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

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

贵州纳朵洞洞穴滴水、现代沉积物δ18O特征及其环境意义

为了研究洞穴滴水及其对应的现代沉积物氧同位素的变化特征和对外界气候环境的指示意义,文章对贵州纳朵洞洞外大气降水、洞穴池水、6处滴水点及其对应的现代沉积物氧同位素进行了近2年的监测。结果显示纳朵洞外大气降水和洞穴池水δ18O值均呈现旱季偏重,雨季偏轻的季节特征,基本能反映洞穴所在区域的气候变化。而滴水沉积物δ18O值和滴水δ18O值自身存在协调同步的季节特征,但二者δ18O值与大气降水δ18 O值却呈现反向的季节变化,这可能是区域地形、岩溶表层带的调节和大气环流共同作用的结果。      

洞穴滴(流)水的双重(滴－侵蚀、沉积)作用——以桂林盘龙洞为例

洞穴滴水主要来源于大气降水的入渗,是岩溶洞穴内的低能量的渗流水,它受控于水- 土- 岩的相互作用。本文通过对桂林盘龙洞滴水一个水文年的动态监测表明,洞穴滴水对大气降水的响应较快,其所记录的滴水特性直接反映大气降水的物理、化学特征,并系统地记录了滴水溶- 侵蚀和沉积过程,以及与生态环境和石漠化的演化历史。常年性滴水的动态监测,揭示在夏半年( 5- 10月)是新碳酸盐的主要沉积时段,表现出新碳酸盐的沉积具有与雨热同季的特点。暴雨或季节性滴水基本保持了雨水的物理化学特性,滴水量大,滴速快,因而具有较强的溶- 侵蚀作用,导致盘龙洞石笋Pa、Pb、Pc 形成后被溶- 侵蚀的体积分别达339872 cm3、13 680 cm3 和33 792 cm3; 在冬半年,常年性滴水由于滴速和滴量较小,其溶- 侵蚀性较弱;而在夏半年,由于滴水的饱和度高,沉积量大,往往将在冬半年形成细微的滴溶蚀凹坑或孔穴填平补齐。      

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.     

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.     

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.     

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.     

A multiple cave deposit assessment of suitability of speleothem isotopes for reconstructing palaeo‐vegetation and palaeo‐temperature

The suitability of speleothems for interpreting palaeoclimate is typically determined by using either the Hendy Test, overlapping analysis or long‐term cave environment monitoring. However, in many cases, these methods are not applicable, because a speleothem lacks clearly traceable layers for the Hendy Test, it is difficult to obtain an overlapping speleothem nearby, or long‐term cave monitoring is impractical. The authors propose a multiple cave deposit approach to assess the suitability of speleothems for palaeoclimate study. Speleothems collected from two sites within Raccoon Mountain Cave, Tennessee (USA) exhibit remarkable spatial variation (δ¹³C: ?10·3‰ to ?2·2‰) over a relatively short distance (ca 260 m). Drip water δ¹⁸O values exhibit a seasonal precipitation signal at Site 1 and an annual signal at Site 2. Combining field observations, water isotope analysis and trace‐element data, the authors propose that the speleothem formation at Site 1 and Site 2 tapped distinct sources of CO₂: (i) CO₂ derived from overlying soils for Site 1; and (ii) limestone dissolved inorganic carbon induced by ground water dissolution for Site 2. Using fresh cave deposits (modern speleothem) δ¹³C (100% C3 vegetation) as an analogue, a simple model was developed to estimate land surface vegetation for speleothems. The speleothem formation temperature estimated using fresh cave deposit δ¹⁸O values generally reflects the mean annual temperature in this region. This study indicates that spatial variations in carbon isotopes could be caused by different carbon sources dominating in different parts of the cave, which should be taken into consideration by researchers when using speleothem δ¹³C values to reconstruct temporal palaeo‐vegetation changes. This study demonstrates a practical sampling strategy for verifying suitability of speleothems for palaeo‐vegetation and palaeo‐temperature reconstructions by analysing multiple cave deposits, especially for cases in which the Hendy Test, parallel sampling and long‐term monitoring of cave environment are not feasible.     

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.     

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.     

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.     

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.     

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.     

重庆金佛山羊口洞滴水δD和δ18O变化特征及其环境意义

为探究重庆金佛山羊口洞滴水δD、δ18O化特征及其环境意义,于2011年10月—2013年8月,在重庆市南川区金佛山逐月采集大气降水样品及羊口洞6个滴水监测点的滴水样品进行氢氧稳定同位素测定。通过比较降水和滴水δD、δ18O的分布特征、季节变化及其与降水量和温度的相关性发现：（1）6个滴水点δD、δ18O较均匀地分布在当地降水线附近,表明从降水到形成滴水的过程受蒸发作用影响不大,滴水δD、δ18O现了当地大气降水δD、δ18O均水平。（2）受洞穴上覆岩土层的调蓄作用影响,羊口洞各滴水点δD和δ18O变化范围（—46.77~—62.09‰,—7.05~—9.96‰）远小于洞外大气降水（5.17~—115.63‰和—1.44~—16.10‰）,且较降水存在明显滞后性。但滴水δD、δ18O体上也表现出与降水相同的夏季偏轻、冬季偏重的趋势,主要受降水水汽源地季节性差异影响。而各个监测点滴水δD和δ18O节变化差异较大,可能受滴水点上覆岩层裂隙管道发育、覆盖层厚度、岩溶水滞留时间、形成滴水前的运移路径、滴水点的高度和滴率、滴水点距离洞穴出入口的距离等多种原因影响。（3）降水δ18O现出＂降水量效应＂和＂负温度效应＂,羊口洞滴水δ18O降水量总体上也呈负相关关系,而与温度（水温、洞温）的关系则呈现多样化：1#、2#、5#、6#监测点滴水δ18O温度不相关,3#点为正相关,4#点为负相关,这与各监测点滴水δ18O节变化差异较大有关。（4）总体而言,羊口洞滴水δD和δ18O季节变化不够明显,利用羊口洞石笋进行季节分辨率的古气候重建可能性较低,但滴水δD和δ18O承了当地大气降水信息,其石笋δ18O用于重建年际~十年际及更长时间尺度的古气候变化。     

桂林洞穴滴水及现代碳酸钙(CaCO3)沉积的碳同位素记录及其环境意义

经过前期(1995~2000年)及近2 a对桂林盘龙洞13个滴水点的2 个水文年的滴水和现代碳酸钙沉积的动态监测, 发现现代洞穴碳酸钙(CaCO3)沉积有两种类型: ①常年性滴水沉积碳酸盐, 其δ13C值记录了全年气候变化特征; ②季节性滴水沉积碳酸盐, 其δ13C值记录了季节性气候变化特征。现代碳酸盐沉积监测和碳同位素分析表明, 桂林盘龙洞外部峰体主要为C3植物(几乎没有C4植物), 现代沉积碳酸盐的δ13C记录显示, 在夏半年, 夏季风强、降水丰沛、生物的活动量大, 现代碳酸盐沉积量大,δ13C值则较偏负, 平均为-13.13‰; 现代碳酸盐的δ13C全年平均值为-12.23‰, 最负值达-14.5‰; 而在冬半年, 由于降水相对较少, 新沉积碳酸盐的δ13C值, 显示稍有增加(或偏正), 其δ13C值为-10‰~-11‰。此外, 当在降大雨或暴雨后(无论是在夏半年或是在冬半年), 滴水在滞后半个月或1个月后沉积形成的碳酸盐, 其δ13C值显示突然偏负, 主要反映的是降雨效应引起的CO2 效应的影响。     

桂林凉风洞洞穴空气及滴水水化学对区域环境的响应

针对广西桂林凉风洞洞穴空气（CO2、δ13CCO2）和滴水的物理、化学指标（水温、电导率、pH、Ca2+、HCO3-）开展一年监测。结果表明:受到洞穴上覆土壤层CO2的影响,洞穴空气CO2和δ13CCO2分别呈现出明显夏季高、偏轻,冬季低、偏重的季节性变化规律;各个监测点CO2和δ13CCO2存在差异的主要因为是受到洞穴内部结构的阻隔作用,以及土壤层CO2在岩溶表层带不同滞留时间的影响,但是δ13CCO2变化相对于CO2对于外界环境的响应更加灵敏,且不同季节洞穴的通风模式差异使得洞穴空气CO2影响因素存在差异,夏季土壤CO2为主要影响因素、冬季大气CO2为主要影响因素。与此同时,洞穴滴水水化学指标也均表现出明显季节性变化特征。虽然雨季携带进入管道或裂隙的CO2增加,但是与表层岩溶带“老水”混合使其整体上呈现为缓慢上升。桂林地区季节性干旱使得洞穴顶部入渗水补给量减少,导致对围岩的溶解量相对降低,使其成为水化学指标快速下降的主要影响因素。此外,每个滴水点的水化学指标变幅因其径流路径的不同存在差异。      

水样中溶解性无机碳同位素测试前处理方法对比研究

水中溶解性无机碳(DIC)的碳同位素前处理方法由传统的BaCl2沉淀法,逐步发展到野外采样后直接通过连续流系统(GasBench-IRMS)测试.当前对于BaCl2沉淀法和连续流测试结果的差异,以及最佳DIC的前处理方法均需要开展深入研究.本文应用BaCl2沉淀法、医用无菌高密度聚乙烯瓶装样、GasBenchⅡ顶空样品瓶野外直接生成CO2气体三种前处理方法,对比研究前处理方法对采自桂林盘龙洞洞穴滴水和地下河水样中DIC碳同位素测试的影响.结果表明,由于BaCl2沉淀法使水样中游离CO2逸出,导致测定的DIC碳同位素值相对于另两种方法均偏正:地下河水样的碳同位素值最大偏正0.26‰;洞穴滴水的碳同位素值最大偏正0.33‰.因为野外水样采集环境的温度、大气压强与实验室内部环境变化较小,没有引起CO2、HCO3的溶解度改变,用医用无菌高密度聚乙烯瓶和GasBenchⅡ顶空样品瓶采集水样的碳同位素测试结果相同;相对而言,利用GasBenchⅡ顶空样品瓶直接产生CO2气体,能够避免外界环境条件变化导致CO2、HCO3-的溶解度发生变化引起碳同位素分馏,是精确测定水中DIC碳同位素最佳的前处理方法.     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.     

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.     

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.