Processes controlling dripwater hydrochemistry variations in Xueyu Cave,SW China: implications for speleothem palaeoclimate signal interpretations

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.     

洞穴滴水地球化学的空间和时间变化及其控制因素--以北京石花洞为例

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SO^{2-₄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。}     

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.     

Temporal and spatial variations in hydro-geochemistry of cave percolation water and their implications for four caves in Guizhou, China

Soil water and cave drip water from four cave systems in Guizhou, Southwest China, were monitored and sampled monthly from April 2003 to May 2004 to understand spatio-temporal variations in hydro-geochemistry of cave percolation water. The results indicated that among the 5 drip water sites from the Liangfeng Cave (LFC), there were no significant differences among the hydro-geochemical parameters. In the Xiniu Cave (XNC), the drip rates were variable and responded quickly to precipitation events in the 3# (No. 3) drip site with variable water head; both bulk and variation in drip rates were smaller in the 2# with constant water head. However, in the Qixing Cave (QXC) and Jiangjun Cave (JJC), drip rates, concentrations of major ions and saturation index for calcite (SI C ) were smaller, and Mg/Ca ratios in Group I (1#, 2#, 6#, 7# and 8# in the QXC; 2# and 3# in the JJC) were larger than those in Group II (3#, 4#, 5# and 9# in the QXC; 1# and 4# in the JJC). These differences might be the result of different hydrogeological processes above the caves, which are divided into five categories based on hydro-geochemistry data. The formation of some proxies in speleothem, such as Mg/Ca, is likely to be affected by those processes.     

Controls on the spatial and temporal variability of vadose dripwater geochemistry: Edwards aquifer, central Texas

A 4-yr study of spatial and temporal variability in the geochemistry of vadose groundwaters from caves within the Edwards aquifer region of central Texas offers new insights into controls on vadose groundwater evolution, the relationship between vadose and phreatic groundwaters, and the fundamental influence of soil composition on groundwater geochemistry. Variations in Sr isotopes and trace elements (Mg/Ca and Sr/Ca ratios) of dripwaters and soils from different caves, as well as phreatic groundwaters, provide the potential to distinguish between local variability and regional processes controlling fluid geochemistry, and a framework for understanding the links between climatic and hydrologic processes.The Sr isotope compositions of vadose cave dripwaters (mean ⁸⁷Sr/⁸⁶Sr = 0.7087) and phreatic groundwaters (mean ⁸⁷Sr/⁸⁶Sr = 0.7079) generally fall between values for host carbonates (mean ⁸⁷Sr/⁸⁶Sr = 0.7076) and exchangeable Sr in overlying soils (mean ⁸⁷Sr/⁸⁶Sr = 0.7088). Dripwaters have lower Mg/Ca and Sr/Ca ratios, and higher ⁸⁷Sr/⁸⁶Sr values than phreatic groundwaters. Dripwater ⁸⁷Sr/⁸⁶Sr values also inversely correlate with both Mg/Ca and Sr/Ca ratios. Mass-balance modeling combined with these geochemical relationships suggest that variations in fluid compositions are predominantly controlled by groundwater residence times, and water-rock interaction with overlying soils and host aquifer carbonate rocks. Consistent differences in dripwater geochemistry (i.e., ⁸⁷Sr/⁸⁶Sr, Mg/Ca, and Sr/Ca) between individual caves are similar to compositional differences in soils above the caves. While these differences appear to exert significant control on local fluid evolution, geochemical and isotopic variations suggest that the controlling processes are regionally extensive. Temporal variations in ⁸⁷Sr/⁸⁶Sr values and Mg/Ca ratios of dripwaters from some sites over the 4-yr interval correspond with changes in both aquifer and climatic parameters. These results have important implications for the interpretation of trace element and isotopic variations in speleothems as paleoclimate records, as well as the understanding of controls on water chemistry for both present-day and ancient carbonate aquifers.     

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.     

洞穴次生碳酸盐沉积的Mg/Ca与Sr/Ca比值研究进展——兼论洞穴次生沉积物Mg/Ca与Sr/Ca的影响机制

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。      

贵州七星洞系统中水文地球化学特征对滴水δ~(13)C_(DIC)的影响及其意义

2003年4月至2004年5月,笔者对贵州七星洞(QXD)进行了较为详细的监测,逐月采集了土壤水和洞穴滴水等样品,分别测定了样品的稳定碳同位素组成和水文地球化学参数。结果显示,9个滴水点同期的溶解无机碳同位素值(δ13CDIC)之间存在着大的差异,最大达6.9‰;δ13CDIC值偏重的Ⅰ组滴水,其Ca、Sr、HCO3、电导率(EC)和方解石饱和指数(SIC)等水文地球化学指标偏小,而Mg/Ca比值偏大,Ⅱ组则相反;不同滴水点的δ13CDIC值分别与相应滴水的Ca、Sr、HCO3、EC、Mg/Ca和SIC等水文地球化学指标之间存在较好的相关关系。进一步分析表明,与土壤水δ13CDIC平均值-9.9‰相比,Ⅰ组1#、2#、6#、7#和8#滴水点δ13CDIC值偏重4.5‰～5.7‰,主要是由大量的基岩溶解以及前期方解石沉积(prior calcite precipitation,PCP)共同作用的结果;Ⅱ组3#、4#、5#和9#滴水点δ13CDIC值偏重0.6‰～1.6‰,受基岩溶解和PCP过程影响较小,尤其是9#滴水点受影响最小。因此,若不考虑基岩溶解和PCP过程影响作用,将会极大地影响洞穴化学沉积物碳同位素记录的准确解释。     

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

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.     

新生碳酸钙沉积矿物形态的影响因素分析

石笋是古气候重建的重要地质载体,文石与方解石是石笋碳酸钙晶体的常见矿物形态。根据现代洞穴监测数据分析洞穴新生碳酸钙沉积物 (Active Speleothem: AS)的矿物形态的研究较少。本文在重庆武隆芙蓉洞三个滴水点 (MP2、MP5、MP9)下放置玻璃片,收集新生碳酸钙沉积物和滴水样品,监测新生碳酸钙沉积物矿物形态、滴水的Mg/Ca比值、pH、滴率和洞穴环境等指标,分析玻璃片正面和反面新生碳酸钙沉积物的δ18O、δ13C和Mg/Ca比值。研究发现:(1) MP2滴水点下的玻璃片正反面新生碳酸钙沉积物的矿物形态均为方解石;MP5和MP9滴水点的正面沉积方解石和文石-方解石混合两种情况,反面沉积文石-方解石,且反面文石多于正面。 (2) MP2滴水Mg/Ca比值小于MP5和MP9,说明滴水Mg/Ca比值是影响新生碳酸钙沉积物矿物形态的重要因素;而滴水pH值对AS矿物形态的影响在不同滴水点有差异。(3) 不论是玻璃片正面还是反面,文石-方解石混合的新生碳酸钙沉积物δ18O和δ13C比以方解石为主的沉积物偏正,说明AS矿物形态的变化会导致δ18O和δ13C发生变化。通过在芙蓉洞的系统监测和分析,发现新生碳酸钙沉积物的矿物形态与地表环境、洞穴上部岩溶水文地质条件密切相关,并验证了洞穴新生碳酸钙沉积物的矿物形态对石笋δ18O和δ13C具有重要影响。      

重庆芙蓉洞滴水现代次生化学沉积物沉积速率与元素特征

为了探讨芙蓉洞现代沉积物沉积速率和微量元素 (Mg,Sr) 的变化特征、控制机制以及气候环境指示意义,于2010年11月到2013年11月对芙蓉洞5个滴水点进行连续现场监测,并采集现代沉积物样品进行沉积速率计算和微量元素测定。结果显示:(1) 芙蓉洞5个滴水点的现代沉积物沉积速率与滴量、pH、Ca2+浓度以及PCO2等指标的关系表现出多样性。 其中MP4和MP5的沉积速率均与滴量呈正相关 (r=0.75, n=11, p<0.01; r=0.63, n=11, p<0.05),两个滴水点的沉积速率整体表现出雨季高、旱季低的变化规律,表明MP4和 MP5的沉积作用主要发生在雨季,其沉积速率的变化可以对季节性干湿度变化做出响应。(2) 2012-2013年年降水量明显增加,在稀释作用、水岩作用以及植物对元素差异性吸收作用的影响下,各滴水点现代沉积物整体呈现出Mg浓度减小而Sr浓度增大的趋势,Mg/Ca和Sr/Ca比值呈反相关关系,它们响应了年际尺度上降水量增加的气候信息。      

Trace elements in speleothems as recorders of environmental change

Speleothems are now established as important palaeoenvironmental archives and contain a number of suitable proxies, although trace elements have been much less widely used than oxygen and carbon isotopes. The complexity of the cave environment helps to explain this since the fluids from which speleothems form vary greatly in composition in space (even within a cave chamber), seasonally, and over longer periods. Understanding the forcing factors for this variability is the key to decoding the significance of the trace element records.A variety of techniques are available for trace element work and it is important to understand the strengths and limitations of each and also to seek an understanding, e.g. by micro-imaging techniques, of whether the elements are associated with inclusions in the CaCO₃, or are isolated within the crystal lattice. For some elements there is a more-or-less predictable relationship between element ratios to Ca in the water and in the calcite. Individual trace elements may be derived from atmospheric deposition, superficial deposits or bedrock and can be recycled in soil processes before being transferred to the cave. Some components show an instantaneous response to water infiltration, whereas others are only leached by slow-flowing seepage waters. Changing in the proportion of water from fracture-fed and seepage-flow aquifer compartments is an important factor in influencing trace element supply. High flows lead to higher fluxes of soil-derived colloidally transported elements. Conversely, under relatively dry conditions, degassing of CO₂ results in “prior calcite precipitation” upflow of the site of speleothem deposition and leads to higher ratios of Sr/Ca and Mg/Ca. Some trace element variations in speleothems over time are induced during crystal growth whereby faster growth leads to a greater departure from equilibrium element partitioning.Despite the demonstrated temperature-dependence of Mg partitioning into calcite, attempts at deriving palaeotemperature records from speleothems have been so far confounded by variations in solution Mg/Ca and/or crystallographic effects. A number of case studies have effectively used trace elements such as speleothem Mg as records of palaeo-aridity, using supporting arguments from modern monitoring or covariations with other parameters such as stable isotopes. Sr and U isotopes can also be indicators of palaeohydrology, although Sr isotope variations can also reflect varying aeolian input. Considerable progress has been made in decoding the meaning of annual trace element variations using criteria for understanding dripwater hydrology and pH. This should lead in the future to more specific interpretations of how seasonality evolves through time.     

重庆丰都雪玉洞群洞穴现代监测与古环境研究回顾和展望

重庆丰都雪玉洞群包括羊子洞、雪玉洞和水鸣洞,西南大学的研究团队从2008年开始对雪玉洞群开展了系统的现代过程监测,以了解洞穴系统气候和环境信息的传输、转化和记录过程。通过对雪玉洞洞穴内外的大气、植被、土壤、基岩、滴水和洞穴沉积物等的动态监测,研究了碳酸盐沉积过程的水化学指标变化,揭示了现代洞穴滴水的影响因素和变化过程,以及碳酸盐沉积物对现代气候环境变化的响应,也为古气候的定量化研究提供了基础支撑。现代过程监测记录表明:雪玉洞CO₂主要来源于上覆土壤,其季节变化受降水的影响较大;在短时间尺度上受到游客旅游活动的影响明显,但幅度远远小于自然过程引起的变化。雪玉洞内次生沉积物的沉积速率具有明显的旱季、雨季特征,不同滴水点下方沉积物的沉积速率变化较大。雪玉洞群三个洞穴的石笋古环境记录研究表明,本区石笋的230Th/232Th比值较适合高精度铀系测年;部分石笋沉积速率较快,平均沉积速率达到0.25 mm·a?1,可以开展高分辨率的气候和环境变化研究。羊子洞YZ1石笋的年龄范围在116~3 ka B.P.之间（平均测年精度2σ,269年）,覆盖了整个末次冰期,δ18O和δ13C的变化曲线和东亚季风区的其他记录具有明显的一致性。同位素测试的时间分辨率平均为88年,成功记录了一些百年－千年尺度的气候突变事件,如Heinrich事件、7.2 ka事件、小冰期等。在精确年代学的基础上,雪玉洞群石笋具有重建高分辨率气候环境变化的潜力。      

溶洞穴滴水元素季节变化及其气候指示意义研究—以贵州省麻黄洞为例

为揭示岩溶洞穴滴水元素季节变化特征及其对外界气候环境变化的响应关系,对贵州绥阳双河洞系支洞麻黄洞内3处滴水的Mg、Ca、Sr元素进行了为期13个月的监测。结果显示:(1)3个滴水点M1、M2和M3的水化学类型主要为HCO3·Ca型,岩溶水对于方解石与白云石等矿物的溶解处于饱和状态;(2)上覆土壤和岩层厚度逐渐增加,导致水-土-岩作用时间也随之增加;(3)Ca^2+、Mg^2+、Sr^2+浓度变化总体上呈逐级递增的特点,各离子浓度在高温多雨季节波动幅度大,低温少雨季节变化平稳;(4)Mg/Ca、Sr/Ca均表现出雨季低、旱季高的特征,反映该地区外界干湿条件的变化;(5)由模型模拟显示,3个滴水点皆以PCP/ICD作用为主,M1对降雨响应不敏感,M2滴率与离子浓度呈雨季高、旱季低的变化规律,M3位于洞穴最深、顶板最厚处,滴率与离子浓度无显著季节变化特征。结合各滴水点洞穴环境变化规律,推断M2更能准确响应外界气候环境变化。     

Origin and palaeoenvironmental significance of lamination in stalagmites from Katerloch Cave,Austria

The origin and environmental dependencies of lamination in stalagmites from Katerloch, common in speleothems from other cave sites, are examined in detail. Petrographic observations and chemical analyses (including isotopes) of stalagmites and modern calcite were combined with multi‐annual cave monitoring. All investigated stalagmites are composed of low‐Mg calcite and show white, porous laminae and typically thinner, translucent dense laminae. The binary lamination pattern results from changes in the calcite fabric: white, porous laminae are characterized by a high porosity and abundant fluid inclusions and also by enhanced vertical growth and thinning towards the flanks. Translucent, dense laminae exhibit a compact fabric and constant thickness of individual growth layers. U‐Th dating supports an annual origin of the lamination and the seasonally changing intensity of cave ventilation provides a robust explanation for the observed relationships between lamination, stable C isotopic compositions and trace elements (Mg, Sr and Ba). The seasonally variable air exchange, driven by temperature contrasts between the cave interior and outside atmosphere, modulates the rate and amount of CO₂ degassing from the drip water and affects the hydrochemistry and consequently the fabric of the precipitating calcite. Although cave air composition and drip rate are both major variables in controlling CO₂ degassing from the drip water, the seasonally changing ventilation in Katerloch exerts the primary control and the results suggest a secondary (amplifying/attenuating) influence of the drip rate. Drip rate, however, might be the controlling parameter for lamina development at cave sites experiencing only small seasonal cave air exchange. Importantly, the seasonally variable composition of drip water does not reflect the seasonal cycle of processes in the soil zone, but results from exchange with the cave atmosphere. The alternating porous and dense calcite fabric is the expression of a variable degree of lateral coalescence of smaller crystallites forming large columnar crystals. The white, porous laminae represent partial coalescence and form during the warm season: low calcite δ¹³C values are linked to low δ¹³C values of cave air and drip water during that time. This observation corresponds to times of reduced cave ventilation, high pCO₂ of cave air, low drip water pH, lower calcite supersaturation and typically high drip rates. In contrast, the translucent, dense laminae represent more or less complete lateral coalescence (inclusion‐free) during the cold season (high calcite, drip water and cave air δ¹³C values), i.e. times of enhanced cave ventilation, low cave air pCO₂, increased drip water pH, relatively high calcite supersaturation and typically low drip rates. In essence, the relative development of the two lamina types reflects changes in the seasonality of external air temperature and precipitation, with a strong control of the winter air temperature on the intensity of cave‐air exchange. Thick translucent, dense laminae are favoured by long, cold and wet winters and such conditions may be related closely to the North Atlantic Oscillation mode (weak westerlies) and enhanced Mediterranean cyclone activity during the cold season. Studies of speleothem lamination can thus help to better understand (and quantify) the role of seasonality changes, for example, during rapid climate events.     

贵州七星洞滴水的水文水化学特征及其意义

本文对贵州都匀七星洞9个滴水点进行厂为期1年的动态临测，结果显示滴水的物质组成直接源自于洞穴环境，即土壤和岩石。而大气降雨携带的物质成分较少。洞穴滴水的化学组成中元素含量变化主要由水运移过程中水-土、水-岩作用导致的岩石溶解-方解石沉淀过程所控制。QXD-1#、QXD-2#、QXD-6#、QXD-7#、QXD-8#由于水运移过程中经过的土壤较薄。水-岩作用对滴水化学特性的贡献略大。稀释作用发生在干旱条件下的QXD-2#滴水点，活塞作用在雨季对QXD-7#、QXD-9#滴水产生影响，在不同的季节，QXD-1#、QXD-3#、QXD-8#滴水点的滴率产生跳跃式变化。这些作用均受控于水的来源差异。所有这些过程对滴水点水化学产生影响但其效果较弱。滴水的Mg／Ca指示了大气降雨的变化，其值受控于洞穴顶板内水运移过程中水-土、水-岩作用下的水文地球化学过程即岩石的溶解、方解石沉淀过程及土壤物理、化学、生物学过程等。     

贵州凉风洞洞穴滴水水文水化学过程分析

通过对贵州荔波凉风洞5个滴水点进行为期1年的动态监测,表明除大气降雨携带的较少物质成份外,凉风洞滴水中的物质主要来源于土壤,同时,示踪结果显示出凉风洞滴水对大气降雨的响应较快,滴水的物质组成直接源自于洞穴环境。洞穴滴水的化学组成中元素含量的变化主要由水运移过程中水-土、水-岩作用导致的方解石溶解-沉淀过程所控制,稀释作用、水来源的差异或者活塞流产生了一定的效果,但其影响较弱,表明凉风洞滴水点的次生沉积物可能记录了环境变化信息。但水在洞穴顶板内运移过程中发生的水文地球化学过程(岩石的溶解、方解石沉淀作用过程)以及洞穴滴水响应大气降雨的时间尺度、水动力过程、水流形式等因素,影响到凉风洞洞穴次生沉积物过去环境记录指标。因此,岩溶次生沉积物过去环境变化指标的解译应该有洞穴滴水水动力地球化学过程的结果作为支撑。这些过程的清晰化可以更好地为研究洞穴环境次生沉积记录的高分辨率、短时间尺度的过去变化提供依据。     

Sr/Sr and Sr/Ca in speleothems for paleoclimate reconstruction in Central China between 70 and 280 kyr ago

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 (33^o40N′ 109^o05′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.     

Stable Carbon Isotope Variations in Cave Percolation Waters and their Implications in Four Caves of Guizhou, China

Monitoring and sampling of main plants,soil CO2,soil water,bedrock,spring water,drip water and its corresponding speleothem were performed at four cave systems of Guizhou,Southwest China,from April 2003 to May 2004,in order to understand stable carbon isotope ratios variations of dissolved inorganic Carbon(DIC) in cave percolation waters(δ13CDIC) and their implications for paleoclimate.Stable carbon isotopic compositions and ions(Ca,Mg,Sr,SO4,Cl etc.) were measured for all samples.The results indicate that there are significant differences among the δ13CDIC values from inter-cave,even inter-drip of intra-cave in the four caves.The δ13CDIC values from the Liangfeng Cave(LFC) is lightest among the four caves,where vegetation type overlying the cave is primary forest dominated by tall trees with lighter average δ13C value(–29.9‰).And there are remarkable differences in δ13CDIC values of different drip waters in the Qixing Cave(QXC) and Jiangjun Cave(JJC),up to 6.9‰ and 7.8‰,respectively.Further analyses show that the δ13CDIC values in cave drip waters are not only controlled by vegetation biomass overlying the cave,but also hydro-geochemical processes.Therefore,accurate interpreting of δ13C recorded in speleothems cannot be guaranteed if these effects of the above mentioned factors are not taken into consideration.