Textural and carbon isotopic evidence of monsoonal changes recorded in a composite-type speleothem from Korea since MIS 5a     

Kyoung-nam Jo  Hai Cheng  Yongjin Wang  Xiuyang Jiang 《Quaternary Research》2010,74(1):100-66

Textural and stable isotopic records of a composite-type speleothem from Gwaneum Cave in the eastern part of the Korean peninsula show prominent paleoenvironmental changes since MIS (marine oxygen isotope stage) 5a. Based on ²³⁰Th/²³⁴U dating, the speleothem experienced growth from 90.9 ± 6.5 ka to 1.2 ± 0.5 ka with several hiatuses. Four growth phases (A, B, C and D) are recognized based on speleothem type and texture. Very irregular and laterally discontinuous growth laminae in Phases B and C indicate that the cave coralloids grew over the stalagmite (Phase A) when the supply of dripping water became limited. Variations within the δ¹³C time series of Phase A are interpreted as responses to millennial-scale fluctuations of the East Asian monsoon intensity during MIS 5a. The monsoonal interpretation is based on the idea that δ¹³C values reflect the isotopic composition of soil-derived CO₂, which, in turn, should relate to monsoon-driven changes in terrestrial productivity above the cave during the MIS 5a. Our reconstruction reveals that the significant monsoonal changes on the Korean peninsula occurred in conjunction with changes in sea level and/or oceanic circulations during the transition period from MIS 5a to MIS 4.  相似文献   

Several distinct wet periods since 420 ka in the Namib Desert inferred from U-series dates of speleothems     

Mebus A. Geyh  Klaus Heine 《Quaternary Research》2014

The scarcity of numerical dates of the arid areas in southern Africa is a challenge for reconstructing paleoclimate. This paper presents a chronological reconstruction in the central part of the Namib Desert, Namibia, for the last 420,000 yr. It is based on ²³⁰Th/U dates (TIMS) from a large stalagmite and a thick flowstone layer in a small cave located in the hyper-arid central Namib Desert. The results provide for the first time evidence of three or possibly four succeeding wet periods of decreasing intensity since 420 ka through which speleothem deposited at approximately 420–385 ka, 230–207 ka and 120–117 ka following the 100-ka Milankovitch cycle. Speleothem growth was not recorded for the Holocene. These wet periods interrupted the predominantly dry climate of the Namib Desert and coincided with wet phases in deserts of the northern hemisphere in the Murzuq Basin, Sahara, the Negev, Israel, the Nafud Desert, Saudi Arabia, and the arid northern Oman, Arabian Peninsula.  相似文献   

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments   总被引：2，自引：0，他引：2  

A. Immenhauser  D. Buhl  A. Niedermayr  M. Dietzel 《Geochimica et cosmochimica acta》2010,74(15):4346-74

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ²⁶Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ²⁶Mg values of loess-derived soil above the cave (−1.0 ± 0.5‰), soil water (−1.2 ± 0.5‰), the carbonate hostrock (−3.8 ± 0.5‰), dripwater in the cave (−1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; −4.3 ± 0.6‰), cave loam (−0.6 ± 0.1‰) and runoff water (−1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000lnα_Mg-cc-Mg(aq) = −2.4‰. A similar Mg-isotope fractionation (1000lnα_Mg-cc-Mg(aq) ≈ −2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, ²⁶Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg²⁺ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.  相似文献   

ESR and Th/U dating of speleothems from Aladağlar Mountain Range (AMR) in Turkey     

Ülkü Ulusoy  Gül Anbar  Serdar Bayarı  Tonguç Uysal 《Quaternary Research》2014

Electron spin resonance (ESR) and ²³⁰Th/²³⁴U ages of speleothem samples collected from karstic caves located around 3000 m elevation in the Alada?lar Mountain Range (AMR), south-central Turkey, were determined in order to provide new insight and information regarding late Pleistocene climate. ESR ages were validated with the ²³⁰Th/²³⁴U ages of test samples. The ESR ages of 21 different layers of six speleothem samples were found to range mostly between about 59 and 4 ka, which cover the Marine Oxygen Isotope Stages (MIS) MIS 3 to MIS 1. Among all, only six layers appear to have deposited during MIS 8 and 5. Most of the samples dated were deposited during the late glacial stage (MIS 2). It appears that a cooler climate with a perennial and steady recharge was more conducive to speleothem development rather than a warmer climate with seasonal recharge in the AMR during the late Quaternary. This argument supports previous findings that suggest a two -fold increase in last glacial maximum mean precipitation in Turkey with respect to the present value.  相似文献   

The timing of sea-level high-stands during Marine Isotope Stages 7.5 and 9: Constraints from the uranium-series dating of fossil corals from Henderson Island     

Morten B. Andersen  Claudine H. Stirling  Emma-Kate Potter  Steve G. Blake  Bridget F. Ayling 《Geochimica et cosmochimica acta》2010,74(12):3598-7020

Direct dating of fossil coral reefs using the U-series chronometer provides an important independent test of the Milankovitch orbital forcing theory of climate change. However, well-dated fossil corals pre-dating the last interglacial period (>130 thousand years ago; ka) are scarce due to, (1) a lack of sampling localities, (2) insufficient analytical precision in U-series dating methods, and (3) diagenesis which acts to violate the assumption of closed-system U-series isotopic decay in fossil corals. Here we present 50 new high-precision U-series age determinations for fossil corals from Henderson Island, an emergent coral atoll in the central South Pacific. U-series age determinations associated with the Marine Isotope Stage (MIS) 9 interglacial and MIS 7.5 interstadial periods are reported. The fossil corals show relatively little open-system U-series behaviour in comparison to other localities with fossil coral reefs formed prior to the last glacial cycle, however, open-system U-series behaviour is still evident in most of the dated corals. In particular, percent-level shifts in the [²³⁰Th/²³⁸U]_act composition are observed, leading to conventional U-series ages that are significantly younger or older than the true sample age. This open-system U-series behaviour is not accounted for by any of the open-system U-series models, indicating that new models should be derived. The new U-series ages reported here support and extend earlier findings reported in Stirling et al. (2001), providing evidence of prolific coral reef development on Henderson Island at ∼320 ka, most likely correlated with MIS 9.3, and subsequent reef development at ∼307 ka during MIS 9.1, while relative sea-level was potentially ∼20 m lower than during MIS 9.3. The U-series ages for additional well-preserved fossil corals are suggestive of minor reef development on Henderson Island during MIS 7.5 (245-230 ka) at 240.3 ± 0.8 and 234.7 ± 1.3 ka. All U-series observations are consistent with the Milankovitch theory of climate change, in terms of the timing of onset and termination of the dated interglacial and interstadial periods. The best preserved samples also suggest that the oceanic ²³⁴U/²³⁸U during MIS 9 and MIS 7.5 was within five permil of the modern open ocean composition.  相似文献   

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

Edward J. Hodge  David A. Richards  Peter L. Smart  Bartolom Andreo  Dirk L. Hoffmann  Dave P. Mattey  Antonio Gonzlez-Ramn 《Quaternary Research》2008,69(3):447-457

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

Paleoclimate and growth rates of speleothems in the northwestern Iberian Peninsula over the last two glacial cycles     

Heather M. Stoll  Ana Moreno  Ana Mendez-Vicente  Saul Gonzalez-Lemos  Montserrat Jimenez-Sanchez  Maria Jose Dominguez-Cuesta  R. Lawrence Edwards  Hai Cheng  Xianfeng Wang 《Quaternary Research》2013

Speleothem growth requires humid climates sufficiently warm to stimulate soil CO₂ production by plants. We compile 283 U/Th dates on 21 stalagmites from six cave systems in the NW coast of Spain to evaluate if there are patterns in stalagmite growth that are evidence of climatic forcing. In the oldest stalagmites, from marine oxygen isotope stage (MIS) 7–5, growth persists through the glacial period. Hiatuses and major reductions in growth rate occur during extreme minima in summer insolation. Stalagmites active during the last interglaciation cease growth at the MIS 5–4 boundary (74 ka), when regional sea-surface temperature cooled significantly. During MIS 3, only two stalagmites grew; rates were highest between 50 and 60 ka during the maximum in summer insolation. One stalagmite grew briefly at 41 ka, 36.5 and 28.6 ka, all during warm phases of the Dansgaard–Oeschger cycles. A pronounced Holocene optimum in stalagmite growth occurs from 9 to 6 ka. The cessation of most growth by 4.1 ka, coincident with broad increases in aridity over the Mediterranean and areas influenced by the North African Monsoon, suggest that regions such as NW Spain, with dominant Atlantic moisture sources, also experienced increased aridity at this time.  相似文献   

Timing of glaciation and last glacial maximum paleoclimate estimates from the Fish Lake Plateau, Utah     

David W. Marchetti  M. Scott Harris  Thure E. Cerling 《Quaternary Research》2011,75(1):183-195

The High Plateaus of Utah include seven separate mountain ranges that supported glaciers during the Pleistocene. The Fish Lake Plateau, located on the eastern edge of the High Plateaus, preserves evidence of at least two glacial advances. Four cosmogenic ³He exposure ages of boulders in an older moraine range from 79 to 159 ka with a mean age of 129 ± 39 ka and oldest ages of 152 ± 3 and 159 ± 5 ka. These ages suggest deposition during the type Bull Lake glaciation and Marine Oxygen Isotope Stage (MIS) 6. Twenty boulder exposure ages from four different younger moraines indicate a local last glacial maximum (LGM) of ~ 21.1 ka, coincident with the type Pinedale glaciation and MIS 2. Reconstructed Pinedale-age glaciers from the Fish Lake Plateau have equilibrium-line altitudes ranging from 2950 to 3190 m. LGM summer temperature depressions for the Fish Lake Plateau range from −10.7 to −8.2°C, assuming no change in precipitation. Comparison of the Fish Lake summer temperature depressions to a regional dataset suggests that the Fish Lake Plateau may have had a slight increase (~ 1.5× modern) in precipitation during the LGM. A series of submerged ridges in Fish Lake were identified during a bathymetric survey and are likely Bull Lake age moraines.  相似文献   

Speleothem evidence of warm episodes in northeast France during Marine Oxygen Isotope Stage 3 and implications for permafrost distribution in northern Europe     

Edwige Pons-Branchu  Bruno Hamelin  Stephane Jaillet 《Quaternary Research》2010,74(2):246-251

U-Th ages have been obtained by TIMS on the growth periods of a stalagmite from the “Grotte des Puits de Pierre-la-Treiche” (northeastern France), during the middle part of the “Weichselian glaciation” (Marine Isotope Stage 3), between 55.36 ± 0.95 and 53.34 ± 0.49 ka and around 45.85 ± 0.49 ka. These episodes are contemporaneous with abrupt climatic variations recorded in Greenland ice cores (Greenland interstadials 12, 14 and 15) that have been previously recognized in European speleothems. They also coincide with two interstadials, known as “Goulotte” and “Pile” in the Grande Pile pollen sequence (eastern France), which have been correlated with the Moershoofd complex in the Netherlands. Such evidence of speleothem deposition related to temperate episodes gives a strong indication of the absence of continuous shallow permafrost during the middle part of MIS 3 in northeastern France.  相似文献   

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

K. Wainer  D. Genty  D. Blamart  M. Daëron  M. Bar-Matthews  H. Vonhof  Y. Dublyansky  E. Pons-Branchu  L. Thomas  P. van Calsteren  Yves Quinif  N. Caillon 《Quaternary Science Reviews》2011,30(1-2):130-146

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

Carbon and oxygen stable isotope compositions of late Pleistocene mammal teeth from dolines of Ajoie (Northwestern Switzerland)     

Laureline Scherler  Thomas Tütken  Damien Becker 《Quaternary Research》2014

Fossils of megaherbivores from eight late Pleistocene ¹⁴C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51–27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ¹³C values for both periods, ranging from − 14.5 to − 9.2‰, indicate that the megaherbivores lived in a C₃ plant-dominated environment. Enamel δ¹⁸O_PO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ¹⁸O_PO4–δ¹⁸O_H2O-calibrations for modern mammals and a present-day precipitation δ¹⁸O_H2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51–27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures.  相似文献   

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada     

L.A. Neymark  Y.V. Amelin 《Geochimica et cosmochimica acta》2008,72(8):2067-2089

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of ²³⁸U and ²³²Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my⁻¹) contain excess ²⁰⁶Pb and ²⁰⁸Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable ²⁰⁶Pb/²³⁸U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect ²⁰⁷Pb/²³⁵U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages.Opal and calcite from outer (younger) portions of coatings have ²³⁰Th/U ages from 94.6 ± 3.7 to 361.3 ± 9.8 ka and initial ²³⁴U/²³⁸U activity ratios (AR) from 4.351 ± 0.070 to 7.02 ± 0.12, which indicate ²³⁴U enrichment from percolating water. Present-day ²³⁴U/²³⁸U AR is ∼1 in opal/chalcedony from older portions of the coatings. The ²⁰⁷Pb/²³⁵U ages of opal/chalcedony samples range from 0.1329 ± 0.0080 to 9.10 ± 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my⁻¹, in good agreement with previous results. Measured ²³⁴U/²³⁸U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ± 0.006 to 2.091 ± 0.006 and are >1 in most samples. The range of ⁸⁷Sr/⁸⁶Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool.In the U-poor calcite samples, measured ²⁰⁶Pb/²⁰⁷Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both ²⁰⁶Pb and ²⁰⁷Pb derived from Rn diffusion and from direct α-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains ²⁰⁶Pb and ²⁰⁸Pb excesses, but no appreciable ²⁰⁷Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect ²⁰⁶Pb-²³⁸U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.  相似文献   

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

Eleonora Regattieri  Giovanni Zanchetta  Russell N. Drysdale  Ilaria Isola  John C. Hellstrom  Adriano Roncioni 《Quaternary Research》2014

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

Speleothem calcite farmed in situ: Modern calibration of δO and δC paleoclimate proxies in a continuously-monitored natural cave system     

Darrel M. Tremaine  Philip N. Froelich 《Geochimica et cosmochimica acta》2011,75(17):4929-4950

Understanding the relationships between speleothem stable isotopes (δ¹³C δ¹⁸O) and in situ cave forcing mechanisms is important to interpreting ancient stalagmite paleoclimate records. Cave studies have demonstrated that the δ¹⁸O of inorganically precipitated (low temperature) speleothem calcite is systematically heavier than the δ¹⁸O of laboratory-grown calcite for a given temperature. To understand this apparent offset, rainwater, cave drip water, groundwater, and modern naturally precipitated calcite (farmed in situ) were grown at multiple locations inside Hollow Ridge Cave in Marianna, Florida. High resolution micrometeorological, air chemistry time series and ventilation regimes were also monitored continuously at two locations inside the cave, supplemented with periodic bi-monthly air gas grab sample transects throughout the cave.Cave air chemistry and isotope monitoring reveal density-driven airflow pathways through Hollow Ridge Cave at velocities of up to 1.2 m s⁻¹ in winter and 0.4 m s⁻¹ in summer. Hollow Ridge Cave displays a strong ventilation gradient in the front of the cave near the entrances, resulting in cave air that is a mixture of soil gas and atmospheric CO₂. A clear relationship is found between calcite δ¹³C and cave air ventilation rates estimated by proxies pCO₂ and ²²²Rn. Calcite δ¹³C decreased linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ¹³C_CaCO3 = −7‰. A whole-cave “Hendy test” at multiple contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ¹³C offset between calcite precipitated in a ventilation flow path and calcite precipitated on the edge or out of flow paths. This interpretation of the “Hendy test” has implications for interpreting δ¹³C records in ancient speleothems. Calcite δ¹³C_CaCO3 may be a proxy not only for atmospheric CO₂ or overlying vegetation shifts but also for changes in cave ventilation due to dissolution fissures and ceiling collapse creating and plugging ventilation windows.Farmed calcite δ¹⁸O was found to exhibit a +0.82 ± 0.24‰ offset from values predicted by both theoretical calculations and laboratory-grown inorganic calcite. Unlike δ¹³C_CaCO3, oxygen isotopes showed no ventilation effects, i.e. Δδ¹⁸O_CaCO3 appears to be a function of growth temperature only although we cannot rule out a small effect of (unmeasured) gradients in relative humidity (evaporation) accompanying ventilation. Our results support the findings of other cave investigators that water-calcite fractionation factors observed in speleothem calcite are higher that those measured in laboratory experiments. Cave and laboratory calcite precipitates may differ mainly in the complex effects of kinetic isotope fractionation. Combining our data with other recent speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments: