四川黄龙大湾-张家沟钙华沉积剖面的古气候记录研究

本文通过对黄龙景区大湾张家沟钙华剖面的系统研究,确认大湾张家沟14.0～85.0 ka B.P.钙华剖面的沉积层序,该剖面不是自下而上由老到新的正常层序,而可能是多期次(最少两期)沉积形成的.通过钙华氧碳同位素分析重建了钙华沉积过程中环境的变化:在钙华剖面形成的早期,夏季风强盛,气温较高,夏半年降水较多;在钙华形成的中晚期,气候干冷且变化较大.最后,依据钙华的沉积特征和年代学数据,初步探讨了该区钙华的沉积模式.     

云南白水台钙华景区的水化学和碳氧同位素特征及其在古环境重建研究中的意义

采用水化学仪器自动记录、现场滴定和样品碳氧稳定同位素测试相结合等方法,对云南中甸白水台钙华景区的水化学和碳氧稳定同位素特征进行了综合分析。主要结论是:形成白水台钙华的泉水具有很高的钙和重碳酸根离子浓度,相应地,泉水的CO₂分压显著高于土壤生物成因所能产生的CO₂分压。结合泉水出露的地质条件及其碳稳定同位素特征(^δ13C=-1.23‰)的分析,进一步发现,高CO₂分压主要与深部地热成因的CO₂有关,而非原来普遍认为的“是温暖湿润气候的产物”。可见,白水台钙华属于热成因类钙华。由此,根据白水台不同时代钙华氧稳定同位素组成的差异,对钙华形成时的水温进行了计算。结果发现自白水台钙华形成以来,水温变化高达11℃,即从最老(<35万年)钙华形成时的21℃降至现在的10℃。这可能与本地区强烈抬升导致的气温降低有关,也可能反映出地热对水温的影响在降低。此外,本文对用热成因类钙华进行古环境重建研究中值得注意的问题也做了讨论。这些问题包括放射性碳测年中“死碳”(来自深部碳酸盐碳和深部CO₂)的干扰及由深源CO₂和CO₂自水中逸出导致的钙华¹³C富集,后者在利用类似热成因碳酸盐沉积的^δ13C进行古植被重建时也是必须考虑的问题     

云南白水台雨水线及钙华δ18O的季节和空间变化特征

通过对云南白水台地区大气降水的δ18O和δD分析,建立了该地区大气降水线,并通过对过量氘的季节性变化特征分析,发现白水台地区冬、夏季风期间降雨云团有不同的源区.对现代钙华δ18O的季节变化分析,发现钙华的氧同位素值与降雨量有着较好的线性负相关关系,这一发现为下一步利用古钙华的δ18O数据重建古降水量提供了基础.研究还发现,水中富含轻氧稳定同位素16O的H2O向大气蒸发以及富含轻氧稳定同位素16O的CO2向大气逸出,是下游方向钙华δ18O增加的主要原因.     

基于钙均衡估算黄龙钙华沉积速率的探讨

从黄龙钙华的成因研究出发,结合地质历史分析及长观资料对核心景区景观水系统的相对稳定性作出了评价。通过对景观水中钙离子及其它组分含量在时间及空间上变化特征的分析研究,揭示了钙离子含量在时间上的相对稳定以及在空间上自上游而下逐渐降低的规律,这为采用钙均衡模式来研究钙华堆积区内的年沉积量提供了重要保证。在此基础上,进一步通过同位素测年、物探、测绘等综合手段对钙华堆积区内的历史与现代的平均沉积速率进行系统研究,并与前人的研究成果对比,验证了钙均衡模型的可行性和可靠性。计算结果表明,黄龙核心景区钙华的平均沉积速率为1～ 4. 86mm /a。      

云南白水台现代内生钙华微层的特征及其古气候重建意义

在云南白水台采集一现代内生钙华样品,该样品形成于1998年5月至2001年11月。切片观察,钙华中可见薄的褐色疏松微层和厚的白色致密微层,且交替出现。结合钙华样品的高分辨率碳氧稳定同位素测试,发现薄的褐色疏松微层(1.5~2.2mm)在每年的雨季(4~9月)形成,而厚的白色致密微层(5~8mm)在旱季(10~3月)形成。通过与气象记录的对比,建立起了这些钙华亚年层厚度和稳定同位素特征与气候变化的关系。结果发现:薄的微层及其低δ13C和δ18O值形成于温暖湿润的雨季。在雨季,雨水的稀释作用导致了内生钙华沉积的减慢和低的13C含量,而钙华的低18O值则主要与亚热带季风地区的雨量效应有关。因此,钙华微层厚度,以及δ13C和δ18O的显著降低反映了高的降雨条件,反之,则反映干旱的气候条件。本研究说明钙华可以提供有价值的年际甚至季节尺度的气候变化信息。     

四川九寨沟景区钙华起源初探

九寨沟风景区以绝美的景色闻名于世。钙华作为其独特景观的重要构成要素,有着重要的观赏价值和研究价值。为了弄清九寨沟钙华的起源,特别是CO2的来源,对九寨沟主要水体的水化学和碳氢氧同位素以及现代钙华的碳同位素进行了取样分析。结果发现:(1)九寨沟水体来源于大气降水的补给;(2)水体中碳酸氢根离子和钙离子浓度较低,主要来源于土壤CO2对碳酸盐岩的溶解;(3)根据碳的来源分类,九寨沟钙华应为大气成因类钙华(或表生钙华);(4)九寨沟珍珠滩钙华与碳酸氢根间较大的碳同位素分馏表明,此处生长的藻类对钙华的形成可能有重要作用。      

山西娘子关泉钙华记录的MIS12/11以来的气候和植被历史

对山西娘子关绵河不同阶地上沉积的泉钙华进行了高精度的230Th定年和碳氧稳定同位素组成测定。结果发现,绵河II级阶地沉积的娘子关泉钙华的最老年龄在407～466ka,远老于早前通过钙华中的石英砂热发光法(TL)获得的年龄,即绵河II级阶地上的娘子关泉钙华是在中更新世MIS12/11阶段形成的,而非原来认为的是晚更新世的产物。由此推测,绵河III级阶地娘子关泉钙华形成的年代更早,可能是中更新世的MIS14/13阶段。230Th测年获得的绵河I级阶地顶部的钙华形成于5ka前,即是在全新世中期以前形成的。结合钙华规模及其碳氧稳定同位素组成分析进一步发现,上述绵河三级阶地上的娘子关泉钙华均主要是湿热气候下的产物。然而,自II级阶地钙华形成至今,气候总体上在向干冷方向发展,泉域植被则呈现退化的趋势。     

碳酸钙沉积溪流中地球化学指标的空间分布和日变化特征:以云南白水台为例

目前,国内外利用碳酸钙沉积物进行古环境和古气候重建的研究,空间上主要涉及到地球化学指标的区域分布差异,时间上则将分辨率提高到了年,甚至季节尺度,但对于地球化学指标在同一区域的空间分布和日变化特征则注意不多.采用仪器自动记录、现场滴定和样品室内测试相结合的方法,对正在发生碳酸钙(钙华)沉积的云南白水台溪流和引渠中的地球化学指标的空间和日变化特征进行了研究.结果发现,在碳酸钙大量快速沉积前(方解石饱和指数 SIc小于 1.0),向下游方向,水的 CO2分压降低, pH值和 SIc升高.但当 SIc大于 1.0后,碳酸钙沉积开始 快速产生,此后向下游方向,水的 CO2分压趋于稳定,甚至略有升高;同时,水的 pH值和 SIc也不再升高,而呈现下降现象.与此有关,在溪流下游观测点,由于白天碳酸钙的快速沉积,水的 pH值和 SIc是下降的,而其 CO2分压则升高.这一现象很可能是白天碳酸钙大量快速沉积时产生的 CO2在水中聚集,来不及向大气释放的结果;此外,流速对碳酸钙沉积具有显著的控制作用,表现在流速快的地形陡坎部位, Ca2 和降低更快,因而沉积速率也更大.研究还发现,富含轻碳稳定同位素 12C的 CO2向大气的释放是向下游方向钙华碳稳定同位素组成(δ 13C) 和中午水中溶解无机碳δ 13C增加的主要原因,增加幅度分别可达 1‰ /100 m和 0.6‰～1.3‰(昼夜差);同时,碳酸钙沉积时,水中溶解无机碳与钙华存在碳稳定同位素的动力分馏效应,与沉积速率有关,分馏值为 0‰～3.22‰.     

云南白水台雨水线及钙华δ^18O的季节和空间变化特征

通过对云南白水台地区大气降水的δ^18O和δD分析,建立了该地区大气降水线,并通过对过量氘的季节性变化特征分析,发现白水台地区冬、夏季风期间降雨云团有不同的源区。对现代钙华δ^180的季节变化分析,发现钙华的氧同位素值与降雨量有着较好的线性负相关关系,这一发现为下一步利用古钙华的占δ^18O数据重建古降水量提供了基础。研究还发现,水中富含轻氧稳定同位素^16O的H2O向大气蒸发以及富含轻氧稳定同位素^16O的CO2向大气逸出,是下游方向钙华δ^18O增加的主要原因。     

黄龙钙华纹层石特征与成因分析

为了探究黄龙钙华纹层石剖面褐-白相间混积纹层的特征与成因,对黄龙钙华样品进行了采集和分析。通过微波消解法分析不同颜色纹层钙华样品有机碳含量,并用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、元素分析仪等对样品的晶相、形貌、元素和Mg/Ca比等进行了分析。结果表明,黄龙钙华褐-白纹层有机碳含量、Mg/Ca比存在明显差异,褐色纹层有机碳含量、Mg/Ca分别高于相邻的白色纹层,有机碳的含量随着沉积顺序(由老到新)逐渐变大。钙华剖面年层中的褐-白相间纹层不仅受到微生物、植物等生物的影响,还受不同温度、水动力等气候因素的调控,即黄龙钙华剖面年层中出现褐-白相间纹层为生物-气候双成因。其结果可为寻找黄龙钙华沉积过程中生物参与证据提供一定的理论基础。     

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.     

Intra-annual perturbations of stable isotopes in tufas: Effects of hydrological processes

Tufas, which are freshwater carbonates, are potential archives of terrestrial paleoclimate. Time series of stable isotopic compositions commonly show regular seasonal patterns controlled by temperature-dependent processes, and some perturbation intrinsic to the locality. We examined three tufa-depositing sites in southwestern Japan with similar temperate climates, to understand the origin of local characteristics in the isotopic records. Seasonal change in the oxygen isotope is principally reflected by temperature-dependent fractionation between water and calcite but was perturbed after heavy rainfalls overwhelming the stability of the δ¹⁸O value of the groundwater at one site. Isotopic mass balance indicates an undersaturated and relatively small aquifer at this locality. Water δ¹⁸O values at the other two sites were stable, reflecting a regular seasonal change in the δ¹⁸O value of tufa. Perturbation of the δ¹³C values in tufa is largely due to CO₂ degassing from the stream, which significantly increases the δ¹³C values of dissolved inorganic carbon (DIC). At a site with remarkably high pCO₂ in springwater and a sensitive response of flow rate to rainfall, the amount of CO₂ degassing changed distinctly with flow rate. In contrast, the other two sites having low pCO₂ springwater reflect a regular seasonal pattern of δ¹³C in DIC and tufa specimens.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

C and O stable isotope variability in recent freshwater carbonates (River Krka, Croatia)

Three types of recent carbonate precipitates from the River Krka, Croatia, were analysed: (1) bulk tufa from four main cascades in a 34 km long section of the river flow through the Krka National Park; (2) a laminar stromatolite‐like incrustation formed in the tunnel of a hydroelectric power plant close to the lowest cascade; and (3) recent precipitates collected on artificial substrates during winter, spring and summer periods. Stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in the carbonate and organic carbon (δ¹³C_org) were determined and compared with δ¹⁸O of water and δ¹³C of dissolved inorganic carbon (DIC). The source of DIC, which provides C for tufa precipitation, was determined from the slope of the line ([DIC]/[DIC₀]?1) vs. (δ¹³C‐DIC × ([DIC]/[DIC₀])) ( Sayles & Curry, 1988 ). The δ¹³C value of added DIC was ?13·6‰, corresponding to the dissolution of CO₂ with δ¹³C between ?19·5 and ?23·0‰ Vienna Pee Dee Belemnite (VPDB). The observed difference between the measured and calculated equilibrium temperature of precipitation of bulk tufa barriers indicates that the higher the water temperature, the larger the error in the estimated temperature of precipitation. This implies that the climatic signals may be valid only in tufas precipitated at lower and relatively stable temperatures. The laminar crust comprising a continuous record of the last 40 years of precipitation shows a consistent trend of increasing δ¹³C and decreasing δ¹⁸O. The lack of covariation between δ¹³C and δ¹⁸O indicates that precipitation of calcite was not kinetically controlled for either of the elements. δ¹³C and δ¹⁸O of precipitates collected on different artificial substrates show that surface characteristics both of substrates and colonizing biota play an important role in C and O isotope fractionation during carbonate precipitation.     

Climatic change recorded by stable isotopes and trace elements in a British Holocene tufa

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

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

Laminated tufa sediments formed from overflow karst springs: Controls on their deposition and carbon–oxygen isotope records

Tufa sediments are freshwater carbonates that precipitate in karst regions after degassing of carbon dioxide from groundwater in contact with the atmosphere. When laminated, these carbonates can provide high‐resolution records for the study of climate, hydrological and environmental conditions at the time of their precipitation. The formation of these carbonates directly depends on the hydrological regime, and in karst regions discontinuous discharges are often recorded. This study investigates the record of recent laminated tufa sediments precipitated downstream overflow springs in Trabaque Canyon (central Spain). The hydrological dynamics of the karst system were monitored for over three years and a stable isotope record was obtained from laminated tufa carbonates precipitated from an overflow spring. Additionally, a hydrological model of overflow springs was generated and a tufa δ¹⁸O record under constrained parameters was simulated. Temperature is the dominant control of the variation in tufa δ¹³C and δ¹⁸O values within each lamina, although when comparing different laminae, δ¹³C_DIC and δ¹⁸O of river water are also major controls. The positive correlation between tufa δ¹³C values and water temperature is caused by the fractionation occurred by carbon dioxide degassing due to the thermal dependence of carbon dioxide solubility. Additionally, the system recorded a temperature‐independent degassing process caused by the large gradient between groundwater and atmospheric carbon dioxide that is limited to the proximity of the spring. This study cautions on the risk of assuming continuous deposition when studying laminated tufa sediments and highlights the potential of their stable isotope records to provide hydrological information of their aquifers during the past.     

Seasonal temperatures from δ18O in recent Spanish tufa stromatolites: Equilibrium redux!

This study focuses on recent debate over the value of stable isotope‐based environmental proxies recorded in riverine tufa stromatolites. A twelve‐year record (1999 to 2012) of river‐bed tufa stromatolites in the River Piedra (north‐east Spain) was recovered in this study, along with a partly overlapping fifteen‐year record (1994 to 2009) of accumulations in a drainage pipe: both deposits formed in water with near identical physico/chemical parameters. Measured water temperature data and near‐constant δ ¹⁸O_water composition allowed selection of an ‘equilibrium’ palaeotemperature equation that best replicated actual temperatures. This study, as in some previous studies, found that just two published formulas for water temperature calculation from equilibrium calcite δ ¹⁸O compositions were appropriate for the River Piedra, where tufa deposition rates are high, with means between 5·6 mm and 10·8 mm in six months. The δ ¹⁸O_calcite in both the river and the pipe deposits essentially records the full actual seasonal water temperature range. Only the coldest times (water temperature <10°C), when calcite precipitation mass decreased to minimum, are likely to be unrepresented, an effect most noticeable in the pipe where depositional masses are smaller and below sample resolution. While kinetic effects on δ ¹⁸O_calcite‐based calculated water temperature cannot be ruled out, the good fit between measured water temperature and δ ¹⁸O_calcite‐calculated water temperature indicates that temperature is the principal control. Textural and deposition rate variability between the river and pipe settings are caused by differences in flow velocity and illumination. In the river, calcification of growing cyanobacterial mat occurred throughout the year, producing composite dense and porous laminae, whereas in the pipe, discontinuous cyanobacterial growth in winter promoted more abiogenic calcification. High‐resolution δ ¹⁸O_calcite data from synchronous pipe and river laminae show that reversals in water temperature occur within laminae, not at lamina boundaries, a pattern consistent with progressive increase in calcite precipitation rate as cyanobacterial growth re‐established in spring.     

Isotopic evidence for temporal variation in proportion of seasonal precipitation since the last glacial time in the inland Pacific Northwest of the USA

Large-scale atmospheric circulation patterns determine the quantity and seasonality of precipitation, the major source of water in most terrestrial ecosystems. Oxygen isotope (δ¹⁸O) dynamics of the present-day hydrologic system in the Palouse region of the northwestern U.S.A. indicate a seasonal correlation between the δ¹⁸O values of precipitation and temperature, but no seasonal trends of δ¹⁸O records in soil water and shallow groundwater. Their isotope values are close to those of winter precipitation because the Palouse receives  75% of its precipitation during winter. Palouse Loess deposits contain late Pleistocene pedogenic carbonate having ca. 2 to 3‰ higher δ¹⁸O values and up to 5‰ higher carbon isotope (δ¹³C) values than Holocene and modern carbonates. The late Pleistocene δ¹⁸O values are best explained by a decrease in isotopically light winter precipitation relative to the modern winter-dominated infiltration. The δ¹³C values are attributed to a proportional increase of atmospheric CO₂ in soil CO₂ due to a decrease in soil respiration rate and ¹³C discrimination in plants under much drier paleoclimate conditions than today. The regional climate difference was likely related to anticyclonic circulation over the Pleistocene Laurentide and Ice Sheet.     

Genesis of fumarolic emissions as inferred by isotope mass balances: CO2 and water at Vulcano Island, Italy

We have developed a quantitative model of CO₂ and H₂O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H₂O and CO₂ and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H₂O and CO₂ content and the δD, δ¹⁸O, and δ¹³C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits.The δ¹³C_CO2 of the magmatic gases varies around −3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO₂ concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (−1 to −‰ vs. standard mean ocean water [SMOW]), as well as the above δ¹³C_CO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect.The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ¹³C of the entire hydrothermal system, including mixed H₂O-CO₂ vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and −2 to −6.5‰ vs. PDB for CO₂. On these grounds, we think that Mediterranean marine water (δD_H2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks, reaching oxygen isotope equilibrium at high temperatures. Interaction processes between magmatic gases and the evolving seawater also seem to occur, causing the dissolution of isotopically fractionated aqueous CO₂ and providing the source for hydrothermal carbon. These results have important implications concerning fluid circulation beneath Vulcano and address the more convenient routine of geochemical surveillance.