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。}     

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。     

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.     

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.     

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.     

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.     

岩溶洞穴现代沉积间断的影响因素研究--以河南鸡冠洞为例

岩溶洞穴次生沉积物--石笋因其独有的高精度测年和高分辨率记录的优势已越来越成为过去全球变化研究中重要的支柱。进行洞穴碳酸盐沉积机理研究对于理解石笋沉积速率,结晶形态、准确解译气候替代指标和现代洞穴合理保护具有重要意义。以我国南北交汇带亚洲季风敏感区河南鸡冠洞为例,通过对2010-2015年连续6个水文年对鸡冠洞滴水和碳酸盐沉积的监测发现:①洞内滴水水化学指标与沉积速率表现出很好的一致性,雨季大气降水增加,气温升高,生物活动加强,土壤CO₂含量增加,滴水滴速、Ca2+、HCO₃-、电导率（EC）和沉积速率同时增加,旱季反之;洞内CO₂对方解石沉积的抑制作用被滴水饱和度掩盖。②受2012-2013年年降雨量显著减少的影响,水岩作用减弱,2014年滴水饱和度降至最低,出现为期一年的沉积间断,直至2014年下半年降水增加,于11月重新接收到方解石沉积。③自2013年下半年开始,受人为淋滤洞穴影响,滴水NO₃-上升数十倍,模拟实验显示其对CaCO₃溶解的能力较之前提高约60%,表明NO₃-对方解石沉积存在抑制作用,这可能是个别月份滴水饱和度高却没有回收到CaCO₃沉积的原因,建议景区在进行补水的同时要考虑水质对岩溶作用的影响。     

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.     

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.     

北京石花洞空气环境主要因子季节性变化特征研究

洞穴大气CO2浓度不仅是影响洞穴沉积物沉积（或者溶蚀）的重要因素之一,而且在旅游洞穴,它关系到沉积物景观的稳定性以及旅游环境的舒适性。本文通过对石花洞洞穴大气温度、湿度及CO2浓度近4个水文年的观测,结果表明：（1）洞穴温度在15℃上下波动,夏季约高1℃,主要与洞内外温差的季节性变化和旅游活动有关;（2）洞穴CO2浓度随着大气温度上升而缓慢升高,至每年的7月上旬雨季来临时,气温、降水及土壤中CO2大幅提高,降水溶解大量的土壤CO2并渗入洞穴中,导致洞穴CO2浓度迅速上升,8月观测到的最高浓度可达到4 334ppm,在雨季结束后,随着大气温度降低,CO2浓度缓慢下降,2月份平均值达到最低,为360~458 ppm。另外,在5月份和10月份的旅游黄金周,旅游人数的增加,洞穴CO2浓度异常增高。在进行洞穴管理与规划时,应综合考虑自然和人为因素对洞穴的影响。     

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。     

北京石花洞洞穴滴水中硫酸根浓度的时空变化及其意义

硫是环境地球化学循环中重要的元素之一,是区域及全球性环境变化的重要驱动因子。本文通过对石花洞洞穴4个滴水点（JG,SH,PL1和PL2）硫酸根浓度近3个水文年的分析测定（BL点观测近两年）,结果表明:响应降雨快的滴水点（SH和JG点）滴水SO42-浓度升高幅度最明显,且滴水SO42-浓度与滴率成指数关系;滞后响应降雨的观测点滴水SO42-浓度雨季升高幅度不明显,但在长期观测期间有明显增加的趋势;对降雨没有响应的滴水点,其SO42-浓度低且雨季没有明显变化。通过分析表明,在快速响应降水的滴水点,滴水硫酸根浓度大幅升高可能在一定程度上影响滴水pH值,这也可能是导致雨季时,快速下渗进入洞穴的滴水碳酸钙饱和度降低,从而抑制滴水沉积的一个不可忽略的因素。      

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.     

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。      

A high‐resolution multi‐proxy stalagmite record from Mechara,Southeastern Ethiopia: palaeohydrological implications for speleothem palaeoclimate reconstruction

An annually laminated stalagmite from Southeastern Ethiopia grew for 443±8 yr starting at 5023 yr BP (±160 yr) as determined by lamina‐tuned U‐Th dating. The speleothem shows three growth phases: (1) an initial phase where the stalagmite has a candlestick shape, deposited by relatively slow rate drip water; (2) a middle growth phase where laminae grow on the flanks, suggesting faster drip rates; and (3) a final growth phase where the speleothem becomes narrower owing to a decrease in drip water supply towards the end of deposition. Morphometry, annual growth rate, fluorescence index, and ²³⁴U/²³⁸U isotope ratio show marked differences between the growth phases, while δ¹³C and δ¹⁸O do not show significant variation, except within the third phase towards the top of the stalagmite, where they have higher values. The study indicates that the multiproxy approach is crucial as the different proxies respond to single climate forcing in different manners. Our results can be widely applied to speleothem studies distinguishing the relative importance of the various proxies in recording cave ‘external’ (climate, hydrology) and cave ‘internal’ (e.g. evaporation) processes. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

Oxygen and carbon isotopic systematics of aragonite speleothems and water in Furong Cave, Chongqing, China

To understand oxygen and carbon stable isotopic characteristics of aragonite stalagmites and evaluate their applicability to paleoclimate, the isotopic compositions of active and fossil aragonite speleothems and water samples from an in situ multi-year (October 2005-July 2010) monitoring program in Furong Cave located in Chongqing of China have been examined. The observations during October 2005-June 2007 show that the meteoric water is well mixed in the overlying 300-500-m bedrock aquifer, reflected by relatively constant δ¹⁸O, ±0.11-0.14‰ (1σ), of drip waters in the cave, which represents the annual status of rainfall water. Active cave aragonite speleothems are at oxygen isotopic equilibrium with drip water and their δ¹⁸O values capture the surface-water oxygen isotopic signal. Aragonite-to-calcite transformation since the last glaciation is not noticeable in Furong stalagmites. Our multi-year field experiment approves that aragonite stalagmite δ¹⁸O records in this cave are suitable for paleoclimate reconstruction. With high U, 0.5-7.2 ppm, and low Th, 20-1270 ppt, the Furong aragonite stalagmites provide very precise chronology (as good as ±20s yrs (2σ)) of the climatic variations since the last deglaciation. The synchroneity of Chinese stalagmite δ¹⁸O records at the transition into the Bølling-Allerød (t-BA) and the Younger Dryas from Furong, Hulu and Dongge Caves supports the fidelity of the reconstructed East Asian monsoon evolution. However, the Furong record shows that the cold Older Dryas (OD) occurred at 14.0 thousand years ago, agreeing with Greenland ice core δ¹⁸O records but ∼200 yrs younger than that in the Hulu record. The OD age discrepancy between Chinese caves can be attributable to different regionally climatic/environmental conditions or chronological uncertainty of stalagmite proxy records, which is limited by changes in growth rate and subsampling intervals in absolute dating. Seasonal dissolved inorganic carbon δ¹³C variations of 2-3‰ in the drip water and 5-7‰ in the pool and spring waters are likely attributed to variable degrees of CO₂ degassing in winter and summer. The variable δ¹³C values of active deposits from −11‰ to 0‰ could be caused by kinetically mediated CO₂ degassing processes. The complicated nature of pre-deposition kinetic isotopic fractionation processes for carbon isotopes in speleothems at Furong Cave require further study before they can be interpreted in a paleoclimatic or paleoenvironmental context.     

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     

δC profiles along growth layers of stalagmites: Comparing theoretical and experimental results

The isotopic carbon ratio of a calcite-precipitating solution flowing as a water film on the surface of a stalagmite is determined by Rayleigh distillation. It can be calculated, when the -concentration of the solution at each surface point of the stalagmite and the fractionation factors are known. A stalagmite growth model based entirely on the physics of laminar flow and the well-known precipitation rates of a supersaturated solution of calcite, without any further assumptions, is employed to obtain the spatial distribution of the -concentration, which contributes more than 95% to the dissolved inorganic carbon (DIC). The δ¹³C profiles are calculated along the growth surface of a stalagmite for three cases: (A) isotopic equilibrium of both CO₂ outgassing and calcite precipitation; (B) outgassing of CO₂ is irreversible but calcite precipitation is in isotopic equilibrium. (C) Both CO₂ outgassing and calcite precipitation are irreversible. In all cases the isotopic shift δ¹³C increases from the apex along the distance on a growth surface. In cases A and B, calcite deposited at the apex is in isotopic equilibrium with the solution of the drip water. The difference between δ¹³C at the apex and the end of the growth layer is independent of the stalagmite’s radius, but depends on temperature. For case A, it is about half the value obtained for cases B and C. In case C, the isotopic composition of calcite at the apex equals that of the drip water, but further out it becomes practically identical with that of case B. The growth model has been applied to field data of stalagmite growth, where the thickness and the δ¹³C of calcite precipitated to a glass plate located on the top of a stalagmite have been measured as function of the distance from the drip point. The calculated data are in good agreement to the observed ones and indicate that deposition occurred most likely under conditions B, eventually also C. A sensitivity analysis has been performed, which shows that within the limits of observed external parameters, such as drip rates and partial pressure of carbon dioxide P_CO2 in the cave, the results remain valid.     

洞穴现代沉积物δ13C值的生物量效应及机理探讨:以贵州4个洞穴为例

在贵州选择一组植被退化系列的4个洞穴系统(荔波凉风洞、都匀七星洞、镇宁犀牛洞和安顺将军洞)为具体研究对象,对其地表植被生物量、植被和洞穴现代沉积物的δ13C值进行了对比分析.结果显示洞穴现代沉积物的δ13C值与生物量有着很强的负相关关系,说明洞穴沉积物的δ13C值在空间上可能存在生物量效应,与洞穴石笋所揭示的时间序列上的生物量效应相对应.根据已有的数据和认识,推断这种生物量效应主要由地表植被δ13C值及土壤CO2δ13C值的微生物作用共同控制:在地表植被生物量较大变化情况下,沉积物δ13C值的生物量效应主要受植被δ13C值变化主导;而在地表植被生物量较小变化的情况下,沉积物δ13C值的生物量效应主要受微生物作用主导,而植被δ13C值变化的影响相对较弱.