variations in the discharge and organic matter content of stalagmite drip waters in lower cave bristol six drip waters which were actively depositing stalagmites in lower cave bristol were analysed both for discharge and luminescence properties drip discharges were determined for two different years and show a complex response to surface precipitation variations inter annual variability in drip discharge is demonstrated to be significantly higher than intra annual variability and discharge was demonstrated both to increase and decrease non linearly with increased precipitation drip waters demonstrate a correlation between their luminescence intensity and drip discharge with increased luminescence in winter as more organic matter is flushed through the aquifer the strength of the relationship between luminescence intensity and discharge increases with increased discharge the results presented here have implications for the palaeoenvironmental interpretation of annual growth laminae and the growth rates of stalagmite samples 1997 john wiley sons ltd

an irrigation experiment to compare soil water and speleothem tetraether membrane lipid distributions measurement of glycerol dialkyl glycerol tetraethers gdgts preserved in speleothems offers a potential proxy for past temperature but in general their origin is unknown to understand the source of speleothem gdgts we undertook an irrigation experiment to activate drip sites within a hydrogeochemically well characterised cave the cave drip water was analysed for gdgts inorganic elements major ions and trace elements stable isotopes and dissolved organic matter concentration and character published speleothem gdgt records from the site have been observed to be dominated by isoprenoid gdgts and interpreted as deriving from in situ microbial communities within the cave or vadose zone the drip water in our irrigation experiment had a gdgt distribution distinct from that of soil and speleothem samples providing direct evidence that the distinctive gdgt signature in speleothems is derived from a subsurface source analysis of gdgts in this context allowed further elucidation of their source and transport in cave systems enhancing our understanding of how they might be used as a temperature proxy

speleothern luminescence intensity and spectral characteristics signal calibration and a record of palaeovegetation change abstract the intensity and spectral characteristics of speleothem luminescence are investigated for signs of any potential palaeoenvironmental signals luminescence in speleothems has been demonstrated to have an organic acid source acids being transported from the overlying soil to the speleothem via the groundwater system luminescence spectral characteristics confirm a humic fulvic acid source of the luminescence but are unable to distinguish between plant acids derived from different vegetation systems spectral characteristics also differ between solid and dissolved speleothem calcite the influence of six factors on luminescence intensity are considered changes in organic acid concentration organic acid structural type depth of the sample below the surface dilution effects through changes in water discharge rate dilution effects through changes in speleothem growth rate and the effects of luminescence quenching due to the presence of metal ions in a holocene stalagmite sample from sutherland a period of low luminescence intensity is observed which is demonstrated to correlate with periods of blanket bog expansion recorded in the regional pollen record this suggestion is supported by a study of 18 recently deposited samples from northwest europe and 5 cave water samples feeding stalagmites in a british cave when a relationship to vegetation is evident with very low luminescence intensity observed from sites overlain by blanket bog deposits this is thought to be due to both low organic acid concentrations in feedwaters and also the low luminescence efficiency of the humic acids from bog sites due to their structural characteristics

sedimentary and structural evidence for 2 7 ga continental arc oceanic arc collision in the savant sturgeon greenstone belt western superior province canada the western superior province sustained rapid crustal growth in the interval 2 72 2 68 ga through amalgamation of microcontinental crustal blocks and juvenile oceanic terranes recent field isotopic and geophysical surveys provide insight on the nature timing and scale of this accretionary growth however few places offer the rich tectono stratigraphic and structural detail with which to establish accretion of oceanic and continental blocks as does the savant sturgeon area here 3 4 2 8 ga continental crust of the winnipeg river terrane is juxtaposed with 2 775 2 718 ga juvenile oceanic rocks of the western wabigoon terrane across a 2 85 2 75 ga southwest facing continental margin sequence the continental margin was reactivated at 2 715 ga with the establishment of an arc recorded by 2 715 2 70 ga tonalite and associated intermediate volcanic rocks this magmatic activity is interpreted to reflect north and east dipping subduction that led to consumption of a small tract of oceanic crust betwe

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

trace elements in speleothems as recorders of environmental change speleothems are now established as important palaeoenvironmental archives and contain a number of suitable proxies although trace elements have been much less widely used than oxygen and carbon isotopes the complexity of the cave environment helps to explain this since the fluids from which speleothems form vary greatly in composition in space even within a cave chamber seasonally and over longer periods understanding the forcing factors for this variability is the key to decoding the significance of the trace element records a variety of techniques are available for trace element work and it is important to understand the strengths and limitations of each and also to seek an understanding e g by micro imaging techniques of whether the elements are associated with inclusions in the caco3 or are isolated within the crystal lattice for some elements there is a more or less predictable relationship between element ratios to ca in the water and in the calcite individual trace elements may be derived from atmospheric deposition superficial deposits or bedrock and can be recycled in soil processes before being transferred to the cave some components show an instantaneous response to water infiltration whereas others are only leached by slow flowing seepage waters changing in the proportion of water from fracture fed and seepage flow aquifer compartments is an important factor in influencing trace element supply high flows lead to higher fluxes of soil derived colloidally transported elements conversely under relatively dry conditions degassing of co2 results in prior calcite precipitation upflow of the site of speleothem deposition and leads to higher ratios of sr ca and mg ca some trace element variations in speleothems over time are induced during crystal growth whereby faster growth leads to a greater departure from equilibrium element partitioning despite the demonstrated temperature dependence of mg partitioning into calcite attempts at deriving palaeotemperature records from speleothems have been so far confounded by variations in solution mg ca and or crystallographic effects a number of case studies have effectively used trace elements such as speleothem mg as records of palaeo aridity using supporting arguments from modern monitoring or covariations with other parameters such as stable isotopes sr and u isotopes can also be indicators of palaeohydrology although sr isotope variations can also reflect varying aeolian input considerable progress has been made in decoding the meaning of annual trace element variations using criteria for understanding dripwater hydrology and ph this should lead in the future to more specific interpretations of how seasonality evolves through time

speleothems and climate a special issue of the holocene speleothems cave dripstones are formed as a part of the meteoric water cycle and therefore vari ations in their growth rate and composition reflect environmental changes on the land surface above the cave since they are continental deposits and possess a remarkably accurate dating potential using tims u series techniques speleothems are important palaeoclimatic archives for the terrestrial environment complementing the marine and ice core records the climatic proxies that can be deciphered from speleothems are growth rate stable isotope composition d18o d13c organic humic matter and trace element composition as well as luminescent laminae which may display annual rhythms the nine papers in this special issue oftheholocene present the latest results in palaeoclimatic analysis from speleothems

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

molecular organic matter in speleothems and its potential as an environmental proxy abstract organic matter preserved in speleothems has considerable potential to record changes in the surrounding environment particularly in the overlying vegetation here we review three types of organic matter analysis relevant to speleothems organic fluorescence lipid biomarker analysis and amino acid racemisation organic matter luminescence provides a useful non destructive and rapid method for assessing dissolved organic matter quantity and quality while biomarker analysis amino acids and lipids has the potential to provide a more detailed signal related to specific parts of the surrounding ecosystem such as the dominant vegetation regime and bacterial activity amino acid analysis has yet to prove demonstrably useful in stalagmites due to the inability to characterise the sources of proteinaceous matter however the small but increasing body of work on lipid biomarker analysis in stalagmites has shown that a wide variety of recognisable biomarkers are preserved over long periods of time 100 ka can be recovered at temporal resolutions of

late holocene annual growth in three alpine stalagmites records the influence of solar activity and the north atlantic oscillation on winter climate annual growth rates and the ratio of dark to light colored calcite within single annual laminae in three contemporaneously deposited holocene speleothems from grotta di ernesto an alpine cave in northern italy respond to changes in surface temperature rather than precipitation based on monitoring of present day calcite growth and correlation with instrumental data for surface climatic conditions we interpret a higher ratio of dark to light colored calcite and the simultaneous thinning of annual laminae as indicative of colder than present winters such dark and thin laminae occur in those parts of the three stalagmites deposited from ad 1650 to 1713 and from ad 1798 to 1840 as reconstructed through lamina counting these periods correspond to the well known maunder and dalton minima of solar activity an 11 yr cyclicity in growth rate coupled with reduced calcite deposition during the historic minima of solar activity is indicative of a solar influence on lamina thickness spectral analysis of the lamina thickness data also suggests that the north atlantic oscillation variability influenced winter temperatures based on the present day controls on cave calcite formation we infer that high frequency changes in solar activity modulated the seasonal duration of soil co2 production

hydrogeochemistry and fractionation pathways of mg isotopes in a continental weathering system lessons from field experiments abstract the potential of magnesium isotope records from cave carbonate archives speleothems has been documented but remains underexplored this is due to the limited knowledge regarding the complex suite of physico chemical and biological disequilibrium fractionation processes affecting meteoric fluids in the soil zone the carbonate hostrock and calcite precipitation in the cave this study presents 26 mg data from a monitored cave in germany bunker cave including rain water 26 mg 0 70 0 14 soil water 26 mg 0 51 0 10 and drip waters 26 mg 1 65 0 08 sampled between november 2009 and may 2011 field precipitation experiments i e calcite precipitated on watch glasses 26 mg 3 56 0 26 may 2006 to june 2010 were found to be of limited use this is because of experimental crystallographic and sampling artefacts conversely variations in soil and drip water 26 mg over time are predominantly related to seasonal variations in water availability and air temperature affecting the subtle weathering ratio between mg bearing clay minerals in the soil here mainly chlorite and montmorillonite and the low mg calcite hostrock bunker cave 26 mg drip water values display a significant dependency on the air temperature outside the cave this is because air temperature influences co 2 levels in the soil and hence rock water interaction for fast drip sites the direct correlation of 26 mg soil water and 26 mg drip water documents a relative short residence time of the fluid in the carbonate aquifer and thus limited isotope equilibration and mixing of different reservoirs this result is encouraging and adds new evidence to the poorly understood hydro geochemistry of carbonate aquifers slow seepage flow drip sites display an annual 26 mg drip water pattern that is geochemically unrelated to that of the soil water further research including laboratory experiments must focus on the complex fractionation between drip water and speleothem calcite mg isotope record

a cromerian complex stalagmite from the mendip hills england in order to provide a better chronological constraint on a british middle pleistocene interglacial a large stalagmite boss from the mendip hills was selected for palaeoclimate data using pollen analysis dating analyses by thermal ionisation mass spectrometry tims of uranium thorium ratios and by magnetostratigraphy constrain the age of the sample to 450 780 ka the isotopic consistency of the tims analyses plus the presence of luminescence laminations suggest that the sample has been preserved under closed system conditions pollen assemblages have been recovered from the speleothems despite the fact that the ph of calcite deposition is usually greater than 7 furthermore the evidence presented here indicates that the pollen was probably transported by the speleothem feedwater rather than entering the cave aerially the pollen record contained within the stalagmite is interpreted as early mid interglacial but does not have clear cromerian affinity 1997 john wiley sons ltd

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

isotopic characterization of cave environments at varying altitudes on the eastern adriatic coast croatia implications for future speleothem based studies abstract an important step in the implementation of paleoclimate reconstructions from speleothems cave carbonate deposits is to evaluate the sensitivity of the host cave environment to regional climate accordingly we studied three caves at different altitudes 74 m 570 m and 1250 m a s l along a transect from the dalmatian islands to velebit mountain peaks in coastal croatia to characterize their environments in terms of each cave s suitability to host speleothems that would be capable of yielding robust paleoclimate reconstructions we conducted cave microclimate 2 years and dripwater 1 year monitoring and analysed the isotopic composition of precipitation cave dripwater and modern spelean calcite as for the water isotopic imprints the isotopic values of meteoric waters reaching the two lower altitude caves in spite of an altitude difference of 500 m lie on local meteoric water lines lmwls of similar slope and intercept 2 h 6 61 18 o 4 92 and 2 h 6 69 18 o 6 86 their slopes lower than that of gmwl indicate enhanced evaporation during the warm season as expected the lmwl of the highest cave region 2 h 7 83 18 o 14 45 resembles the slope of the gmwl but the values of deuterium excess obtained for all three caves between 15 2 and 16 6 match that of western mediterranean sourced waters 15 monthly d excess values suggest atlantic sourced air masses can reach the sites throughout the year but never dominate the rainfall composition the altitude effect was noted both in precipitation and in dripwater isotopic composition but with notably different 18 o 100 m gradients 0 33 and 0 11 respectively stable isotope variations of the dripwaters in all caves were attenuated in relation to the rainwater even those of the drip sites with fracture flow behaviour based on stable cave microclimate conditions relatively steady discharges and modern calcite apparently precipitated at or close to isotopic equilibrium with dripwater the two caves at lower altitudes show the greatest potential for future paleoclimate studies the cave at the highest altitude experiences large cave air temperature amplitudes 5 3 c and pronounced ventilation making the isotopic signal susceptible to kinetic fractionation which might preclude quantification of environmental changes but on the other hand it accentuates isotopic events making them easier to identify

luminescent microbanding in speleothems high resolution chronology and paleoclimate when illuminated by ultraviolet light many calcite speleothems stalagmites stalactites flowstones display luminescence caused by the presence of organic humic substances occluded in the calcite the amplitude of luminescence varies in a banded pattern parallel to growth layering through 14 c and thermal ionization mass spectrometry uranium series dating we show that cyclical oscillations in the luminescence have periodicities ranging from a few days to 10 5 yr a well defined annual cycle is present in many vadose zone speleothems and can be used to define the chronology of short term events this cycle is probably a response to hydrological events in the recharge to the cave longer term oscillations are inferred to be controlled by climate through its effect on organic activity in the overlying soil

sensitivity of bunker cave to climatic forcings highlighted through multi annual monitoring of rain soil and dripwaters abstract the last two decades have seen a considerable increase in studies using speleothems as archives of past climate variability caves under study are now monitored for a wide range of environmental parameters and results placed in context with speleothem data the present study investigates trends from a seven year long monitoring of bunker cave northwestern germany in order to assess the hydraulic response and transfer time of meteoric water from the surface to the cave rain soil and dripwater were collected from august 2006 to august 2013 at a monthly to bimonthly resolution and their oxygen and hydrogen isotope composition was measured furthermore drip rates were quantified due to different drip characteristics annual mean values were calculated for the drip rates of each drip site correlations of the annual mean drip rate of each site with precipitation and infiltration demonstrate that the annual infiltration and thus the annual precipitation control the inter annual drip rate variability for all except one site the hydraulic response is not delayed on an annual basis all drip sites display identical long term trends which suggests a draining of a common karst reservoir over these seven years of monitoring correlations of soil and dripwater monthly 18o and d values with atmospheric temperature data reveal water transfer times of 3 months to reach a depth of 40 cm soilwater at site bw 2 and 4 months for 70 cm depth soilwater at site bw 1 finally the water reaches the cave chambers 15 to 30 m below land surface after ca 2 5 years consequently a temporal offset of 29 to 31 months ca 2 5 years between the hydraulic response time no time lag on annual basis and the water transfer time time lag of 29 to 31 months was found which is negligible with regard to bunker cave speleothems because of their slow growth rates here proxies recording precipitation infiltration and temperature are registered on a decadal scale variations in drip rate and thus precipitation and infiltration are recorded by 13c and mg ca ratios in speleothem calcite speleothem 18o values reflect both temperature and precipitation signals due to drip rate related fractionation processes we document that long term patterns in temperature and precipitation are recorded in dripwater patterns of bunker cave and that these are linked to the north atlantic oscillation nao

the hekla 3 volcanic eruption recorded in a scottish speleothem recent research has demonstrated the presence of annual luminescent growth banding in a stalagmite from sutherland n w scotland baker smart edwards and richards 1993 the banding record of this sample contains a short duration increase in annual band width indicating a doubling of growth rate for a period of four years predicted growth rates derived from calcite precipitation kinetics are compared with observed growth rate variability to demonstrate that such a doubling of growth rate would not be expected within the probable range of normal climate variation the growth rate peak is dated to 1135 130 bc by thermal ionization mass spectrometric 238u 234 u 230th dating not inconsistent with the timing of the hekla 3 volcanic eruption this event may explain the observed variation in growth rate and provide a new source of evidence for interpretation of the effects of large explosive eruptions

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

paleoclimate implications of mass spectrometric dating of a british flowstone the timing of growth phases in a cave flowstone from yorkshire england has been precisely dated by thermal ionization mass spectrometric 238u 234u 230th dating six growth periods of both short duration and fast growth rate are separated by nondepositional hiatuses the ages of these phases were determined to be 128 8 2 7 103 1 1 8 84 7 1 2 57 9 1 5 49 6 1 3 and 36 9 0 8 ka there is a remarkably good correlation between the periods of active speleothem growth and the timing of solar insolation maxima derived from orbital parameters which has not previously been reported speleothem growth theory and evidence from other terrestrial paleoclimate records suggest that episodic rapid growth phases at the insolation maxima are most likely to be caused by changes in either precipitation intensity or volume which caused switching in the routing of water flow in the unsaturated zone above the cave such a result provides new evidence of the importance of variations in solar insolation for terrestrial paleoclimate and offers the potential for derivation of a paleowetness index from speleothem growth

solute transport processes in a karst vadose zone characterized by long term tracer tests the cave system of postojnska jama slovenia summary the processes influencing the solute transport in the karst vadose zone were studied by long term tracer tests with artificial tracers the results of three successive tracer tests with different modes of injection were compared tracer breakthrough curves were monitored at three drips of different hydrological types inside one of the cave galleries of the system of postojnska jama over several years comparison of the results indicates the highly significant influence of preceding hydrological conditions dry vs wet injection mode artificial flushing vs natural infiltration by subsequent rainfall and on a bare rock vs on an overlying layer and geologic heterogeneities within the vadose zone on solute transport in the karst vadose zone injection with artificial flushing resulted in rapid infiltration and the tracer traversed almost one hundred meters of bedrock in hours however the majority of tracer can be stored within less permeable parts of the vadose zone and then gradually flushed out after additional abundant and intensive precipitation in the period of several years long continued sampling in each of the tests proved to be important for reliable characterization of the long term solute transport dynamics

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

spatial variability in cave drip water hydrochemistry implications for stalagmite paleoclimate records the identification of vadose zone hydrological pathways that most accurately transmit climate signals through karst aquifers to stalagmites is critical for accurately interpreting climate proxies contained within individual stalagmites a three year cave drip hydrochemical study across a spectrum of drip types in crag cave sw ireland reveals substantial variability in drip hydrochemical behaviour stalagmites fed by very slow drips 2 ml min sites apparently unconnected with local meteorological events water from these drips was typically undersaturated with respect to calcite and thus did not result in calcite deposition data presented here suggest that drips in this flow regime also experience flow re routing and blocking and that any stalagmites developed under such drips are unsuitable as mid to high resolution paleoclimate proxies most drip sites demonstrated seasonal ca2 and mg2 variability that was probably linked to water excess prior calcite precipitation along the flowpath affected the chemistry of slowly dripping sites while dilution predominantly controlled the water chemistry of the more rapidly dripping sites this research underscores the importance of understanding drip hydrology prior to selecting stalagmites for paleoclimate analysis and before interpreting any subsequent proxy data

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

annual growth banding in a cave stalagmite the presence of microscopic luminescence banding in cave calcite deposits speleothems has recently been reported1 3 the luminescence seems to be caused by excitation of humic and fulvic acids derived from the overlying soil and subsequently incorporated into the calcite3 4 we have tested whether such luminescence corresponds to annual growth layers using high precision thermal ionization mass spectrometric 238u 234u 230 th ages from banded sections of a holocene stalagmite we report here that the timespans yielded by counting bands on the assumption that they are annual agree within error limits with those obtained by our uranium thorium dating this demonstration that the banding is annual should make banded speleothems valuable resources for providing high resolution records of past climate in which precipitation can be estimated from growth rates5 6 and temperatures from stable isotope measurements7 and solar terrestrial correlations as the luminescence intensity can be related to the solar sunspot cycle1 3

high resolution characterization of the asian monsoon between 146 000 and 99 000 years b p from dongge cave china and global correlation of events surrounding termination ii abstract speleothem samples from hulu eastern china 32 30 n 119 10 e and dongge southern china 25 17 n 108 5 e caves provide a nearly continuous record of the asian monsoon over the last 160 ka wang y j cheng h edwards r l an z s wu j y shen c c dorale j a 2001 a high resolution absolute dated late pleistocene monsoon record from hulu cave china science 294 2345 2348 yuan d cheng h edwards r l dykoski c a kelly m j zhang m qing j lin y wang y wu j dorale j a an z cai y 2004 timing duration and transitions of the last interglacial asian monsoon science 304 575 578 we have obtained higher resolution data in the interval between 99 and 146 ka b p providing a detailed account of 18o variations over most of mis 5 and the latter portion of mis 6 precise 230th dating has replicated the chronology of the samples within error the higher resolution data set confirms the timing of asian monsoon termination ii the midpoint of the negative shift in 18o marking the onset of the last interglacial asian monsoon placing it at 129 0 0 9 ka b p the bulk of this transition 1 7 took place within approximately 70 years with the total range of the transition being 3 the most abrupt portion of the shift in 18o values 1 1 marking the end of the last interglacial asian monsoon occurred in 120 years the midpoint of which is 120 7 1 0 ka b p the dongge cave monsoon 18o record over late mis 6 exhibits a series of sub orbital millennial scale climate shifts that average 1 3 in magnitude and occur on average every 1 8 ky abrupt shifts in 18o of up to 1 also occurred throughout the last interglacial asian monsoon with periods at multi decadal to centennial timescales similar to the amplitude and periodicities of events found by dykoski et al dykoski c a edwards r l cheng h yuan d cai y zhang m lin y an z revenaugh j 2005 a high resolution absolute dated holocene and deglacial asian monsoon record from dongge cave china earth and planetary science letters 233 71 86 during the holocene in the dongge record these shifts cover more than 1 2 of the amplitude of millennial scale and multi centennial scale interstadial events during the last glacial period wang y j cheng h edwards r l an z s wu j y shen c c dorale j a 2001 a high resolution absolute dated late pleistocene monsoon record from hulu cave china science 294 2345 2348 and millennial scale and multi centennial scale interstadial events during the penultimate glacial period in china this study abrupt decadal to millennial scale climate events therefore appear to be a general feature of both glacial and interglacial climate we demonstrate that monsoon intensity correlates well with atmospheric ch4 concentrations over the transition into the bolling allerod the bolling allerod and the younger dryas in addition we correlate an abrupt jump in ch4 concentration with asian monsoon termination ii on the basis of this correlation we conclude that the rise in atmospheric co2 antarctic warming and the gradual portion of the rise in ch4 around termination ii occur within our weak monsoon interval wmi an extended interval of heavy 18o between 135 5 1 0 and 129 0 1 0 ka b p prior to asian monsoon termination ii and northern hemisphere warming antarctic warming over the millennia immediately preceding abrupt northern warming may result from the bipolar seesaw mechanism as such warming albeit to a smaller extent also preceded asian monsoon termination i the bipolar seesaw mechanism may play a critical role in glacial terminations

stalactite growth mediated by biofilms example from nani cave cayman brac british west indies growth lines evident in cross sections through stalactites from nani cave provide a temporal record of their growth many of these dark organic rich laminae developed as biofilms that are recognized by the presence of 1 a diverse microbial biota that is dominated by actinomycetes 2 calcified filaments 3 films formed of extracellular polymeric substances eps 4 grain coating sheets of calcite crystals that grew in eps 5 biterminal calcite crystals and 6 etching this biosignatures suite encompasses a variety of constructive and destructive processes where fully developed the features generated by the biofilms form a distinctive microstratigraphic succession collectively 50 m thick which can be traced laterally across the stalactite s surface the use of speleothems in paleoclimate studies is commonly framed against a chronology that relies at least in part on annual growth couplets the dark organic rich lamina that forms one part of the growth couplet is typically ascribed to abiotic precipitation that incorporated exogenic organic matter that was flushed into the cave following the first major rainfall of the wet season this assumption ignores the possibility that dark organic rich growth laminae can be the record of biofilms that developed on the surface of the stalactites and hence may not be a record of annual events

paleohydrological records from peat profiles and speleothems in sutherland northwest scotland abstract paleohydrological changes during the late holocene are inferred from humification testate amoebae and pollen evidence from three blanket peat profiles in northwest scotland replicate peat humification records from the traligill basin share the same patterns of change for a 600 yr period of overlap between 1800 and 2400 cal yr b p the shared patterns inferred from samples with a resolution of 5 13 yr represent basinwide hydrological changes in a nearby but hydrologically separate area with caves beneath peat the luminescence emission wavelength measured in two speleothem samples correlated with the humification record in the overlying peat this correlation implies that speleothem luminescence emission wavelength depends primarily on decay rates in the soils from which drip waters are derived as long as there is no major change in soil or vegetation the peat and speleothem records from the cave site further correlate with the peat records from the traligill basin taken together the records thus represent a regional climatic signal peaks in surface wetness replicated in two or more records occur at ca 2300 2090 2030 1820 1600 and 1440 cal yr b p further peaks occur at 800 570 and 115 cal yr b p in the humification and stalagmite records that extend to the present day correlative changes have been observed not only in other peat records from scotland but also in ice accumulation at gisp2 these further correlations imply that precipitation regimes in scotland and greenland were in phase during the late holocene

comparative application of two methods cop and paprika for groundwater vulnerability mapping in mediterranean karst aquifers france and spain a comparative test of two vulnerability mapping methods cop and paprika specifically dedicated to for karst aquifers was carried out on two mediterranean carbonate aquifers the vulnerability maps obtained for each aquifer present important differences to identify and determine the origin of these differences the results were statistically analyzed using sensitivity analysis coefficients of determination and scatter graphs in addition the global vulnerability gv parameter was used to measure the general vulnerability of the aquifer and to compare the results obtained this statistical analysis led us to conclude that the main cause of differences between these two methods used to assess aquifer vulnerability lie in the relative importance of the parameters employed in calculating the vulnerability index for the paprika method the variable related to infiltration slope and karst features has the most influence with less weight being assigned to the protective capacity of layers overlying the aquifer for the cop method the most influent variable is defined by the layers overlying the aquifer together with infiltration characteristics determined by the relative importance of different forms of infiltration in each aquifer the vulnerability mappings performed using the cop method present greater coherence with the known hydrogeological behavior of the study areas especially the spanish aquifers nevertheless further hydrogeological investigations are needed such as ones to validate the obtained vulnerability maps

non linearities in drip water hydrology an example from stump cross caverns yorkshire drip rate data have been collected at 15 min intervals at six locations in stump cross caverns n england since 1998 the different drip sites cover a wide range of drip rates from 2 drips s to 2 drips h and in general the variability of drip rate increases with mean drip rate in our continuous data sampling we observe rapid discharge increases which appear to be synchronous between drips sites and which can be explained by flow switching of the water overlying the cave during times of high infiltration rate such as intense rain storms or rapid snowmelt a test for non linearity white test in the drip series provides very strong evidence that many of the drip sequences are non linear we conclude that at our drip sites there is a non linear input weather and non linearities within the karst system leading to non linear dripping which is independent of drip rate our results have implications for stalagmite palaeoclimatology where such widespread non linearities have not been taken account of

comparison of the luminescence properties of waters depositing flowstone and stalagmites at lower cave bristol discharge and luminescence properties of waters feeding a flowstone in lower cave bristol were measured at both three weekly and 30 minute sampling intervals within rainfall events over the period april 1994 april 1995 and july december 1995 respectively results are compared with the discharge and luminescence of lower 0 01 ml s 1 feeding flowstones when 30 minute sampling results are considered dilution and hysteresis effects can be observed in the discharge luminescence relationship both on an intra event basis and over the winter as a whole exhaustion of organic matter within the karst groundwater system over the hydrological year may also be important a very rapid flux of luminescent organic matter in early autumn generates a non linear order of magnitude change in water luminescence intensity flowstone water luminescence properties can be interpreted as having i higher concentrations of luminescent organic matter compared with stalagmites from luminescence intensity data 2 a greater proportion of humic acid in relation to fulvic acid from luminescence wavelength data 3 a more rapid response to surface rainfall events and 4 a consequently greater proportion of non linear responses to surface rainfall variations these results are considered in terms of the utility of the analysis of luminescence variations in solid samples of stalagmites and flowstones in aiding the reconstruction of past rainfall variations and it is suggested that stalagmites are more useful than flowstones

controls on water drop volume at speleothem drip sites an experimental study summary the growth of speleothem under cave drip sites is closely related to local climate events and provides an increasingly important means of deciphering past climate change since calcite precipitation rates depend on the water discharge at the drip site the drip rate and mass of water drops detaching from stalactites are fundamental controls on speleothem growth and we have investigated factors that control the volume of water drops in this environment the classical investigations on the volume of falling water drops are reviewed but there have been no measurements of the volume of drops detaching from curved surfaces equivalent to tips of stalactites in this study we have used an acoustic drop counting method to measure the variation of the mass of water drops detaching from tubes representing soda straw stalactites and artificial stalactites with spherical terminations representing massive stalactites as a function of tube radius or surface curvature and the drip rate the experimental method corroborates classical measurements of drop mass detaching from tubes and for massive stalactites we derive a simple empirical relationship between drop mass and radius of curvature of a spherical surface based on 100 000 drop counts from artificial stalactites with 19 different radii ranging from 3 6 mm to 500 mm the results of this study allow discharge to be calculated from drip interval measurements and provide a quantitative basis for theoretical modelling of speleothem growth from drip sites

applications of stalagmite laminae to paleoclimate reconstructions comparison with dendrochronology climatology abstract laminated stalagmites observed in either ultra violet or visible light or recognized via trace elements are now widely recognized as a common deposition form annually laminated stalagmites should be expected in caves which have an overlying climate that has a strong seasonality similar climate zones to where trees grow with distinct annual rings continuous laminated stalagmite chronologies up to several thousand years should be expected where some mixing of stored water occurs such stalagmites can be used to reconstruct climate particularly through variations in lamina width such climate records would be relatively damped by mixing of event water with stored groundwater constraining the amount of high frequency climate signals contained in the stalagmite but relatively long continuous lamina sequences permit the preservation of low frequency centennial scale climate signals this contrasts with numerous tree ring climate records which are frequently limited in preserving multi centennial trends due to the necessary removal of age related noise from relatively short tree segments laminated stalagmites and tree rings should therefore to some degree provide complementary climate information appropriate methods for compiling stalagmite layer chronologies and climatologies are presented

mass spectrometric dating of flowstones from stump cross caverns and lancaster hole yorkshire palaeoclimate implications a terrestrial flowstone sequence 97 cm thick from stump cross caverns yorkshire has been dated by both mass spectrometric and alpha spectrometric 238u 234u 230th dating and is demonstrated to have been deposited predominantly during interstadial periods over the last 170 ka with no growth in periods of glaciation or within the oxygen isotope stage 5 interglacial growth also occurs within oxygen isotope stages 4 and 6 the former possibly correlating with interstadials recognised in high resolution ice and ocean core records comparison with the timing of growth of a mass spectrometrically dated lancaster hole flowstone also from the same region demonstrates only limited agreement these differences are due to two factors limiting deposition at stump cross flooding of the cave passage in warm periods and the development of continuous permafrost or glacier cover in periods of severe climatic deterioration deposition at lancaster hole was controlled by limitations in ground water supply rather than flooding of the cave passage the results presented here demonstrate that in addition to regional palaeoclimate factors local site conditions may limit speleothem growth we conclude that in future palaeoclimate studies the growth record from several coeval speleothem samples must be considered before a regional palaeoclimate interpretation can be made

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

a high resolution multi proxy stalagmite record from mechara southeastern ethiopia palaeohydrological implications for speleothem palaeoclimate reconstruction an annually laminated stalagmite from southeastern ethiopia grew for 443 8 yr starting at 5023 yr bp 160 yr as determined by lamina tuned u th dating the speleothem shows three growth phases 1 an initial phase where the stalagmite has a candlestick shape deposited by relatively slow rate drip water 2 a middle growth phase where laminae grow on the flanks suggesting faster drip rates and 3 a final growth phase where the speleothem becomes narrower owing to a decrease in drip water supply towards the end of deposition morphometry annual growth rate fluorescence index and 234u 238u isotope ratio show marked differences between the growth phases while 13c and 18o do not show significant variation except within the third phase towards the top of the stalagmite where they have higher values the study indicates that the multiproxy approach is crucial as the different proxies respond to single climate forcing in different manners our results can be widely applied to speleothem studies distinguishing the relative importance of the various proxies in recording cave external climate hydrology and cave internal e g evaporation processes copyright 2006 john wiley sons ltd

fluorescence intensity variations of speleothem forming groundwaters implications for paleoclimate reconstruction groundwater discharges onto 16 speleothems and surface climate parameters have been measured in an oolitic limestone site in england groundwater recharge is demonstrated to lag behind periods of hydrologically effective precipitation by 30 50 days with the exception of short periods of high rainfall intensity or quantity summer rainfall has no effect on groundwater discharge onto the speleothems because of the development of a soil moisture deficit the first groundwater fluorescence intensity increase was demonstrated to lag the autumn increase in groundwater discharge by 10 20 days suggesting that the first groundwater comprises old stored groundwater whereas later water derives from the overlying soil and has a high organic acid concentration despite the lags the structure of autumn and winter moisture availability is reflected within the annual fluorescence intensity variations suggesting that fluorescent organic acids when trapped within speleothem calcite may provide a proxy for past winter moisture variations for temperate latitudes

organic acid fluorescence applications to speleothem palaeoenvironmental reconstruction abstract recent advances in fluorescence spectrophotometry permit the non destructive analysis of speleothems secondary carbonate cave deposits with a view to palaeoenvironmental reconstruction the fluorescence of speleothems is derived from organic acids that have been carried by groundwater from the overlying soil and coprecipitated with the speleothem calcite organic acids are formed as one of the many products of humification and their chemical structures are such that they are particularly suitable for analysis by fluorescence spectrophotometry numerous studies have been carried out that have demonstrated the structure and hence the fluorescence properties of organic acids to be influenced by many factors including extraction method concentration source ph metal and inorganic ion complexing and most importantly in the case of speleothems soil type and climate and vegetation change on the basis of this recent investigations carried out on contemporary historical and quaternary samples have shown it to be possible to obtain palaeoenvironmental information from the fluorescence properties of organic acids in speleothems

molecular signatures of dissolved organic matter in a tropical karst system karst areas are widespread landforms present on all continents formed by the dissolution of carbonate or evaporite host rock little is known about the composition and nature of dissolved organic matter dom as it moves through karst systems although karst dom has been recognized as important for a range of natural processes microbial communities living in karst systems are some of the most diverse and intriguing on the planet and their metabolism and life cycle can give clues related to the development of a host of different life forms karst areas are also of interest due to their mostly subterranean hydrology and the repercussions of these processes on local carbon cycles we illustrate some of the processes acting on dom in karst waters through the analysis of soil drip and cave pool waters at the tropical site of yok balum cave in southern belize water samples were analyzed using ultra high resolution electrospray ionization fourier transform ion cyclotron resonance mass spectrometry esi ft icr ms a technique that enables the resolution of single molecular formulae within a dom spectrum we perform multivariate statistics to detect trends in the data and identify provenance of detected molecular components in addition to karst waters four aliquots of a powdered stalagmite sample from the same cave system are analyzed our results show a clear gradient between the soil and the cave system we hypothesize that both sorption on mineral surfaces and microbial reworking are responsible for the observed trend in dom composition the stalagmite extracts show an anomalous dom pattern which may be due to a variety of factors including microbial activity on the stalagmite surface and different affinities of compounds to incorporation in the carbonate the goal of this study was to follow the molecular transformations of dom on its journey from the surface to the cave and to provide a molecular basis for the establishment of stalagmite dom proxies in karst systems

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