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1.
Limestone cave deposits (speleothems) provide archives for past changes in regional climates over a range of timescales. While δ18O and δ13C in speleothem calcite have been commonly used for reconstruction of paleoclimates, we report here further efforts in the use of 87Sr/86Sr and Sr/Ca signals in speleothem calcite to deduce paleomonsoon variability near the Loess Plateau of central China. A two end-member mass-balance model of concentration and isotopic composition of strontium in a cave system is used to estimate variation of the 87Sr/86Sr ratio in sediments overlying a limestone cave. We show that this ratio reflects climate-driven variations in the provenance and the extent of chemical weathering of the epikarstic sediments. The measurements of 87Sr/86Sr made on a well-dated stalagmite, SFL, from Buddha Cave (33o40N′ 109o05′E) show ratios of 0.71092 to 0.71133 (±0.00001 as 2σ) during relatively cold periods (e.g., Marine Isotope Stage (MIS) 5b, 5d, and 8), lower than ratios of 0.71133 to 0.71194 during relatively warm periods (e.g., MIS 5a, 5c, 5e, and 7). As changes in the Sr/Ca ratio may affect speleothem 87Sr/86Sr, we show that the direct use of speleothem 87Sr/86Sr is less ideal than our modeled 87Sr/86Sr for the exogenic Sr source above the cave as a paleomonsoon proxy. Using the δ18O, δ13C, Sr/Ca, and 87Sr/86Sr records of the stalagmite, we reconstruct the variability of the East Asian monsoon for the time period between 70 and 280 kyr ago. The results show that summer monsoons were more intense during interglacial periods than during glacial periods.  相似文献   

2.
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.  相似文献   

3.
Combined stable isotope (δ18O and δ13C) and trace element (Mg, Sr) geochemistry from bulk tufa calcite and ostracod shell calcite from an early Holocene British tufa reveal clear records of Holocene palaeoclimatic change. Variation in δ18O is caused principally by change in the isotopic composition of Holocene rainfall (recharge), itself caused mainly by change in air temperature. The δ13C variability through much of the deposit reflects increasing influence of soil‐zone CO2, owing to progressive woodland soil development. Bulk tufa Mg/Ca and Sr/Ca are controlled by their concentrations in the spring water. Importantly, Mg/Ca ratios are not related to δ18O values and thus show no temperature dependence. First‐order sympathetic relationships between δ13C values and Mg/Ca and Sr/Ca are controlled by aquifer processes (residence times, CO2 degassing and calcite dissolution/reprecipitation) and probably record intensity of palaeorainfall (recharge) effects. Stable isotope records from ostracod shells show evidence of vital effects relative to bulk tufa data. The ostracod isotopic records are markedly ‘spiky’ because the ostracods record ‘snapshots’ of relatively short duration (years), whereas the bulk tufa samples record averages of longer time periods, probably decades. The δ18O record appears to show early Holocene warming, a thermal maximum at ca. 8900 cal. yr BP and the global 8200 yr BP cold event. Combined δ13C, Mg/Ca and Sr/Ca data suggest that early Holocene warming was accompanied by decreasing rainfall intensity. The Mg/Ca data suggest that the 8200 yr BP cold event was also dry. Warmer and wetter conditions were re‐established after the 8200 yr BP cold event until the top of the preserved tufa sequence at ca. 7100 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

4.
微量元素是岩溶洞穴沉积中非常重要的一类古气候环境替代指标,为近20年来国内外的一个研究热点。总结前人的研究,主要取得了以下一些重要认识:（1）洞穴上覆土壤 和围岩是洞穴次生碳酸盐沉积Mg、Sr的主要来源;（2）Mg/Ca与Sr/Ca能够指示气候环境变化,但需结合其它指标综合考虑。（3）洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca受多种气候环境因素（包括土壤和围岩的组成和性质、水-岩相互作用、先期碳酸盐沉积、分配系数等）影响,其古气候环境指示意义具有多解性;（4）矿物结晶作用对Mg/Ca与Sr/Ca有一定的影响,特别是文石在向方解石转变的过程中容易丢失Mg、Sr,此外,杂质的混入也将抑制Mg、Sr进入方解石,从而引起洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca比值的变化。今后应进一步加强对石笋中这些微量元素的影响机制研究,尤其是对一些影响因素与微量元素含量变化之间的定量关系进行探讨。   相似文献   

5.
Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ13C values of the primary and secondary calcites range from +6 to −9‰ and δ18O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ13C and relatively invariant δ18O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO2 during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C3 and C4 vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.  相似文献   

6.
Cai, B., Zhu, J., Ban, F. & Tan, M. 2011: Intra‐annual variation of the calcite deposition rate of drip water in Shihua Cave, Beijing, China and its implications for palaeoclimatic reconstructions. Boreas, Vol. 40, pp. 525–535. 10.1111/j.1502‐3885.2010.00201.x. ISSN 0300‐9483. Monthly in situ monitoring of the calcite deposition rate, drip‐water chemistry and surrounding cave environment was carried out at Shihua Cave, Beijing, China, through two hydrological years (from January 2006 to February 2008) to determine the seasonal variability and mechanisms of stalagmite growth in Shihua Cave. Calcite deposition rates exhibit significant intra‐annual variation, with the lowest values during the summer monsoonal rainy season (July–August) and peak values from autumn to spring. The temporal change in the calcite deposition rate is negatively correlated with the drip rate, cave‐air PCO2 (CO2 partial pressure) and Ca concentration, and positively correlated with the pH of the feeding drip water. The seasonal recharge regime of drip water is likely to be the primary control on the drip‐water quality and quantity, which, in turn, control the calcite deposition rate in Shihua Cave. During the summer rainy season, periodic and intense rainstorms increase the drip rate and cave‐air PCO2, leading to drip water with a lower pH and saturation index of calcite, thereby reducing the calcite precipitation. It seems that the high cave‐air PCO2 is the dominant control on the calcite deposition rate during the rainy season. Our previous study on the dissolved organic carbon of drip water concluded that the thin luminescent bands in stalagmite laminae from Shihua Cave form during the rainy season. The lower calcite deposition rate during the rainy season further supports this suggestion. The significant intra‐seasonal variability of the calcite deposition rate implies that the seasonal bias of δ18O of stalagmites should be considered when stalagmite δ18O is used as a high‐resolution palaeoclimatic archive.  相似文献   

7.
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.  相似文献   

8.
Cave dripwater hydrochemistry responds to environmental changes, both within and outside of the cave, and thereby conveys this information to any stalagmite fed by the drips. As stalagmites are important archives of climate proxy information, understanding how dripwater hydrochemistry responds to environmental forcing is critical. However, despite the large number of speleothems in SW China, the response of dripwater to regional climate variability is not yet adequately understood. A 3‐year study of three drip sites in Xueyu Cave, Chongqing Municipality, SW China, revealed the most important mechanisms controlling dripwater chemical variability. The principal chemical indices (pH, specific conductivity, Ca2+, Mg2+, Sr2+ and ) in collected dripwaters and the local climate data were analysed in this study. The principal controls on the hydrochemistry were found to be the external climate and its changes, groundwater residence time, cave ventilation and prior calcite precipitation (PCP) processes. Dripwater hydrochemistry showed strongly coherent seasonal patterns despite the fact that all sites are Ca–HCO3 type waters and supersaturated with calcite. Seasonal changes in dripwater hydrochemistry were influenced by the soil and vadose zone CO2 content as well as groundwater residence time in the upper karst zone. Cave‐air CO2 seasonal variations were consistent with changes in dripwater PCO2 and cave ventilation. Trace element ratios (Mg/Ca and Sr/Ca) of dripwater were controlled by PCP processes. Seasonal variations in dripwater Mg/Ca and Sr/Ca ratios in Xueyu Cave showed inverse changes with the Asia Monsoon Index during the monitoring period, reflecting the seasonal climate changes that may have been recorded in the speleothems. Based on a linear regression of PCO2 and the Ca2+ data in the cold–dry winter season, a 130‐ppm shift in cave‐air PCO2 results in a 1‐ppm shift in dripwater Ca2+ concentration in Xueyu Cave. This study illustrates the importance of understanding factors controlling the changes in the composition of dripwater before it reaches the speleothem.  相似文献   

9.
Each of two calcitic stalagmites from Grotte de Clamouse, Herault, southern France, displays a discrete aragonite layer dated at around 1100 yr BP. The layer of fanning aragonite ray crystals is immediately preceded by calcite with Mg and Sr compositions that are uniquely high for the past 3 kyr. Trace element compositions close to the boundary between original aragonite and calcite are consistent with quasi‐equilibrium partitioning of trace elements between the phases. Study of modern dripwaters demonstrates that pronounced covariation of Mg/Ca and Sr/Ca ratios in dripwater occurs owing to large amounts of calcite precipitation upflow of the drips that fed the stalagmites. Trace element to Ca ratios are enhanced during seasonally dry periods. Ion microprobe data demonstrate a pronounced covariation of trace elements, including Mg and Sr in calcite, and Sr, U and Ba in aragonite. The mean peak spacing is close to the long‐term mean of annual growth rates determined by differences in U‐series ages and so the trace element peaks are interpreted as annual. The trace element chemistry of the stalagmites on annual to inter‐annual scales thus directly reflects the amounts of prior calcite precipitation, interpreted as an index of aridity. The longer‐term context is a multi‐decadal period of aridity (1200–1100 yr BP) possibly correlated with an analogous episode in Central America. The arid period culminated in the nucleation of aragonite, but within a decade was followed by a return to precursor conditions. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

10.
洞穴沉积物—石笋已成为研究岩溶区环境气候变化历史的重要载体。在我国湘西地区,某些洞穴石笋原始沉积多为不稳定的文石矿物,极易发生重结晶,可能使石笋中相关化学元素含量最终偏离原生矿物的特征,限制了文石石笋某些代用指标在古气候研究中的应用。文章以前人研究成果为基础,总结梳理了文石石笋发生重结晶的影响因素及其对石笋记录古气候的影响:（1）石笋剖面特征、XRD结果、显微镜观察和地球化学元素特征等可作为石笋发生重结晶的判别依据;（2）洞穴滴水和石笋孔隙水饱和度、文石晶体缺陷和晶体之间的方解石胶结物以及岩溶水体中Mg2+浓度等均会影响文石石笋的矿物转变;（3）在文石向方解石转变过程中,石笋铀含量会有一定程度的流失,可导致放射性铀系定年的异常或年代倒序;（4）矿物重结晶可导致δ18O、δ13C及石笋微量元素浓度（或比值）等指标发生改变,其变化特征因洞穴而异,从而影响其作为环境指示器的可靠性;（5）湖南龙山惹迷洞石笋（RM2）发生了不均一的矿物重结晶,自顶部至20.3 cm以放射状为主,20.3 cm至底部主要为糖粒状,并结合年代结果发现文石重结晶对石笋铀系定年产生了影响,而重结晶作用对该石笋其他指标的影响还有待进一步研究。   相似文献   

11.
Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ18O signal measured on the same material, to calculate the δ18Ow, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor DSr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in DMg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The DSr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.  相似文献   

12.
石笋矿物类型、成因及其对气候和环境的指示   总被引：5，自引：2，他引：3  
洞穴石笋的矿物组成分为方解石、文石和文石-方解石三种类型。本文总结了国内外已有的研究成果,并结合野外观测现象和数据,讨论了影响石笋矿物形成和转变的因素,分析了利用石笋矿物类型特征研究古气候和古环境变化的可行性。洞内滴水饱和度和滴水中Mg/Ca比值是影响石笋矿物类型的主要因素:当滴水Mg/Ca 比值较低（Mg/Ca＜1或<<1）时,滴水饱和度较低易形成方解石,而文石沉积则需要更高的滴水饱和度;当滴水Mg/Ca 比值较高（Mg/Ca≥1）时,方解石相对文石沉积需要更高的滴水饱和度。洞穴围岩镁含量高且滴水多而稳定的洞内环境是我国南方大量文石笋发育的主要原因。长期处于滴水淋滤环境的文石笋容易向方解石转变,但若滴水中Mg2+浓度较大,此转变过程会受到抑制。在围岩镁含量较低的洞穴中,干旱时期渗流水滞留时间长、滴水速率变慢,会造成滴水中Mg/Ca比值升高并引起文石沉积。因此,石笋矿物类型及矿物相转变可指示气候和环境的变化。   相似文献   

13.
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.  相似文献   

14.
通过对北京石花洞滴水地球化学一个水文年的观测,揭示了洞穴滴水水文地球化学季节变化与外界气候变化的关系,3个滴水点的滴率随降雨量的增加都有明显的变化,但不同滴水点滞后时间不同。滴水滴率、Mg2+和SO2-4含量的季节变化数据显示,雨季洞穴滴水主要来源于当季降水,但也存在岩层滞留水的混入。滴水中Mg/Ca比值存在明显季节变化,旱季较低而雨季较高,但在雨季初期出现较大的波动。分析洞穴上覆土壤和洞内裂隙土壤数据,认为雨季初期滴水中Mg/Ca比值的波动是由土壤中Mg2+的快速淋溶造成的,上覆土壤结构性质和组分变化均影响滴水地球化学特征。  相似文献   

15.
The variations of environmental conditions (T°, pH, δ13CDIC, [DIC], δ18O, Mg/Ca, and Sr/Ca) of ostracod habitats were examined to determine the controls of environmental parameters on the chemical and isotopic composition of ostracod valves. Results of a one-year monitoring of environmental parameters at five sites, with depths of between 2 and 70 m, in Lake Geneva indicate that in littoral to sub-littoral zones (2, 5, and 13 m), the chemical composition of bottom water varies seasonally in concert with changes in temperature and photosynthetic activity. An increase of temperature and photosynthetic activity leads to an increase in δ13C values of DIC and to precipitation of authigenic calcite, which results in a concomitant increase of Mg/Ca and Sr/Ca ratios of water. In deeper sites (33 and 70 m), the composition of bottom water remains constant throughout the year and isotopic values and trace element contents are similar to those of deep water within the lake. The chemical composition of interstitial pore water also does not reflect seasonal variations but is controlled by calcite dissolution, aerobic respiration, anaerobic respiration with reduction of sulphate and/or nitrate, and methanogenesis that may occur in the sediment pores. Relative influence of each of these factors on the pore water geochemistry depends on sediment thickness and texture, oxygen content in bottom as well as pore water. Variations of chemical compositions of the ostracod valves of this study vary according to the specific ecology of the ostracod species analysed, that is its life-cycle and its (micro-)habitat. Littoral species have compositions that are related to the seasonal variations of temperature, δ13C values of DIC, and of Mg/Ca and Sr/Ca ratios of water. In contrast, the compositions of profundal species are largely controlled by variations of pore fluids along sediment depth profiles according to the specific depth preference of the species. The control on the geochemistry of sub-littoral species is a combination of controls for the littoral and profundal species as well as the specific ecology of the species.  相似文献   

16.
Many Recent and fossil freshwater tufa stromatolites contain millimetre‐scale, alternating laminae of dense micrite and more porous or sparry crystalline calcites. These alternating laminae have been interpreted to represent seasonally controlled differences in the biotic activity of microbes, and/or seasonally controlled changes in the rate of calcification. Either way, couplets of these microbially mediated alternating calcified laminae are generally agreed to represent annual seasonality. Combined stable isotope (δ18O and δ13C) and trace element (Mg, Sr, Ba) geochemistry from Recent tufa stromatolites show that seasonal climatic information is available from these calcites. Variability in δ18O (and in one case Mg concentration) has been shown to be controlled primarily by stream temperature change, usually driven by solar insolation. In arid climates, seasonal evaporation can also cause δ18O enrichment by at least 1‰. Variability in δ13C results potentially from: (1) seasonal change in plant uptake of 12C‐enriched CO2; (2) seasonal change in degassing of 12C‐enriched CO2 in the aquifer system; and (3) precipitation of calcite along the aquifer or river flow path, a process that increases δ13C of dissolved inorganic carbon (DIC) in the remaining water. Mechanisms 2 and 3 are linked because calcite precipitates in aquifers where degassing occurs, e.g. air pockets. The latter mechanism for δ13C enrichment has also been shown to cause sympathetic variation between trace element/Ca ratios and δ13C because trace elements with partition coefficients much greater than 1 (e.g. Sr, Ba) remain preferentially in solution. Since degassing in air pockets will be enhanced during decreased recharge when water saturation of the aquifer is lowest, sympathetic variation in trace element/Ca ratios and δ13C is a possible index of recharge and therefore precipitation intensity. High‐resolution geochemical data from well‐dated tufa stromatolites have great potential for Quaternary palaeoclimate reconstructions, possibly allowing recovery of annual seasonal climatic information including water temperature variation and change in rainfall intensity. However, careful consideration of diagenetic effects, particularly aggrading neomorphism, needs to be the next step. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

17.
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.  相似文献   

18.
Stalagmites are important palaeo-climatic archives since their chemical and isotopic signatures have the potential to record high-resolution changes in temperature and precipitation over thousands of years. We present three U/Th-dated records of stalagmites (MA1–MA3) in the superhumid southern Andes, Chile (53°S). They grew simultaneously during the last five thousand years (ka BP) in a cave that developed in schist and granodiorite. Major and trace elements as well as the C and O isotope compositions of the stalagmites were analysed at high spatial and temporal resolution as proxies for palaeo-temperature and palaeo-precipitation. Calibrations are based on data from five years of monitoring the climate and hydrology inside and outside the cave and on data from 100 years of regional weather station records.Water-insoluble elements such as Y and HREE in the stalagmites indicate the amount of incorporated siliciclastic detritus. Monitoring shows that the quantity of detritus is controlled by the drip water rate once a threshold level has been exceeded. In general, drip rate variations of the stalagmites depend on the amount of rainfall. However, different drip-water pathways above each drip location gave rise to individual drip rate levels. Only one of the three stalagmites (MA1) had sufficiently high drip rates to record detrital proxies over its complete length. Carbonate-compatible element contents (e.g. U, Sr, Mg), which were measured up to sub-annual resolution, document changes in meteoric precipitation and related drip-water dilution. In addition, these soluble elements are controlled by leaching during weathering of the host rock and soils depending on the pH of acidic pore waters in the peaty soils of the cave’s catchment area. In general, higher rainfall resulted in a lower concentration of these elements and vice versa. The Mg/Ca record of stalagmite MA1 was calibrated against meteoric precipitation records for the last 100 years from two regional weather stations. Carbonate-compatible soluble elements show similar patterns in the three stalagmites with generally high values when drip rates and detrital tracers were low and vice versa. δ13C and δ18O values are highly correlated in each stalagmite suggesting a predominantly drip rate dependent kinetic control by evaporation and/or outgassing. Only C and O isotopes from stalagmite MA1 that received the highest drip rates show a good correlation between detrital proxy elements and carbonate-compatible elements. A temperature-related change in rainwater isotope values modified the MA1 record during the Little Ice Age (～0.7–0.1 ka BP) that was ～1.5 °C colder than today. The isotopic composition of the stalagmites MA2 and MA3 that formed at lower drip rates shows a poor correlation with stalagmite MA1 and all other chemical proxies of MA1. ‘Hendy tests’ indicate that the degassing-controlled isotope fractionation of MA2 and MA3 had already started at the cave roof, especially when drip rates were low. Changing pathways and residence times of the seepage water caused a non-climatically controlled isotope fractionation, which may be generally important in ventilated caves during phases of low drip rates. Our proxies indicate that the Neoglacial cold phases from ～3.5 to 2.5 and from ～0.7 to 0.1 ka BP were characterised by 30% lower precipitation compared with the Medieval Warm Period from 1.2 to 0.8 ka BP, which was extremely humid in this region.  相似文献   

19.
The calcium-isotope composition (δ44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca2+aq-CaCO3-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition. Biological carbonates generally have lower δ44/42Ca values than inorganic marine cements, and there appears to be no fractionation between seawater and marine inorganic calcite. A kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against 44Ca in biological carbonates when compared to inorganic precipitates. This is supported by a well-defined correlation of the δ44/42Ca values with Sr concentrations in Cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration. No significant temperature dependence of Ca-isotope fractionation was found in shells of Cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from δ18O values and Mg concentrations. The reconstruction of secular variations in the δ44/42Ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and Cretaceous biological carbonates, independent of chemical composition or mineralogy. Despite these variations that may be due to still unidentified biological fractionation mechanisms, the δ44/42Ca values of Cretaceous skeletal calcite suggest that the δ44/42Ca value of Cretaceous seawater was 0.3-0.4‰ lower than that of the modern ocean.  相似文献   

20.
Few terrestrial Holocene climate records exist from south‐eastern Europe despite its important geographical position as a transitional climatic zone between the Mediterranean and mainland continental Europe. Here we present new petrographic and stable isotope data for two Holocene speleothems from Modri? Cave, Croatia (44°15′N, 15°32′E), a coastal Adriatic site (120 m inland). Modern meteorological and cave conditions have been monitored for 2 years to understand the links between climate variability and stable isotope time‐series records in speleothems. Typical of a Mediterranean‐type climate, a negative water balance exists between April and September, so that recharge of the aquifer is restricted to the winter months. The weighted mean δ18O of the rainfall is ?5.96‰ (2σ = 2.83), and the weighted mean D/H rainfall value is ?36.83‰ (2σ = 19.95), slightly above the Global Meteoric Water Line, but well below the Mediterranean Meteoric Water Line. Modern calcite from the tops of each stalagmite exhibits δ18O values that are close to isotopic equilibrium with their respective drip water values. Unfortunately, the relatively young ages and low uranium contents (ca. 50 p.p.b.) of both stalagmites hamper the use of U‐series dating. Radiocarbon dates have been used instead to constrain their chronology using a dead carbon correction. Apart from some Isotope Stage 3 material (ca. 55 ka), both stalagmites were deposited during the late Holocene. Climatic conditions during the late Holocene are inferred to have been sufficiently wet to maintain stalagmite growth and any hiatuses appear to be relatively short lived. Inferred changes in the stalagmite diameters during deposition are linked to δ13C and δ18O variations, indicating alternating periods of drier and wetter conditions. Drier conditions are inferred for the late Roman Ages warm period and the mid‐Medieval Warm Period. Wetter conditions are associated with the Little Ice Age. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

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