Evidence of rainfall variations in Southern Brazil from trace element ratios (Mg/Ca and Sr/Ca) in a Late Pleistocene stalagmite

Trace element ratios in the Bt2 stalagmite from Botuverá cave, Southern Brazil, are explored as a proxy for changes in the local rainfall recharge during the last 116 ky. BP Mg/Ca and Sr/Ca ratios, measured with an electron microprobe, are significantly positively correlated with one another throughout the entire record, and vary in a way that is very consistent with variations of δ¹⁸O in the same speleothem during the last glacial period. We suggest that prior calcite precipitation in the vadose zone of the cave system is the main factor affecting the incorporation of Mg and Sr into calcite of the stalagmite. This interpretation is supported by trace element correlation patterns and by results from a hydrochemistry study performed in a cave located in the same region and in a similar environmental setting. Therefore, we conclude that higher (lower) Mg/Ca and Sr/Ca values are associated with lower (higher) levels of recharge into the karstic aquifer, as such conditions lead to an increase (decrease) in the volume of calcite precipitated in the unsaturated zone above the cave during dry (wet) climate periods.Trace element variations point to generally dryer (wetter) conditions during lower (high) phases of summer insolation in the southern hemisphere. These periods coincide with decreased (increased) activity of the South American summer monsoon, as revealed by δ¹⁸O stalagmite records. In addition trace element variations show that rather wet conditions persisted throughout most of the last glacial period from approximately 70 to 17 ky BP. We suggest that during this period the glacial boundary conditions, especially ice volume buildup in the northern hemisphere, played an important role for monsoon rainfall intensification in the region.     

Modeling speleothem δC variability in a central Sierra Nevada cave using C and Sr/Sr

Carbon isotopes in speleothems can vary in response to a number of complex processes active in cave systems that are both directly and indirectly related to climate. Progressing downward from the soil zone overlying the cave, these processes include soil respiration, fluid-rock interaction in the host limestone, degassing of CO₂ and precipitation of calcite upflow from the speleothem drip site, and calcite precipitation at the drip site. Here we develop a new approach to independently constrain the roles of water-rock interaction and soil processes in controlling stalagmite δ¹³C. This approach uses the dead carbon proportion (dcp) estimated from coupled ¹⁴C and ²³⁰Th/U measurements, in conjunction with Sr isotope analyses on stalagmite calcite from a central Sierra Nevada foothills cave in California, a region characterized by a highly seasonal Mediterranean-type climate, to determine the roles of water-rock interaction and soil processes in determining stalagmite δ¹³C. Increases in stalagmite dcp between 16.5 and 8.8 ka are coincident with decreased δ¹³C, indicating a varying yet substantial contribution from the soil organic matter (SOM) reservoir, likely due to significantly increased average age of SOM in the soil veneer above the cave during wet climatic intervals.We use geochemical and isotope mixing models to estimate the host-carbonate contribution throughout the δ¹³C time series and determine the degree of degassing and calcite precipitation that occurred prior to precipitation of stalagmite calcite. The degree of degassing and prior calcite precipitation we calculate varies systematically with other climate indicators, with less degassing and prior calcite precipitation occurring during wetter climatic intervals and more during drier intervals. Modeled δ¹³C values and degassing calculations suggest that some degree of prior calcite precipitation is necessary at all time intervals to explain measured stalagmite δ¹³C values, even during relatively wet intervals. These results illustrate the importance of constraining degassing and prior calcite precipitation in the interpretation of speleothem δ¹³C records, particularly those from caves that formed in seasonal semi-arid to arid environments.     

Ostracod Mg/Sr/Ca and 87Sr/86Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering

Jin, Z. D., Bickle, M. J., Chapman, H. J., Yu, J., An, Z., Wang, S. & Greaves, M. J. 2010: Ostracod Mg/Sr/Ca and ⁸⁷Sr/⁸⁶Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering. Boreas, 10.1111/j.1502‐3885.2010.00184.x. ISSN 0300‐9483 Lacustrine sediment serves as a valuable archive for tracing catchment weathering processes associated with past climatic and/or tectonic changes. High‐resolution records of fossil ostracod Mg/Ca, Sr/Ca and ⁸⁷Sr/⁸⁶Sr ratios from a lake sediment core from the central Tibetan Plateau reveal a temporal link between lake‐water chemistry and catchment weathering and distinct monsoonal oscillations over the early to mid‐Pleistocene. Between 2.01 and 0.95 Ma, lake‐water chemistry was dominated by a high proportion of carbonate weathering related to variations in the Indian monsoon, resulting in relatively low and constant ostracod ⁸⁷Sr/⁸⁶Sr but obvious fluctuations in Mg/Ca, Sr/Ca and δ¹⁸O. Across the mid‐Pleistocene transition (MPT), a significant increase in ⁸⁷Sr/⁸⁶Sr and frequently fluctuating ratios of ostracod Mg/Ca, Sr/Ca and δ¹⁸O are coincident with increases in both Chinese loess grain size and Arabian Sea lithogenic flux. This correlation indicates an increased glaciation and a strong monsoon seasonal contrast over the plateau. The increase in lake‐water ⁸⁷Sr/⁸⁶Sr across the MPT highlights a change in catchment weathering patterns, rather than one in climate‐enhanced weathering intensity, with an increased weathering of ⁸⁷Sr‐rich minerals potentially induced by marked extensive glaciation and strong seasonality in the central plateau.     

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

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.     

Sr isotopic and elemental characteristics of calcites in the Chinese deserts: Implications for eolian Sr transport and seawater Sr evolution

Calcite content, Sr concentrations, and isotopes of calcites in the Chinese deserts are systematically studied in this paper. Calcite contents, which are calculated according to acid-soluble Ca contents in the deserts, are generally higher in the sandy deserts than in the sandy lands and decrease roughly from northwest to northeast of China. Acid-soluble Sr is well correlated with calcite in the Chinese deserts, implying acid-soluble Sr comes mainly from the calcite dissolution. Sr concentrations in calcites, calculated on the basis of calcite contents and acid-soluble Sr concentrations in the deserts, have an inverse relation to calcite contents, essentially mirroring the degree of Sr substitution for Ca in the calcite development. Desert calcites have regional variations in Sr isotopic ratios. Calcite Sr isotopic ratios depend on geological settings and chemical weathering. The Badain Jaran, and Tengger deserts are probably affected by additional factors such as the remote groundwater cycle or overturning of underlying sand deposits.Only four deserts (Taklimakan, Qaidam, Badain Jaran, and Tengger) appear to be potential sources of eolian deposits in the Chinese Loess Plateau (CLP). Isotopic signatures of calcite Sr and silicate Nd further indicate that the Tengger desert was not an important source for eolian deposits in the CLP. Eolian calcite was probably enriched due to wind sorting from the potential sources to the CLP and suffered weathering–leaching after it accumulated in the CLP. Sr isotopic compositions and Ca/Sr molar ratios of calcites are different between the deserts and the Lingtai profile, due to the integrated effect of wind sorting and weathering–leaching.It is essential to calculate accurately the ⁸⁷Sr/⁸⁶Sr ratio and Sr concentration of eolian calcite entering the oceans according to geochemical data of the Chinese deserts, because of the importance of the Chinese deserts in the global dust cycle. The calculated Sr concentration and ⁸⁷Sr/⁸⁶Sr ratio of eolian calcite entering the North Pacific Ocean, are 11.75 μmol/g and 0.71032, respectively. The calculated values in this study are close to the recommended values by Jacobson [Jacobson A. D. (2004) Has the atmospheric supply of dissolved calcite dust to seawater influenced the evolution of marine ⁸⁷Sr/⁸⁶Sr ratios over the past 2.5 million years? Geochem. Geophys. Geosyst. 5(12), 1–9, Q12002. doi:10.1029/2004GC000750]. Using the same model as that of Jacobson (2004), the effect of Asia dust on the evolution of seawater Sr isotopes is evaluated. (⁸⁷Sr/⁸⁶Sr)_seawater increases by 0.3 × 10⁻⁵ if the lower dust flux of 2.34 × 10⁸ mol Sr/yr is used in the model, suggesting the little effect of Asian dust on the seawater Sr record in the Quaternary. The increase in (⁸⁷Sr/⁸⁶Sr)_seawater is 1.5 × 10⁻⁵ if the higher value of 1.17 × 10⁹ mol Sr/yr is used, as observed in the Quaternary Sr record. These results further support the suggestions of Jacobson (2004).     

Adsorbed silica in stalagmite carbonate and its relationship to past rainfall

Despite considerable work on other trace elements, the incorporation of dissolved silicon from cave waters into speleothems has not been previously investigated. In this study, the controls on dissolved Si in cave waters and on adsorbed Si in resulting speleothems are therefore investigated. Bedrock (dolomite), soil water, dripping water, and cave carbonates were retrieved from Heshang Cave situated in the central Yangtze valley of China and were subjected to analysis of dissolved Si content (plus accompanying Ca and Fe analyses). Soil waters have Si/Ca of 45.5 mmol/mol, compared to only 3.2 mmol/mol in the dolomite bedrock, demonstrating that >80% of the dissolved Si must come from dissolution of silicate minerals in the soil. Drip waters have a dissolved Si concentration of ≈4.2 μg/mL, similar to that in the overlying soil water. Actively growing cave carbonates have a Si/Ca of 0.075 mmol/mol suggesting a partition coefficient for incorporation of dissolved silicon of 0.0014, in good agreement with previous laboratory studies. Extrapolating the results of these laboratory studies to the cave environment suggests that changes in Si/Ca in cave carbonates are likely to be primarily controlled by changes in drip-water Si/Ca. The drip-water Si/Ca will, in turn, be controlled by the rate of wind-blown silicate supply; by soil weathering rates; by rainfall dilution; and by precipitation of calcite. The general expectation is that these effects combine to produce high Si/Ca in speleothems during times of low rainfall. A δ¹⁸O record from a Heshang Cave stalagmite which grew between 20 and 11 thousand years ago allows these controls to be tested. Correlation of high Si/Ca with high δ¹⁸O demonstrates that regional rainfall exerts significant (but not complete) control on speleothem Si/Ca. With further understanding, speleothem Si/Ca may provide a proxy for past rainfall to complement existing proxies such as δ¹⁸O and Mg/Ca.     

87Sr/86Sr in kimberlitic carbonates by ion microprobe: Hydrothermal alteration,crustal contamination and relation to carbonatite

Carbonates in a 30 cm wide zoned kimberlite dyke from the De Beers Mine, Kimberley, S. Africa were studied by cathodoluminescence and electron microprobe techniques and their ⁸⁷Sr/⁸⁶Sr ratios were measured using an AEI-IM20 ion microprobe. Primary carbonates (including calcite dendrites, rhombohedral calcites in segregation vesicles and mosaic dolomite) have high Sr (0.69–1.35 wt.% SrO) and Ba (0.24–0.44% BaO) and ⁸⁷Sr/⁸⁶Sr ratios in the range 0.7046 to 0.7056. Secondary sparry calcite in amygdales and veins is characterised by low Ba (<0.05% BaO) and ⁸⁷Sr/⁸⁶Sr near 0.72. Rhombohedral calcite 0.5 cm from a contact with 2,900 my. old biotite-gneiss has minor element chemistry like that of primary carbonate, but an elevated ⁸⁷Sr/⁸⁶Sr ratio of 0.7103, possibly indicating crustal contamination in a boundary layer of the kimberlite magma. Amygdale-like segregations of carbonate and/or serpentine originated as gas-cavities and were not formed by liquid immiscibility. They are now filled either by secondary calcite or by minerals precipitated from residual kimberlite liquid. However, dendritic calcite and primary dolomite and calcite with high Sr, Ba and low ⁸⁷Sr/⁸⁶Sr demonstrate shared chemical characteristics between these carbonates and carbonatite. The primary kimberlite magma had initial ⁸⁷Sr/⁸⁶Sr close to 0.7046.     

Seasonal dripwater Mg/Ca and Sr/Ca variations driven by cave ventilation: Implications for and modeling of speleothem paleoclimate records

A 4-year study in a central Texas cave quantifies multiple mechanisms that control dripwater composition and how these mechanisms vary at different drip sites. We monitored cave-air compositions, in situ calcite growth, dripwater composition and drip rate every 4-6 weeks. Three groups of drip sites are delineated (Groups 1-3) based on geochemical variations in dripwater composition. Quantitative modeling of mineral-solution reactions within the host carbonate rock and cave environments is used to identify mechanisms that can account for variations in dripwater compositions. The covariation of Mg/Ca (and Sr/Ca) and Sr isotopes is key in delineating whether Mg/Ca and Sr/Ca variations are dictated by water-rock interaction (i.e., calcite or dolomite recrystallization) or prior calcite precipitation (PCP). Group 1 dripwater compositions reflects a narrow range of the extent of water-rock interaction followed by varying amounts of prior calcite precipitation (PCP). Group 2 dripwater compositions are controlled by varying amounts of water-rock interaction with little to no PCP influence. Group 3 dripwater compositions are dictated by variable extents of both water-rock interaction and PCP. Group 1 drip sites show seasonal variations in dripwater Mg/Ca and Sr/Ca, whereas the other drip sites do not. In contrast to the findings of most previous dripwater Mg/Ca-Sr/Ca studies, these seasonal variations (at Group 1 drip sites) are independent of changes in water flux (i.e., rainfall and/or drip rate), and instead significantly correlate with changes in cave-air CO₂ concentrations. These results are consistent with lower cave-air CO₂, related to cool season ventilation of the cave atmosphere, enhancing calcite precipitation and leading to dripwater geochemical evolution via PCP. Group 1 dripwater Mg/Ca and Sr/Ca seasonality and evidence for PCP as a mechanism that can account for that seasonality, have two implications for many other regions where seasonal ventilation of caves is likely: (1) speleothem trace-element records may provide seasonal signals, and (2) such records may be biased toward recording climate conditions during the season when calcite is depositing. Additionally, we use our results to construct a forward model that illustrates the types of speleothem Mg/Ca and Sr/Ca variations that would result from varying controls on dripwater compositions. The model provides a basis for interpreting paleo-dripwater controls from high frequency Mg/Ca and Sr/Ca variations for speleothems from caves at which long term monitoring studies are not feasible.     

CO clumping in speleothems: Observations from natural caves and precipitation experiments

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ¹⁸O. Interpreting speleothem δ¹⁸O records in terms of absolute paleotemperatures and δ¹⁸O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ₄₇ (a geochemical variable reflecting the statistical overabundance of ¹³C¹⁸O bonds in CO₂ evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ₄₇ value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation.Here we report Δ₄₇ values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ₄₇ and heavier δ¹⁸O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ₄₇ disequilibrium and that of δ¹⁸O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ¹⁸O and Δ₄₇ values, probably inherited from prior degassing within the cave system.In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ₄₇ in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ₄₇ in inorganic carbonates.     

Patterns of Ca/Sr and Sr/Sr variation before and after a whole watershed CaSiO3 addition at the Hubbard Brook Experimental Forest, USA

Forty-one metric tons of the mineral wollastonite (CaSiO₃) was applied to an 11.8 hectare watershed at the Hubbard Brook Experimental Forest (HBEF; White Mountains, New Hampshire, USA) with the goal of restoring the Ca estimated to have been depleted from the soil exchange complex by acid deposition. This experiment provided an opportunity to gain qualitative information on whole watershed hydrologic flow paths by studying the response of stream water chemistry to the addition of Ca. Because the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of wollastonite strongly contrast that of other Ca sources in the watershed, the wollastonite-derived Ca can be identified and its amount estimated in various ecosystem components. Stream water chemistry at the HBEF varies seasonally due to shifts in the proportion of base flow and interflow. Prior to the wollastonite application, seasonal variations in ⁸⁷Sr/⁸⁶Sr ratios indicated that ⁸⁷Sr/⁸⁶Sr was higher during base flow than interflow, due largely to greater amounts of biotite weathering along deeper flow paths. After the application, Ca/Sr and ⁸⁷Sr/⁸⁶Sr changed markedly as the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr wollastonite dissolved and mixed with stream water. The Ca addition provided information on the response times of various flow paths and ion exchange processes to Ca addition in this small upland watershed. During the first year after the addition, wollastonite applied to the near stream zone dissolved and was partially immobilized by cation exchange sites in the hyporheic zone. In the second and third years after the addition we infer that much of this Ca and Sr was subsequently desorbed from the hyporheic zone and was exported from the watershed in stream flow. In the fourth through ninth years after the addition, Ca and Sr from wollastonite that had dissolved in upland soils was transported to the stream by interflow during wet periods when the ground water table was elevated. Between years three and nine the minimum annual Ca/Sr ratio (in late summer base flow) increased, providing evidence that Ca and Sr had increasingly infiltrated to the deepest flow paths. Strong seasonal variations in Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of stream water resulted from the wollastonite addition to upland forest soils, and these ratios have become sensitive to changing flow paths during the annual cycle. Most notably, high flow events now produce large excursions in stream geochemistry toward the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr ratios of wollastonite. Nine years after the application we estimate that ∼360 kg of Ca from wollastonite has been exported from the watershed in stream flow. The rate of export of Ca from wollastonite dissolution has stabilized at about 11 kg of Ca per year, which accounts for ∼30% of the dissolved Ca in the stream water. Given that 19 metric tons of Ca were applied to the watershed, and assuming this current rate of loss, it should take over 1000 years for this added Ca to be transported from the watershed.     

Analysis of coupled Sr/Ca and Sr/Sr variations in enamel using laser-ablation tandem quadrupole-multicollector ICPMS

We present in this study results obtained with a laser-ablation coupled with both a quadrupole and a multi-collector ICPMS. The simultaneous in situ Sr/Ca and ⁸⁷Sr/⁸⁶Sr measurements along growth profiles in enamel allows the concomitant diet and migration patterns in mammals to be reconstructed. Aliquots of the powdered international standard NIST “SRM1400 Bone Ash” with certified Sr and Ca contents, was sintered at high pressure and temperature and was adopted as the reference material for external reproducibility and calibration of the results. A total of 145 coupled elemental and isotopic measurements of herbivores enamel from the Kruger National Park, South Africa, gives intra-tooth Sr/Ca and ⁸⁷Sr/⁸⁶Sr variations that are well larger than external reproducibility. Sr/Ca profiles systematically decrease from the dentine-enamel junction to the outer enamel whereas ⁸⁷Sr/⁸⁶Sr profiles exhibit variable patterns. Using a simple geometric model of hypsodont teeth growth, we demonstrate that a continuous recording of the ⁸⁷Sr/⁸⁶Sr variations can be reconstructed in the tooth length axis. This suggests that the mobility of a mammal can be reconstructed over a period of more than a year with a resolution of a ten of days, by sampling enamel along growth profiles. Our geometric model of hypsodont teeth growth predicts that an optimal distance between two successive profiles is equal to the enamel thickness. However, this model does not apply to the Sr/Ca signal which is likely to be altered during the enamel maturation stage due to differential maturation processes along enamel thickness. Here, the observed constant decreases of the Sr/Ca ratios in the ungulates of Kruger National Park suggests that they did not changed of diet, while some of them were migrating.     

Ca/Sr and Sr isotope systematics of a Himalayan glacial chronosequence: carbonate versus silicate weathering rates as a function of landscape surface age

We explored changes in the relative importance of carbonate vs. silicate weathering as a function of landscape surface age by examining the Ca/Sr and Sr isotope systematics of a glacial soil chronosequence located in the Raikhot watershed within the Himalaya of northern Pakistan. Bedrock in the Raikhot watershed primarily consists of silicate rock (Ca/Sr ≈ 0.20 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.77 to 1.2) with minor amounts of disseminated calcite (Ca/Sr ≈ 0.98 to 5.3 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.79 to 0.93) and metasedimentary carbonate (Ca/Sr ≈ 1.0 to 2.8 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.72 to 0.82). Analysis of the exchangeable, carbonate, and silicate fractions of seven soil profiles ranging in age from ∼0.5 to ∼55 kyr revealed that carbonate dissolution provides more than ∼90% of the weathering-derived Ca and Sr for at least 55 kyr after the exposure of rock surfaces, even though carbonate represents only ∼1.0 wt% of fresh glacial till. The accumulation of carbonate-bearing dust deposited on the surfaces of older landforms partly sustains the longevity of the carbonate weathering flux. As the average landscape surface age in the Raikhot watershed increases, the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios released by carbonate weathering decrease from ∼3.6 to ∼0.20 μmol/nmol and ∼0.84 to ∼0.72, respectively. The transition from high to low Ca/Sr ratios during weathering appears to reflect the greater solubility of high Ca/Sr ratio carbonate relative to low Ca/Sr ratio carbonate. These findings suggest that carbonate weathering controls the dissolved flux of Sr emanating from stable Himalayan landforms comprising mixed silicate and carbonate rock for tens of thousands of years after the mechanical exposure of rock surfaces to the weathering environment.     

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

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.     

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 δ¹³C and δ¹⁸O 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.     

Large variations of δ13C values in stalagmites from southeastern China during historical times: implications for anthropogenic deforestation

Variations in speleothem δ¹³C values can reflect changes in overlying surface vegetation, which, over historical time scales, may represent the influence of human activities. Here, we examined δ¹³C variations in two stalagmites growing for the last 2200 years in Shennong Cave, Jiangxi Province, SE China. The two δ¹³C records corroborate well one another and show a prominent 6‰ enrichment of the δ¹³C values from AD 700 to 1100. The isotopic equilibrium for modern calcite and negative correlation between δ¹⁸O and δ¹³C values along the growth axis suggest that the influences of kinetic fractionation are negligible. Varied correlations between Mg/Ca and Sr/Ca ratios and divergent changes between δ¹³C values and Mg/Ca and Sr/Ca ratios from AD 700 to 1100 reveal that the prior calcite precipitation (PCP) and water–rock interaction did not dominate the increase of δ¹³C values. It is plausible that the obvious δ¹³C variation was largely influenced by the changes in vegetation cover overlying the cave. Our δ¹³C results, together with the records of climate and human activity from historical documentary records, suggest that: (i) prior to AD 700, small fluctuations in relatively light δ¹³C values reflect the presence of lush forest coverage above the cave, which was minimally disturbed by human activities; (ii) during AD 700–1100, the drastic increase in δ¹³C values indicates persistent and massive deforestation associated with large‐scale immigration into northern Jiangxi after the Rebellion of An & Shi (AD 755–763) in the Tang Dynasty and the subsequent development of agriculture and economic activity; and (iii) since AD 1100, fluctuations in relatively high δ¹³C values suggest that local vegetation during the last millennium has been sparse. Since the Rebellion of An & Shi, southeastern China was progressively developed, coincident with deforestation and vegetation deterioration caused by human disturbance in the form of deforestation and cultivation.     

Origin of Paleofluids in Dabashan Foreland Thrust Belt:Geochemical Evidence of 13C,18O and 87Sr/86Sr in Veins and Host Rocks

In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and 87Sr/86Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than ?5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate-derived, with the δ13C generally more than ?2.0‰PDB, δ18O less than ?10.0‰PDB, Z value more than 120 and 87Sr/86Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid (including possibly a little mantle-derived fluid or meteoric water), with the δ13C generally ranging from ?2.0‰ to ?8.0‰PDB, δ18O from ?10.0‰ to ?18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to ?10.0‰PDB, δ18O less than ?8.0‰PDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.     

Diagenesis and geochemistry of porites corals from Papua New Guinea: Implications for paleoclimate reconstruction

Coral proxy records of sea surface temperature (SST) and hydrological balance have become important tools in the field of tropical paleoclimatology. However, coral aragonite is subject to post-depositional diagenetic alteration in both the marine and vadose environments. To understand the impact of diagenesis on coral climate proxies, two mid-Holocene Porites corals from raised reefs on Muschu Island, Papua New Guinea, were analysed for Sr/Ca, δ¹⁸O, and δ¹³C along transects from 100% aragonite to 100% calcite. Thin-section analysis showed a characteristic vadose zone diagenetic sequence, beginning with leaching of primary aragonite and fine calcite overgrowths, transitional to calcite void filling and neomorphic, fabric selective replacement of the coral skeleton. Average calcite Sr/Ca and δ¹⁸O values were lower than those for coral aragonite, decreasing from 0.0088 to 0.0021 and −5.2 to −8.1‰, respectively. The relatively low Sr/Ca of the secondary calcite reflects the Sr/Ca of dissolving phases and the large difference between aragonite and calcite Sr/Ca partition coefficients. The decrease in δ¹⁸O of calcite relative to coral aragonite is a function of the δ¹⁸O of precipitation. Carbon-isotope ratios in secondary calcite are variable, though generally lower relative to aragonite, ranging from −2.5 to −10.4%. The variability of δ¹³C in secondary calcite reflects the amount of soil CO₂ contributing ¹³C-depleted carbon to the precipitating fluids. Diagenesis has a greater impact on Sr/Ca than on δ¹⁸O; the calcite compositions reported here convert to SST anomalies of 115°C and 14°C, respectively. Based on calcite Sr/Ca compositions in this study and in the literature, the sensitivity of coral Sr/Ca-SST to vadose-zone calcite diagenesis is 1.1 to 1.5°C per percent calcite. In contrast, the rate of change in coral δ¹⁸O-SST is relatively small (−0.2 to 0.2°C per percent calcite). We show that large shifts in δ¹⁸O, reported for mid-Holocene and Last Interglacial corals with warmer than present Sr/Ca-SSTs, cannot be caused by calcite diagenesis. Low-level calcite diagenesis can be detected through X-ray diffraction techniques, thin section analysis, and high spatial resolution sampling of the coral skeleton and thus should not impede the production of accurate coral paleoclimate reconstructions.     

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO₂ consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO₂ consumption to silicate weathering than methods utilizing Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and ⁸⁷Sr/⁸⁶Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (P_CO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca²⁺-Mg²⁺-HCO₃⁻ waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca²⁺ and Sr²⁺, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and P_CO2 gradients in the Himalaya.The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO₂. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg²⁺, Ca²⁺, and HCO₃⁻ mass balances support interpretations of preferential Ca²⁺ removal by calcite precipitation. On the basis of patterns of saturation state and P_CO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca²⁺ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca²⁺ during riverine transport brings the Ca/Sr and ⁸⁷Sr/⁸⁶Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr²⁺ budget and suggest that the conventional application of two-component Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations has overestimated silicate-derived Sr²⁺ and HCO₃⁻ fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.     

川东南地区石牛栏组碳、氧、锶同位素特征及其地质意义

前人对川东南地区石牛栏组地层已进行了大量的研究工作,但有关同位素地球化学方面的研究尚未见报道。本区石牛栏组沉积成因碳酸盐岩的碳同位素值与前人的研究结果一致,而氧同位素值则有所偏低;白云岩δ^13C值低,δ^18O值高,反映受成岩环境的影响较明显;裂缝中方解石的碳、氧同位素组成分布于两个不同的区间,说明不同期次裂缝充填物形成时的流体性质发生了明显的变化;沉积成因碳酸盐岩具异常低的锶同位素值,与前人研究结果有明显的差异,推测是受贫87Sr同位素的成岩流体的影响;晚期裂缝充填物锶同位素比值较高,也表明它们受到了地表淡水的影响。     

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

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:

1000lnα=16.1(10³T^-1)-24.6