate and calcium bicarbonate nitrate type waters with temperatures that range from 13 8 c to 20 7 c and ph readings from 6 7 to 8 4 equant euhedral crystals precipitate from water with saturation states close to equilibrium visible defects in the equant crystals include incomplete edges between faces and nearly circular mean diameter 9 m to angular holes in faces the holes apparently result from crystallite growth around foreign objects on the crystal surface such as gas bubbles prismatic crystals precipitate from supersaturated water faces of these subhedral crystals are smaller in area than the faces of the equant crystals no intrafacial circular holes are seen but trigonal intercrystallite pores are common in the prismatic crystals the variety in crystal habits from equant to prismatic is due to preferential growth along one crystallographic axis thus in these cave pools crystal habit is related to the saturation state of the water

the coupled δ13c radiocarbon systematics of three late glacial early holocene speleothems insights into soil and cave processes at climatic transitions abstract the coupled 13 c radiocarbon systematics of three european stalagmites deposited during the late glacial and early holocene were investigated to understand better how the carbon isotope systematics of speleothems respond to climate transitions the emphasis is on understanding how speleothems may record climate driven changes in the proportions of biogenic soil carbon and limestone bedrock derived carbon at two of the three sites the combined 13 c and 14 c data argue against greater inputs of limestone carbon as the sole cause of the observed shift to higher 13 c during the cold younger dryas in these stalagmites gar 01 from la garma cave n spain and so 1 from sofular cave turkey the combined changes in 13 c and initial 14 c activities suggest enhanced decomposition of old stored more recalcitrant soil carbon at the onset of the warmer early holocene alternative explanations involving gradual temporal changes between open and closed system behaviour during the late glacial are difficult to reconcile with observed changes in speleothem 13 c and the growth rates in contrast a stalagmite from pindal cave n spain indicates an abrupt change in carbon inputs linked to local hydrological and disequilibrium isotope fractionation effects rather than climate change for the first time it is shown that while the initial 14 c activities of all three stalagmites broadly follow the contemporaneous atmospheric 14 c trends the younger dryas atmospheric 14 c anomaly can be clearly discerned subtle changes in speleothem initial 14 c activities are linked to climate driven changes in soil carbon turnover at a climate transition

insulating effect of coals and black shales in the appalachian basin western pennsylvania sedimentary rocks rich in organic matter often have lower thermal conductivities than other rock types as a result of this natural insulating effect temperature gradients in carbonaceous strata may become elevated even under conditions of low to average heat flow causing underlying rocks to reach higher temperatures and higher thermal maturities than would otherwise occur this hypothesis was tested by determining the weighted average thermal conductivity of a carboniferous coal bearing section from the conemaugh group of the appalachian basin coals from the sampled section yielded low thermal conductivity values of 0 2 0 15 wm 1 k 1 when measured with a needle probe apparatus measurements of other carbonaceous units also showed low thermal conductivity values 0 9 0 05 wm 1 k 1 for black shales and 1 2 0 20 wm 1 k 1 for dark gray shales relative abundances of all measured lithologies were estimated from a 288 well database these abundances yielded an average conductivity of 1 6 wm 1 k 1 for the entire conemaugh group geothermal gradients for the conemaugh group estimated from thermal conductivity and heat flow data range from 38 to 47 mk m 1 in good agreement with gradients estimated from the actual thermal maturity of coals the additional temperature increment contributed to underlying rocks by this insulating effect may help explain the anomalous thermal maturity of the appalachian basin reducing the need to call upon excessive burial or higher values of heat flow in the past

the effects of geomorphology and seasonality on the chemistry of carbonate groundwater abstract the equilibrium chemistry of carbonate groundwater at the regional and long term scales of aggregation is affected by geomorphic factors and by the seasonality of temperature and recharge regimes the general trend of ca concentration differences between regions is governed by annual mean air or groundwater temperature and by the nature of the solution system higher concentrations result from the coincident system where carbonate material soil air and water are all present together and lower concentrations from the sequential system where carbonate material occurs downstream of the soil air coincident systems occur in areas where carbonate material is present in the regolith either by natural or human activity where a porous or friable bedrock lies at shallow depth or where soils are shallow sequential systems occur where there is a deep non carbonate regolith where there is a non carbonate cap to the carbonate bedrock or where there is a high water table reductions in equilibrium ca concentration can be caused by low soil air volumes relative to percolation volume this may be particularly significant in cool regions where soils are shallow and clayey and where recharge occurs in short high intensity events

modelling of dripwater hydrology and hydrogeochemistry in a weakly karstified aquifer bath uk implications for climate change studies abstract a better knowledge of dripwater hydrology in karst systems is needed to understand the palaeoclimate implications of temporal variations in mg ca and sr ca of calcareous cave deposits quantitative modelling of drip hydrology and hydrochemistry was undertaken at a disused limestone mine brown s folly mine in sw england overlain by 15 m of poorly karstified jurassic limestones with sub vertical fracturing enhanced by proximity to an escarpment discharge was monitored at 15 sites intermittently from the beginning of 1996 and every 10 20 days from later 1996 to early 1998 samples for hydrochemical parameters ph alkalinity cations anions fluorescence were taken corresponding to a sub set of these data and supplemented by bedrock and soil sampling limited continuously logged discharge and soil water observations three sites covering the range of discharge approximately 1 l s 1 to 1 ml s 1 maximum discharge and hydrochemical behaviours were studied in more detail a quantitative flow model was constructed based on two parallel unit hydrographs responsive and relatively unresponsive to discharge events respectively the linear response and conservative mixing assumptions of the model were tested with hydrogeochemical data dripwaters at many of sites are characterized by evidence of prior calcite precipitation in the flowpath above the mine which in the higher discharging sites diminishes at high flow also at low flow rates dripwaters may access seepage reservoirs enriched in mg and or sr dependent on the site the discharge at all three sites can be approximated by the flow model but in each case hydrochemical data show violations of the model assumptions all sites show evidence of non conservative mixing and there are temporal discontinuities in behaviour which may be stimulated by airlocks generated at low flow enhanced mg ca and sr ca often do relate to low flow conditions but the relationships between climate and hydrogeochemical response are non linear

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

reconstructing palaeoprecipitation from an active cave flowstone several drill cores were obtained from a laminated actively forming flowstone from a shallow cave in austria highly resolved petrographic and geochemical analyses combined with multi annual cave monitoring reveal a distinct sensitivity of flowstone growth and composition to late holocene meteoric precipitation the regular sub millimetre scale lamination consists of thicker translucent laminae and thinner organic inclusion rich laminae there is also a macroscopic millimetre scale banding of darker and lighter bands comprising several laminae stable isotope analyses of drill cores and modern calcite precipitates show a pronounced positive covariation of 13c and 18o values indicative of kinetic isotope effects comparing the isotope values with petrography shows gradual changes across several of the annual laminae i e changes of several per mille on a multi annual to decadal timescale the stable isotope and trace element composition as well as the flowstone petrography are mainly controlled by the variable drip water discharge controlling the water film thickness and water residence time on the flowstone surface and consequently the intensity of co2 degassing kinetic isotope enrichment and concomitant calcite precipitation drill core pfu6 provides an isotope record of the last ca 3000 years at near annual resolution a distinct phase of low c and o isotope values interpreted as increased discharge and hence higher meteoric precipitation occurred from ca 300 to 140 a b2k second half of the little ice age and another wet interval occurred around 700 a corresponding to reported medieval glacier advances the roman warm period was also dominated by relatively wet conditions although significant decadal variability prevailed increased precipitation further characterized the intervals from ca 2480 to 2430 and 2950 to 2770 a dry conditions persisted during the medieval climate anomaly although this trend towards reduced precipitation started earlier the highest c isotope values of the last 2 ka are recorded around 750 a and another dry phase is centred at 1480 a this new record shows that inter annual to decadal oscillations are a dominant mode of variation during the last 3 ka in the alps copyright 2011 john wiley sons ltd

a detailed 31 000 year record of climate and vegetation change from the isotope geochemistry of two new zealand speleothems abstract uranium series dating and stable isotope analyses of two speleothems from northwest nelson new zealand record changes in regional climate and local forest extent over the past 31 000 years oxygen isotope variation in these speleothems primarily represents changes in the meteoric waters falling above the caves possibly responding to latitudinal changes in the position of the subtropical front in the tasman sea seven positive excursions can be identified in the oxygen isotope record which coincide with periods of glacier advance known to be sensitive to northward movement of the subtropical front four glacier advances occurred during oxygen isotope stage 2 with the most extreme glacial conditions centered on 19 000 cal yr b p 2 an excursion in the oxygen isotope record from 13 800 to 11 700 cal yr b p provides support for a previously identified new zealand glacier advance at the time of the younger dryas stade but suggests it began slightly before the younger dryas as recorded in greenland ice cores carbon isotope variations in the speleothems record changes in forest productivity closely matching existing paleovegetation records on the basis of vegetation changes stage 2 glacial climate conditions terminated abruptly in central new zealand from 15 700 to 14 200 cal yr b p evidence of continuous speleothem growth at one site suggests that depression of the local treeline was limited to 600 700 m below its present altitude throughout the last 31 000 years

vertical movements of the crust case histories from the northern appalachian basin evidence of former deep burial of ordovician to devonian strata of the northern appalachian basin has been obtained from various techniques of study including fluid inclusion homogenization temperatures 18 o and vitrinite reflectance diagenetic minerals indicate paleotemperatures of 100 200 c maximum depths of burial were calculated from the estimated paleotemperatures a gradient of 26 c km was assumed silurian strata of the basin are interpreted to have reached maximum burial depths of 5 0 km devonian strata in the catskill mountains had former burial depths of 6 5 km lower ordovician carbonate sequences were buried to 7 km middle ordovician strata had paleodepths of 5 km and devonian carbonate strata had paleodepths from 4 5 to 5 km if these strata were buried deeper than previously thought unexpectedly large amounts of uplift and erosion ranging from 4 3 to 7 km must also have taken place to bring these strata to the present land surface the occurrence of such large scale vertical movements of the crust and lithosphere must be recognized in paleogeographic reconstructions such drastic changes represent isostatic unroofing with widespread implications for paleogeography of a kind unrecognized at present

mechanisms controlling rupture shape during subcritical growth of joints in layered rocks during joint propagation the orientation of plume lines on joint faces allows for mapping the path taken by the crack tip line during rupture growth rupture shapes in layered clastic sediments of the devonian catskill delta finger lakes district new york indicate joint growth through three stages where velocity of the tip line v tl varies as a function of the crack tip stress intensity k i the initial stage of growth is characterized by a rupture of approximately circular or elliptical shape that expands from an initiation fl aw with a velocity v tl in some cases primary growth involves self correction where an elliptical rupture redistributes the crack tip stress so that the rupture returns to a more stable circular shape the crack tip line eventually propagates to a bedding interface where properties of either a plastic or a noncohesive bedding interface cause v tl 0 along a portion of the tip line the onset of secondary growth occurs when the rupture tip line intersects both bedding interfaces and splits into two discontinuous segments that propagate synchronously as a single coherent rupture nonuniform nonsystematic v tl eventually interferes with the rupture s ability to grow coherently and thus leads to the transition to tertiary growth characterized by the detachment of the coherent rupture into one or more independently propagating noncoherent tip lines throughout all three stages of rupture growth the k i dependent v tl points to subcritical propagation variation from a smooth to rough plume morphology is consistent with propagation through region i of the subcritical regime with a transition at v tl 10 5 m sec rupture velocity may enter region ii of the subcritical regime but such a broad range of k i must be crossed to reach region iii and quasistatic behavior at the critical stress intensity k ic that region ii acts as a barrier through which few joints pass thus greatly limiting the number of postcritical joints in the catskill delta if not in the crust of the earth

the carbon isotope composition of atmospheric co 2 in paris one characteristic of air pollution in the urban environment is high co2 concentrations resulting from human activities determining the relative contributions of the different co2 sources can be addressed simply and elegantly by combining isotope and concentration measurements using this approach on atmospheric co2 samples collected in paris its suburbs and the open country provides fairly accurate conclusions our results show that air pollution within the first few metres above ground results basically from binary mixtures among which road traffic is the main contributor and in particular vehicles using unleaded gasoline 90 of the total heating sources which account for 50 of the co2 input below the atmospheric inversion level and vehicles using diesel contribute very little human respiration has a recognisable signature at street level under certain circumstances the combined isotope and concentration analysis provides a sensitive tracer of local variations even detecting the occasional prevalence of human respiration and the onset of actions in which natural gas is burnt it also detects surprising inlets of clean air co2 wise in the very centre of the city

consumption of atmospheric methane in a limestone cave in indiana usa abstract recent observations suggest that karst landscapes may be an unaccounted sink for atmospheric ch4 but questions remain about the processes contributing to sub atmospheric ch4 mole fractions in caves the ch4 dynamics associated with karst environments were studied over 18 months at 6 locations in buckner cave southern indiana by measuring the mole fractions and stable isotopic composition of ch4 and carbon dioxide co2 co2 mole fractions were used to infer seasonal changes in airflow samples were obtained on a monthly basis ch4 mole fractions ranged from 1 9 0 1 ppm near the cave entrance to 0 1 0 1 ppm in the more remote parts of the cave the carbon and hydrogen stable isotopic compositions of ch4 in the cave ranged from 58 7 to 7 vpdb and 170 to 10 vsmow respectively the isotopic data suggest that the ch4 dynamics of buckner cave can be described by a seasonally variable mixing system in which atmospheric ch4 enters primarily through the main entrance and is subsequently consumed by methanotrophs additionally at least two smaller ch4 sources are evident when air has been stagnant the results suggest that subterranean karst cavities are an important sink for atmospheric ch4

comment and reply on time temperature burial significance of devonian anthracite implies former great 6 5 km depth of burial of catskill mountains new york

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

fission track analysis of apatite and zircon defines a burial depth of 4 to 7 km for lowermost upper devonian catskill mountains new york apatite and zircon grains separated from a sandstone layer of earliest late devonian age catskill mountains have been subjected to fission track analysis a 125 m y age obtained on the apatite grains requires a temperature for the sediment of less than 120 c during the past 125 m y at some time prior to 125 m y ago temperatures were above 120 c long enough to cause complete fading of tracks analysis of zircon grains resulted in a fission track age of 320 m y zircon data indicate that the temperature of the sediment layer enclosing the grains did not exceed 175 to 200 c over a 235 rn y period time between sedimentation and 125 m y ago if one assumes a typical geothermal gradient of 25 c km a burial depth of between 4 and 7 km is indicated for the lowermost upper devonian atskill mountains

millennial scale asian monsoon variability during the late marine isotope stage 6 from hulu cave china a precisely 230 th dated stalagmite 13 c profile from hulu cave china is presented to characterize the frequency and pattern of millennial scale asian monsoon am variability from 160 6 to 132 5 ka evidence for an antiphased relationship of the 13 c and 18 o on the millennial scale suggests that the 13 c is indicative of the local hydrological cycle associated with changes in am strength owing to the 13 c responding to am changes more sensitively than the 18 o we could identify 15 strong am events that correlate to cold intervals recorded in antarctic ice cores within 230 th dating uncertainty this result supports a dynamic link of am strength and southern hemispheric climates via the cross equatorial airflows power spectrum analysis shows a predominant periodicity of 1 5 2 5 ka for the 13 c profile similar to the dansgaard oeschger frequency during the last glacial period moreover the am events are characterized by rapid transitions at the onset suggesting that the observed millennial scale am variability is likely forced by northern high latitude climates via north south shifts of the intertropical convergence zone associated with the bipolar seesaw mechanism as evidence for a common mechanism for ice age terminations a strong am event 134 ka surrounding termination ii is analogous to the bolling allerod warming interval

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

geochemical evolution of groundwater in the unsaturated zone of a karstic massif using the pco2 sic relationship summary in karstic environments groundwater is strongly influenced by co 2 partial pressure variations of air present in the infiltration zone of these aquifers in order to characterize the geochemical changes in groundwater as it moves through the infiltration zone we monitored various rising springs in the perched karstic aquifer of cussac dordogne france and measured the co 2 partial pressure in air of a nearby cavity the cussac cave for 24 months our method is based on the relationship between the saturation index with respect to calcite sic and the co 2 partial pressure at atmospheric equilibrium with water we distinguished a value for this last parameter when water is at equilibrium with respect to calcite sic 0 called saturation co 2 partial pressure the use of this parameter can provide information on flow conditions and relationships between water air and rock cussac aquifer is a suitable area to apply these methods because of its small size numerous springs and a cave that provides data for co 2 partial pressure condition inside the massif results show that most of the calcium carbonate mineralization is acquired in the epikarst followed by a precipitation phase in the upper part of the infiltration zone groundwater reaches the saturated zone with some degree of saturation depending on co 2 partial pressure variations in air inside the massif

precise dating of dansgaard oeschger climate oscillations in western europe from stalagmite data the signature of dansgaard oeschger events millennial scale abrupt climate oscillations during the last glacial period is well established in ice cores and marine records but the effects of such events in continental settings are not as clear and their absolute chronology is uncertain beyond the limit of 14 c dating and annual layer counting for marine records and ice cores respectively here we present carbon and oxygen isotope records from a stalagmite collected in southwest france which have been precisely dated using 234u 230th ratios we find rapid climate oscillations coincident with the established dansgaard oeschger events between 83 000 and 32 000 years ago in both isotope records the oxygen isotope signature is similar to a record from soreq cave israel and deep sea records indicating the large spatial scale of the climate oscillations the signal in the carbon isotopes gives evidence of drastic and rapid vegetation changes in western europe an important site in human cultural evolution we also find evidence for a long phase of extremely cold climate in southwest france between 61 2 0 6 and 67 4 0 9 kyr ago

monitoring of selected caves as a prerequisite for the speleothem based reconstruction of the quaternary environment in croatia abstract quaternary palaeo environmental changes that have taken place in croatia are likely to be recorded in speleothems secondary carbonate deposits precipitated in caves confident interpretation of well dated speleothem proxy records relies on modern monitoring programs which we provided in three regionally different caves parallel monitoring of the surface and cave air temperature and relative humidity precipitation and cave drip intensity as well as stable isotope modification of meteoric and drip water was carried out in order to estimate the most reliable stalagmites for the interpretation of quaternary landscape history in all three caves nova grgosova 239 m a s l t cave 11 2 c in central croatia lokvarka 780 m a s l t cave 7 5 c in the mountainous part of croatia and modric 32 m a s l t cave 16 6 c in coastal croatia we selected the parts of the caves where the ambient cave conditions appeared to be appropriate for equilibrium deposition of calcite in terms of constant air temperature seasonal amplitudes of 0 73 0 38 and 0 45 c respectively and relative humidity 100 both atlantic and mediterranean moisture influences were detected in all three caves but of different intensities cave hydrological settings governed by karst aquifer properties were resolved by the comparison of the precipitation intensities and drip site responses to the rain events and generally seasonal rainwater isotopic signal was almost completely attenuated except for one drip site such homogenized drip water and stable cave environmental settings give confidence for calcite deposition under equilibrium conditions especially for modric and nova grgosova caves where speleothems inner structures also look promising for potentially quality dating results and stable isotopic profiles the fracture flow drip regime of selected drip sites in lokvarka cave and uncompleted homogenization of the water in the epikarst might point to speleothem samples that are unsuitable for resolving multi annual quaternary climate changes this view is supported by the high porosity internal structure of some lokvarka speleothems so further monitoring sampling and the thorough speleothem examination is therefore necessary for adequate interpretations of palaeo environmental changes