Wet-dry seasonal and spatial variations in the δC and δO values of the modern endogenic travertine at Baishuitai, Yunnan, SW China and their paleoclimatic and paleoenvironmental implications

Seasonal and spatial variations in the δ¹³C and δ¹⁸O values of the modern endogenic (thermogene) travertine deposited in a calcite-depositing canal at Baishuitai, Yunnan, SW China were examined to understand their potential for paleoclimatic and paleoenvironmental implications. The sampling sites were set in the upstream, middle reach and downstream of the canal, and the modern endogenic travertine samples were collected semimonthly to measure their δ¹³C and δ¹⁸O values. It was found that both δ¹³C and δ¹⁸O values of the endogenic travertine were low in the warm rainy season and high in the cold dry season, and correlated with each other. The low δ¹⁸O values in warm rainy season were mainly related to the higher water temperature and the lower δ¹⁸O values of rainwater, and the low δ¹³C values are caused by the dilution effect of overland flow with low δ¹³C values in the warm rainy season and the reduced CO₂-degassing of canal-water caused by the dilution effect of the overland flow. The linear negative correlation between the travertine δ¹⁸O (or δ¹³C) values and rainfall amount may be used for paleo-rainfall reconstruction if one knows the δ¹⁸O (or δ¹³C) values of the fossil endogenic travertine at Baishuitai though the reconstruction was not straightforward. It was also found that there was a progressive downstream increase of the δ¹⁸O and δ¹³C values of the travertine along the canal, the former being mainly due to the preferential evaporation of H₂¹⁶O to the atmosphere and the latter to the preferential release of ¹²CO₂ to the atmosphere during CO₂-degassing. However, the downstream increase of the travertine δ¹⁸O and δ¹³C values was less intensive in rainy season because of the reduced evaporation and CO₂-degassing during the rainy season. To conclude, the downstream travertine sites could be more favorable for the paleo-rainfall reconstruction while the upstream travertine sites are more favorable for the paleo-temperature reconstruction. So, this study demonstrates that endogenic travertine, like epigenic (meteogene) tufa, could also be a good candidate for high-resolution paleoclimatic and paleoenvironmental reconstruction.     

Diurnal Variations of Hydrochemistry in a Travertine-depositing Stream at Baishuitai, Yunnan, SW China

Diurnal variations of hydrochemistry were monitored at a spring and two pools in a travertine-depositing stream at Baishuitai, Yunnan, SW China. Water temperature, pH and specific conductivity were measured in intervals of 5 and 30 min for periods of 1 to 2 days. From these data the concentrations of Ca²⁺, HCO₃⁻, calcite saturation index, and CO₂ partial pressure were derived. The measurements in the spring of the stream did not show any diurnal variations in the chemical composition of the water. Diurnal variations, however, were observed in the water of the two travertine pools downstream. In one of them, a rise in temperature (thus more CO₂ degassing) during day time and consumption of CO₂ due to photosynthesis of submerged aquatic plants accelerated deposition of calcite, whereas in the other pool, where aquatic plants flourished and grew out of the water (so photosynthesis was taking place in the atmosphere), the authors suggest that temperature-dependent root respiration underwater took place, which dominated until noon. Consequently, due to the release of CO₂ by the root respiration into water, which dominated CO₂ production by degassing induced by temperature increase, the increased dissolution of calcite was observed. This is the first time anywhere at least in China that the effect of root respiration on diurnal hydrochemical variations has been observed. The finding has implications for sampling strategy within travertine-depositing streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, pools and wetlands, where aquatic plants may flourish and grow out of water.     

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     

Experimental studies of oxygen isotope fractionation between rhodochrosite (MnCO3) and water at low temperatures

Rhodochrosite crystals were precipitated from Na-Mn-Cl-HCO₃ parent solutions following passive, forced and combined passive-to-forced CO₂ degassing methods. Forced and combined passive-to-forced CO₂ degassing produced rhodochrosite crystals with a small non-equilibrium oxygen isotope effect whereas passive CO₂ degassing protocols yielded rhodochrosite in apparent isotopic equilibrium with water. On the basis of the apparent equilibrium isotopic data, a new temperature-dependent relation is proposed for the oxygen isotope fractionation between rhodochrosite and water between 10 and 40 °C:

1000lnα_{rhodochrosite-water}=17.84±0.18(10³/T)-30.24±0.62     

The quaternary travertine deposits of Europe and Asia Minor

A summary is provided of the published information relating to all aspects of Quaternary travertine formation in Europe west of the Ural Mountains. The deposits have been divided into two broad groups, the meteogene travertines, which result primarily from the degassing of soil-borne aqueous CO₂, and thermogene deposits resulting from the degassing of thermally generated CO₂. Meteogene deposits are rare above latitude 58°N, and in regions where the mean annual air temperature is below 5°C. A significant positive correlation exists between mean air temperature and travertine deposit thickness. The combined effects of temperature and rainfall are used to provide a zoned map showing the travertine-forming potential of limestones within the region. Information from ¹⁴C dating indicates that deposition reached a maximum in the period 5–10 ka BP) and is currently limited by land and water management practices in the populated areas. Thermogene deposits occur in regions of high CO₂ discharge resulting from tectonic activity, such as Italy and Turkey where there is much vulcanism. These travertines are frequently more massive and less readily weathered than meteogene deposits. Fully referenced information is provided for 320 important, mostly well studied sites (227 meteogene, 93 thermogene), of which 156 are currently active.     

Carbon-oxygen isotopic covariation in hydrothermal calcite during degassing of CO2

The effect of the outgassing of CO₂ from a hydrothermal fluid on the C- and O-isotopic compositions of calcite, which is precipitated from this fluid, is quantitatively modelled in terms of batch and Rayleigh distillation equations. Both CO₂ degassing and calcite precipitation are considered to be the removal mechanisms for dissolved carbon species from the fluid. Combined degassing-precipitation models are then developed by taking H₂CO₃ and HCO ₃ ^– , respectively, as the dominant dissolved carbon species. A positive correlation array between ¹³C and ¹³O values of calcite can be yielded by the precipitation of calcite from a H₂CO ₃ ^– -dominant fluid, accompanied by a progressive decrease in temperature during CO₂ degassing, whereas calcite precipitated from a HCO ₃ ^– -dominant fluid under the same conditions tends to display much smaller variation in ¹³C values than in ¹⁸O values. The combined processes of CO₂ degassing and calcite precipitation result in lowering the ¹³C value of calcites with respect to those precipitated in a closed system simply due to temperature effect. Carbon and oxygen isotopic data for calcite from the Kushikino gold-mining area in Japan illustrate the application of quantitative modelling, and degassing of CO₂ is suggested as a more likely cause for the precipitation of the calcite and quartz in this mining area.     

Stable Isotope Fractionation during Experimental Formation of Norsethite (BaMg[CO3]2): A Mineral Analogue of Dolomite

Stable oxygen and carbon isotopefractionation during the experimental formation ofordered norsethite (BaMg[CO₃]₂) from thereaction of anhydrous BaCO₃ (witherite) withrelatively low concentrated sodium-magnesiumbicarbonate solutions has been studied between20° and 135 °C. In the investigatedtemperature range, ¹⁸O and ¹³C are enrichedin norsethite with respect to water and gaseous carbondioxide, respectively. Whereas ¹⁸O/¹⁶Opartitioning is intermediate between those of theBaCO₃–H₂O and MgCO₃–H₂O systems,¹³C/¹²C partitioning is more similar to thatfor BaCO₃–CO₂. Between 20° and90°C, the temperature dependences of the¹⁸O/¹⁶O and ¹³C/¹²C fractionationfactors are represented by the equations (T in °K):10³ ln _BaMg[CO₃]₂-H_2O = 2.83 10⁶T^--2.85, and 10³ln_BaMg[CO₃]₂-CO₂(gas) = 1.78 10⁶T^--10.16. The later equation considers carbon isotope fractionationbetween the dissolved carbonate ion and carbon dioxide measured by Halaset al. (1997). Under standard state conditions (25 °C) the fractionation factors in the system BaMg[CO₃]₂-CO₂-H₂O are: Oxygen isotopes: _BaMg(CO₃)₂-H_2O = 1.02941, _BaMg(CO₃)₂-OH-(aq) = 1.07059,_BaMg(CO₃)₂-CO₂(gas) = 0.98868, and_BaMg(CO₃)₂-H₂CO₃ ^* = 0.98843; carbon isotopes:_BaMg(CO₃)₂-CO₂(gas) = 1.00992,_BaMg(CO₃)₂-H₂CO₃ ^* = 1.01099,_BaMg(CO₃)₂-HCO₃ ^- = 1.00194,_BaMg(CO₃)₂-CO₃ ^2- = 1.00491 or 1.00150.The spontaneous precipitation of aBaMg[CO₃]₂ gel at 20 °C,followed by the alteration of the products at20° or 60°C for 31 days,demonstrated isotope exchange reactions betweensolids and mother solutions dueto recrystallization. Isotope equilibrium, wasnot reached within run time.     

Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures

To determine oxygen isotope fractionation between aragonite and water, aragonite was slowly precipitated from Ca(HCO₃)₂ solution at 0 to 50°C in the presence of Mg²⁺ or SO₄²⁻. The phase compositions and morphologies of synthetic minerals were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The effects of aragonite precipitation rate and excess dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution on oxygen isotope fractionation between aragonite and water were investigated. For the CaCO₃ minerals slowly precipitated by the CaCO₃ or NaHCO₃ dissolution method at 0 to 50°C, the XRD and SEM analyses show that the rate of aragonite precipitation increased with temperature. Correspondingly, oxygen isotope fractionations between aragonite and water deviated progressively farther from equilibrium. Additionally, an excess of dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution results in an increase in apparent oxygen isotope fractionations. As a consequence, the experimentally determined oxygen isotope fractionations at 50°C indicate disequilibrium, whereas the relatively lower fractionation values obtained at 0 and 25°C from the solution with less dissolved CO₂ gas and low precipitation rates indicate a closer approach to equilibrium. Combining the lower values at 0 and 25°C with previous data derived from a two-step overgrowth technique at 50 and 70°C, a fractionation equation for the aragonite-water system at 0 to 70°C is obtained as follows:

     

Metamorphic decarbonation in the Neoproterozoic and its environmental implication

Metamorphic decarbonation reactions and volcanic degassing lead to significant influx of CO₂, a major greenhouse gas, into the ocean-atmosphere system from the solid Earth. Here we present quantitative estimates on CO₂ derived through metamorphic degassing during ultrahigh-temperature (UHT) metamorphism in the Neoproterozoic through the mineralogical and geological analyses of the UHT decarbonation. Our computations show that an extra flux of CO₂ was added to the atmosphere through a Himalayan scale UHT metamorphism to the extent of 6 × 10¹⁶ to 3.0 × 10¹⁸ mol/my, for a duration of 10 my. A calculation of the impact of the extra CO₂ influx to the global mean temperature in the context of carbon cycle and greenhouse effect of CO₂ shows that at the peak influx stage, the steady state temperature would be raised by 4 °C from 15 °C and by 13 °C from 4 °C. Our results have important bearing in evaluating the mechanism of melting and the duration of the Snowball Earth. Our estimate of the maximum degassing rate during UHT metamorphism suggests that the duration of the Marinoan snowball Earth was probably shorter, and the recovery from an ice-covered Earth to ocean-covered Earth was faster than previous estimates.     

Experimental determination of the isotopic fractionation between gaseous CO2 and carbon dissolved in tholeiitic magma

Isotope fractionation of carbon between CO₂ and carbon dissolved in a tholeiitic magma measured in the range 1120–1280 ° C, 7.0–8.4 Kb varies from 4.6 to 4 in favor of CO₂. These results make possible to explain all deep seated ¹³C values from a restricted range of primary mantle ¹³C concentrations. They also suggest that carbon could be dissolved in basaltic magmas in a reduced form.     

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.     

Phosphoric acid fractionation factors for smithsonite and cerussite between 25 and 72°C

The intramolecular kinetic oxygen isotope fractionation between CO₂ and CO₃²⁻ during reaction of phosphoric acid with natural smithsonite (ZnCO₃) and cerussite (PbCO₃) has been determined between 25 and 72°C. While cerussite decomposes in phosphoric acid within a few hours at 25°C, smithsonite reacts very slowly with the acid at 25°C providing yields of CO₂ < 25% after 2 weeks. The low yields result in a low precision for oxygen isotope measurements of the acid-liberated CO₂ (±1.65‰, 1σ, n = 9). The yield and reproducibility of oxygen isotope values of the acid-liberated CO₂ from smithsonite can be improved, the latter to ∼±0.15‰, by increasing the reaction temperature to 50°C for 12 h or to 72°C for 1 h. Our new phosphoric acid fractionation factor for natural cerussite at 25°C deviates significantly from a previously published value on synthetic material. The temperature dependence of the oxygen isotope factionation factor, α between acid-liberated CO₂ and carbonate at 25 to 72°C is given by the following equations

     

Experimental studies of oxygen isotope fractionation in the carbonic acid system at 15°, 25°, and 40°C

In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO₃⁻ and CO₃²⁻ concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO₃⁻, CO₃²⁻, and CO_2(aq)) were investigated at 15°, 25°, and 40°C. To investigate oxygen isotope exchange between HCO₃⁻, CO₃²⁻, and H₂O, NaHCO₃ solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl₂ was added to the NaHCO₃ solutions. This resulted in immediate BaCO₃ precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon (DIC). Data from experiments at 15°, 25°, and 40°C (1 atm) show that the oxygen isotope fractionation between HCO₃⁻ and H₂O as a function of temperature is governed by the equation:

     

Stable Isotope Ratios and the Evolution of Acidulous Ground Water

Ground waters in North Hesse (Germany) are conspicuous by high amounts of dissolved inorganic carbon (DIC) at low pH. The DIC is received from the uptake of soil CO₂ and CO₂ of volcanic origin and the subsequent dissolution ofTriassic and Permian limestone and dolomites. The volcanic CO₂ is related to Miocene basaltic magma which has liberated gaseous CO₂ during thebreakthrough to Triassic and Permian sediments. The volcanic CO₂ (-6 < ¹³CCO₂ < -3, PDB) was trapped within pore spacesand intra- and intergranulares of Permian evaporites and Triassic sandstones and was stored within such reservoirs until recent times. The uptake of volcanic CO₂ occurs as ground water migrates through such reservoirs. The ¹³ C/¹² C-signatures of the DIC indicate mixture of soil-CO₂and CO₂ of volcanic origin for the dissolution of marine limestone and dolomites. The obtained two types for CO₂ of volcanic origin with ¹³C_{CO 2}-values of -10 ± 3 and +2 ± 2 can be explained by diffusion of CO₂ through micropores, faults, and interfacesof solids. This mobilisation of CO₂ is accompanied with a kinetic fractionation of -9. ¹³ C-depleted CO₂ is liberated from the reservoir,whereas ¹³ CO₂ is accumulated in the residue     

土耳其棉花堡与中国黄龙和白水台钙华退化原因对比研究

通过比较中国四川黄龙、中国云南白水台、土耳其帕穆克卡莱棉花堡三地钙华景观的基本环境地质特征、钙华景观水化学、钙华沉积生物因素的差异性,探讨了土耳其棉花堡钙华退化缓慢的影响因素。对比发现,棉花堡景区藻类约为38种,种类单一,植被覆盖率较低,沉积主要受物理化学因素控制,沉积速率较快,多形成较好的层状结构,杂质少,且原生孔隙度较低,结构致密,结晶度较高,不易坍塌损坏;黄龙和白水台景区藻类分别为86种、196种,种类多样,且植被覆盖率皆高达80%以上,沉积主控于化学和生物因素,沉积速率较慢,结构呈多孔疏松状或多孔珊瑚状,原生孔隙度普遍较高,易退化。此外,棉花堡钙华景区泉水各离子含量均高于黄龙和白水台景区,尤其是Ca2+和HCO3-,这能有效促进CaCO₃的沉积。     

A preliminary analysis of the formation of travertine and travertine cones in the Jifei hot spring,Yunnan, China

The Jifei hot spring emerges in the form of a spring group in the Tibet–Yunnan geothermal zone, southwest of Yunnan Province, China. The temperatures of spring waters range from 35 to 81°C and are mainly of HCO₃–Na·Ca type. The total discharge of the hot spring is about 10 L/s. The spring is characterized by its huge travertine terrace with an area of about 4,000 m² and as many as 18 travertine cones of different sizes. The tallest travertine cone is as high as 7.1 m. The travertine formation and evolution can be divided into three periods: travertine terrace deposition period, travertine cone formation period and death period. The hydrochemical characteristics of the Jifei hot spring was analyzed and compared with a local non-travertine hot spring and six other famous travertine springs. The results indicate that the necessary hydrochemical conditions of travertine and travertine cones deposition in the Jifei area are (1) high concentration of HCO₃ ⁻ and CO₂; (2) about 52.9% deep source CO₂ with significantly high value; (3) very high milliequivalent percentage of HCO₃ ⁻ (97.4%) with not very high milliequivalent percentage of Ca²⁺ (24.4%); and (4) a large saturation index of calcite and aragonite of the hot water.     

云南白水台钙华水池中水化学日变化及其生物控制的发现

为弄清云南白水台泉及其下游钙华水池中水化学的日变化,选取1号泉及其流经的两个钙华水池(6号和10号)作为研究对象并对其水温、pH值和电导率进行了自动监测。根据Ca2 、HCO3-与电导率存在的线性关系,用WATSPAC软件计算了水中方解石的饱和指数和PCO2。监测发现:泉水不存在显著的水化学日动态变化,而两个钙华水池表现出显著的日动态变化。其中10号钙华水池在白天温度较高时水中的CO2大量逸出并通过水下水生植物的光合作用加速了水中碳酸钙的沉积。6号钙华水池水生植物生长茂盛,其叶片和部分枝干露出水面,因而光合作用主要发生在空中,所以此处水化学表现为白天pH值降低和电导率升高的反常现象,即由温度主导的根呼吸作用,在白天释放更多的CO2进入水体而使沉积下来的碳酸钙重新溶解。     

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.