Influences of air CO<Subscript>2</Subscript> on hydrochemistry of drip water and implications for paleoclimate study in a stream-developed cave,SW China

Cave air CO₂ is a vital part of the cave environment. Most studies about cave air CO₂ variations are performed in caves with no streams; there are few studies to date regarding the relationship of cave air CO₂ variations and drip water hydrochemistry in underground stream–developed caves. To study the relationship of underground stream, drip water, and cave air CO₂, monthly and daily monitoring of air CO₂ and of underground stream and drip water was performed in Xueyu Cave from 2012 to 2013. The results revealed that there was marked seasonal variation of air CO₂ and stream hydrochemistry in the cave. Daily variations of cave air CO₂, and of stream and drip water hydrochemistry, were notable during continuous monitoring. A dilution effect was observed by analyzing hydrochemical variations in underground stream and drip water after rainfall. High cave air CO₂ along with low pH and low δ¹³C_DIC in stream and drip water indicated that air CO₂ was one of the dominant factors controlling stream and drip water hydrochemistry on a daily scale. On a seasonal scale, stream flows may promote increased cave air CO₂ in summer; in turn, the higher cave air CO₂ could inhibit degassing of drip water and make calcite δ¹³C more negative. Variation of calcite δ¹³C (precipitated from drip water) was in reverse of monthly temperature, soil CO₂, and cave air CO₂. Therefore, calcite δ¹³C in Xueyu Cave could be used to determine monthly changes outside the cave. However, considering the different precipitation rate of sediment in different seasons, it was difficult to use stalagmites to reconstruct environmental change on a seasonal scale.     

Intra‐annual variation of the calcite deposition rate of drip water in Shihua Cave,Beijing, China and its implications for palaeoclimatic reconstructions

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.     

Cave air and hydrological controls on prior calcite precipitation and stalagmite growth rates: Implications for palaeoclimate reconstructions using speleothems

Hourly resolved cave air P_CO2 and cave drip water hydrochemical data illustrate that calcite deposition on stalagmites can be modulated by prior calcite precipitation (PCP) on extremely short timescales. A very clear second-order covariation between cave air P_CO2 and drip water Ca²⁺ concentrations during the winter months demonstrates the effects of degassing-induced PCP on drip water chemistry. Estimating the strength of the cave air P_CO2 control on PCP is possible because the PCP signal is so clear; at our drip site a one ppm shift in Ca²⁺ concentrations requires a P_CO2 shift of between 333 and 667 ppm. This value will undoubtedly vary from site to site, depending on drip water flow rate, residence time, drip water-cave air P_CO2 differential, and availability of low P_CO2 void spaces in the vadose zone above the cave. High-resolution cave environmental measurements were used to model calcite deposition on one stalagmite in Crag Cave, SW Ireland, and modelled growth over the study period (222 μm over 171 days) is extremely similar to the amount of actual calcite growth (240 μm) over the same time interval, strongly suggesting that equations used to estimate stalagmite growth rates are valid. Although cave air P_CO2 appears to control drip water hydrochemistry in the winter, drip water dilution caused by rain events may have played a larger role during the summer, as evidenced by a series of sudden drops in Ca²⁺ concentrations (dilution) followed by much more gradual increases in drip water Ca²⁺ concentrations (slow addition of diffuse water). This research demonstrates that PCP on stalactites, cave ceilings, and void spaces within the karst above the cave partially controls drip water chemistry, and that thorough characterisation of this process at individual caves is necessary to most accurately interpret climate records from those sites.     

Carbon mass-balance modelling and carbon isotope exchange processes in dynamic caves

Diverse interpretations have been made of carbon isotope time series in speleothems, reflecting multiple potential controls. Here we study the dynamics of ¹³C and ¹²C cycling in a particularly well-constrained site to improve our understanding of processes affecting speleothem δ¹³C values. The small, tubular Grotta di Ernesto cave (NE Italy) hosts annually-laminated speleothem archives of climatic and environmental changes. Temperature, air pressure, pCO₂, dissolved inorganic carbon (DIC) and their C isotopic compositions were monitored for up to five years in soil water and gas, cave dripwater and cave air. Mass-balance models were constructed for CO₂ concentrations and tested against the carbon isotope data. Air advection forces winter pCO₂ to drop in the cave air to ca. 500 ppm from a summer peak of ca. 1500 ppm, with a rate of air exchange between cave and free atmosphere of approximately 0.4 days. The process of cave ventilation forces degassing of CO₂ from the dripwater, prior to any calcite precipitation onto the stalagmites. This phase of degassing causes kinetic isotope fractionation, i.e. ¹³C-enrichment of dripwater whose δ¹³C_DIC values are already higher (by about 1‰) than those of soil water due to dissolution of the carbonate rock. A subsequent systematic shift to even higher δ¹³C values, from −11.5‰ in the cave drips to about −8‰ calculated for the solution film on top of stalagmites, is related to degassing on the stalagmite top and equilibration with the cave air. Mass-balance modelling of C fluxes reveals that a very small percentage of isotopically depleted cave air CO₂ evolves from the first phase of dripwater degassing, and shifts the winter cave air composition toward slightly more depleted values than those calculated for equilibrium. The systematic ¹³C-enrichment from the soil to the stalagmites at Grotta di Ernesto is independent of drip rate, and forced by the difference in pCO₂ between cave water and cave air. This implies that speleothem δ¹³C values may not be simply interpreted either in terms of hydrology or soil processes.     

Reconstructing palaeoprecipitation from an active cave flowstone

Several drill cores were obtained from a laminated, actively forming flowstone from a shallow cave in Austria. Highly resolved petrographic and geochemical analyses combined with multi‐annual cave monitoring reveal a distinct sensitivity of flowstone growth and composition to late Holocene meteoric precipitation. The regular sub‐millimetre‐scale lamination consists of thicker, translucent laminae and thinner (organic) inclusion‐rich laminae. There is also a macroscopic millimetre‐scale banding of darker and lighter bands comprising several laminae. Stable isotope analyses of drill cores and modern calcite precipitates show a pronounced positive covariation of δ¹³C and δ¹⁸O values indicative of kinetic isotope effects. Comparing the isotope values with petrography shows gradual changes across several of the annual laminae, i.e. changes of several per mille on a multi‐annual to decadal timescale. The stable isotope and trace‐element composition, as well as the flowstone petrography, are mainly controlled by the variable drip‐water discharge controlling the water‐film thickness and water residence time on the flowstone surface and consequently the intensity of CO₂‐degassing, kinetic isotope enrichment and concomitant calcite precipitation. Drill core PFU6 provides an isotope record of the last ca. 3000 years at near‐annual resolution. A distinct phase of low C and O isotope values – interpreted as increased discharge and hence higher meteoric precipitation – occurred from ca. 300 to 140 a b2k (second half of the Little Ice Age) and another wet interval occurred around 700 a, corresponding to reported Medieval glacier advances. The Roman Warm Period was also dominated by relatively wet conditions, although significant decadal variability prevailed. Increased precipitation further characterized the intervals from ca. 2480 to 2430 and 2950 to 2770 a. Dry conditions persisted during the Medieval Climate Anomaly, although this trend towards reduced precipitation started earlier. The highest C isotope values of the last 2 ka are recorded around 750 a and another dry phase is centred at 1480 a. This new record shows that inter‐annual to decadal oscillations are a dominant mode of variation during the last 3 ka in the Alps. Copyright © 2011 John Wiley & Sons, Ltd.     

Geochemical and hydrological controls on biannual lamination of tufa deposits

Fluvial tufa deposits in southwest Japan commonly develop biannual lamination consisting of dense summer layers and porous winter layers, and the clearness of the laminae varies among the sites. The laminae have been largely attributed to a seasonally variable inorganic precipitation rate of calcite. This rate-controlled hypothesis was examined by using quantitative data for calcite packing-density (CPD) and the precipitation rate of calcite (PWP rate) calculated from water chemistry. The results for four tufa-depositing sites in SW Japan show that a positive correlation between CPD and PWP rate becomes less certain with increasing PWP rate. In the temperature realm of SW Japan, tufas develop regular distinct seasonal change in CPD when deposited in water containing Ca values less than 65 mg/l, which results in a relatively low precipitation rate. The CPD of tufa deposits rarely exceeds 65%, owing to pore space between fine-grained calcite crystals and to porosity derived from decomposed cyanobacteria and other microorganisms. By increasing the Ca content to more than 65 mg/l, the CPD often attains an upper limit and becomes insensitive to seasonal changes in the PWP rate. Therefore, seasonal variations in CPD at sites with a higher Ca content are unclear, as seen in two examples from tropical islands in southern Japan and in one locality in a temperate climate. The flow rate and microbial density on the tufa surface are subordinate factors with respect to the CPD. Seasonal changes in these two factors often enhance the porous/dense contrast of biannual lamination in SW Japan.     

Temporal and environmental significance of microbial lamination: Insights from Recent fluvial stromatolites in the River Piedra,Spain

Despite extensive research, the environmental and temporal significance of microbial lamination is still ambiguous because of the complexity of the parameters that control its development. A 13 year monitored record of modern fast‐accreting calcite stromatolites (mean 14 mm year^?1) from artificial substrates installed in rapid flow in the River Piedra (north‐east Spain) allows comparison of the sedimentological attributes of successive six‐month depositional packages with the known climatic, hydrophysical and hydrochemical parameters of the depositional system. The stromatolites are formed of dense, porous and macrocrystalline composite laminae. The dense and porous composite laminae, which are composed of two to eight laminae consisting largely of calcified cyanobacteria, are characterized by: (i) dense composite laminae, up to 15 mm thick, mostly with successive dense laminae and minor alternating dense and porous laminae; and (ii) porous composite laminae, up to 12 mm thick, consisting mainly of porous laminae alternating with thinner dense laminae. Most of the dense composite laminae formed during the warm periods (April to September), whereas most of the porous composite laminae developed in the cool periods (October to March). Each dense and porous composite lamina represents up to or slightly longer than six months. The alternation of these two types of composite laminae parallels seasonal changes in temperature. The dense and porous laminae result from shorter (for example, intraseasonal) variations in temperature, insolation and hydrological conditions. The macrocrystalline laminae, with crystals >100 μm long, occur isolated and grouped into composite laminae up to 1·7 mm thick. Their occurrence suggests the absence or poor development of microbial mats over periods of weeks to several months. Thus, stromatolite lamination can record different‐order, periodic and non‐periodic changes in the magnitude of environmental parameters over a single year. These results hold important implications for the temporal and environmental interpretation of lamination in microbial structures.     

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     

北京石花洞石笋微层层面有机物质的形成时间及机理初探

通过对北京石花洞滴水水溶性有机碳(DOC)近一个水文年的观测,发现不同点滴水DOC浓度均表现出明显的季节性变化,7月中旬均有一个大的主峰出现。初步说明中国北方石笋微层的层面物质沉积于7月雨季,主要来源于大的雨量对土壤中有机质的淋溶;洞穴顶板较薄的滴水点在5月和8月有明显的DOC次峰,可能与石笋亚年层形成有关。     

The growth mechanism of the aragonitic stalagmite laminae from Yunnan Xianren Cave,SW China revealed by cave monitoring

Duan, W., Cai, B., Tan, M., Liu, H. & Zhang, Y. 2012 (January): The growth mechanism of the aragonitic stalagmite laminae from Yunnan Xianren Cave, SW China revealed by cave monitoring. Boreas, Vol. 41, pp. 113–123. 10.1111/j.1502‐3885.2011.00226.x. ISSN 0300‐9483. Stalagmites from Xianren Cave in Yunnan Province, SW China have visible bands of alternating compact and porous sub‐layers, which have recently been demonstrated to be annual: the compact sub‐layer consists of elongated columnar aragonites with a general longitudinal orientation (parallel to the vertical growth axis), while the porous sub‐layer is composed mainly of needle aragonites forming radiating masses. In order to understand the growth mechanism of this type of stalagmite laminae, factors that could determine the growth rate and crystal structures of modern carbonates, such as cave‐air temperature, CO₂ concentration, drip rate and the hydrochemical parameters of drip water, have been monitored systematically. In this study, we selected five active drip sites to monitor for two years at a monthly frequency. Based on the monitoring results and the analyses of stalagmite laminae, we conclude that the compact sub‐layer forms in winter, when the drip rate is moderate and the degassing is slow, continuous and prolonged. The porous sub‐layer forms in early spring, when the drip rate is lower and Mg/Ca is higher than that during the formation of the compact sub‐layer. We also found exceptionally some calcite laminae. Furthermore, we discovered modern calcites precipitating at all study sites in the first hydrologic year when the rainfall was very abundant. Therefore, it is suggested that the occurrence of localized calcites in an aragonitic stalagmite indicates an interval of higher rainfall.     

洞穴碳酸盐微层研究及其发展方向

近几年,在分辨率气候－环境变化研究中,洞穴碳酸盐微层逐渐受到人们重视。洞穴碳酸盐微层的类型较多,主要为年层。微层是在沉积条件发生高频率的周期性改变时形成的,要受到供水条件和碳酸钙浓度等多因素的控制。洞穴碳酸盐微层的稳定同位素组成,生长速率,微层结构与物质组分,微层厚度与灰度和光学特征等可以反映降水,温度,土壤成分及植被变化等信息。     

Estimation of carbon dioxide flux degassing from percolating waters in a karst cave: Case study from Bijambare cave,Bosnia and Herzegovina

Drip water, collected above three actively forming stalagmites, has been analyzed and the results discussed using a calcite saturation index versus equilibrium carbon dioxide partial pressure theoretical relationship. Percolating water appears to have been originated from a parent solution in equilibrium with a carbon dioxide rich gas phase having a minimum concentration varying between 15,000 ppmv and 26,000 ppmv while large part of the variability recorded in the cave can be explained by different stage of degassing. Similarly, analyses performed at several cave pools confirm that drip water rapidly achieves equilibrium with the cave atmosphere after impact on the stalagmite apex, while oversaturation is retained longer. Using these boundary conditions, the changes in inorganic carbon concentration in the percolating water have been calculated and converted into fluxes using an average effective infiltration flow estimated from the annual water balance.The predicted flux of carbon dioxide degassing from drip water is in the range of 0.03–0.06 μmol m⁻² s⁻¹. This flux has been found to be one of the major sources of carbon dioxide in the cave atmosphere during low ventilation periods.     

Modelling carbon isotopes of carbonates in cave drip water

C isotopes in cave drip water are affected by both the C isotope composition of soil air and host rock carbonate. Furthermore, the C isotope composition of cave drip water strongly depends on the calcite dissolution system, i.e., open, closed and intermediate conditions. Here, we present a calcite dissolution model, which calculates the ¹⁴C activity and δ¹³C value of the dissolved inorganic carbon of the drip water. The model is based on the chemical equations describing calcite dissolution (). The most important improvement, relative to previous models, is the combination of the open and closed system conditions in order to simulate the C isotope composition during intermediate states of calcite dissolution and the application to carbon isotope measurements on cave drip waters from Grotta di Ernesto, Italy. The major changes in the C isotope composition of the drip water occur in response to variations in the open-closed system ratio. Additionally, the ¹⁴C activity and the δ¹³C value of the drip water depend on changes in the partial pressure of soil CO₂. Radiocarbon and δ¹³C values of the Grotta di Ernesto drip water are well reproduced by the model.     

Hyperspectral imaging of speleothems

Proxy records from speleothems are used in palaeoclimatic reconstructions, as the factors controlling their growth rate, nature of their internal structure and chemical composition respond to changes in surface climate. Optical analyses of stalagmites include visual observation of stalagmite images obtained from flatbed scanners or digital cameras. Hyperspectral imaging has not been used in stalagmite research, but potentially has many advantages over standard optical imaging techniques. Hyperspectral images of a set of stalagmites have been obtained in order to demonstrate the application of hyperspectral imaging in speleothem research. Our results highlight the following: (1) Spectra obtained for these calcite stalagmites are similar between a group of stalagmites of different ages, hydrological setting within a cave and from different caves. (2) The largest differences in relative reflectance between areas of dark compact calcite (DCC) and white porous calcite (WPC) are in the range 470–590 nm (this may extend to 680 nm for some of the stalagmites). (3) Imaging in the near infrared (NIR) demonstrates a decrease in reflection at water absorbance wavelengths, suggesting there is potential for mapping H₂O.     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.     

Seasonal records of climatic change in annually laminated tufas: short review and future prospects

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.     

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。}     

Cave air control on dripwater geochemistry, Obir Caves (Austria): Implications for speleothem deposition in dynamically ventilated caves

There are very few process studies that demonstrate the annual variation in cave environments depositing speleothems. Accordingly, we initiated a monitoring program at the Obir Caves, an Austrian dripstone cave system characterized by a seasonally changing air flow that results in a predictable pattern of high pCO₂ during summer and low pCO₂ in winter. Although similar seasonal changes in soil pCO₂ occur, they are not directly connected with the changes in the subsurface since the dripwaters are fed from a well-mixed source showing little seasonal variation. Cold season flushing by relatively CO₂-poor air enhances degassing of CO₂ in the cave and leads to a high degree of supersaturation of dripwater with regard to calcite. Forced calcite deposition during the cold season also gives rise to a pronounced pattern of synchronous seasonal variations in electrical conductivity, alkalinity, pH, Ca and δ¹³C_DIC which parallel variations recorded in δ¹³C_{cave air}. Chemical components unaffected by calcite precipitation (e.g., δD, δ¹⁸O, SiO₂, SO₄) lack a seasonal signal attesting to a long residence in the karst aquifer. Modeling shows that degassing of CO₂ from seepage waters results in kinetically-enhanced C isotopic fractionation, which contrasts with the equilibrium degassing shown from the Soreq cave in Israel. The Obir Caves may serve as a case example of a dripstone cave whose seepage waters (and speleothems) show intra-annual geochemical variability that is primarily due to chemical modification of the groundwater by a dynamic, bidirectional subsurface air circulation.     

The significance of chemical,isotopic, and detrital components in three coeval stalagmites from the superhumid southernmost Andes (53°S) as high-resolution palaeo-climate proxies

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.     

石笋矿物类型、成因及其对气候和环境的指示

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。