迎接地球科学的春天

通过水化学、碳稳定同位素和碳酸盐沉积物沉积速率的对比分析 ,发现在贵州乌江渡坝址灌浆廊道中存在两种不同类型的碳酸盐沉积物 ,即 :放CO2 型和吸CO2 型。前者如通常岩溶洞穴中所见 ,是天然条件下岩溶作用的产物 ;而后者则很特殊 ,它是灌浆帷幕和混凝土发生碳酸盐化的结果。由于碳酸盐化时自大气迅速吸入CO2 ,使得廊道中CO2 浓度降低 ,并每年可产生高达 10cm的碳酸盐沉积物。考虑到世界范围内水泥的大量使用 ,水泥或混凝土碳酸盐化的环境意义 ,即在全球碳循环的研究中对大气CO2 沉降的贡献是不容忽视的。据初步估算 ,该碳贡献量每年约 1亿t左右。     

Effects of carbon anhydrase on utilization of bicarbonate in microalgae: a case study in Lake Hongfeng

A bidirectional labeling method was established to distinguish the proportions of HCO₃^? and CO₂ utilization pathways of microalgae in Lake Hongfeng. The method was based on microalgae cultured in a medium by adding equal concentrations of NaH¹³CO₃ with different δ¹³C values simultaneously. The inorganic carbon sources were quantified according to the stable carbon isotope composition in the treated microalgae. The effects of extracellular carbonic anhydrase (CAex) on the HCO₃^? and CO₂ utilization pathways were distinguished using acetazolamide, a potent membrane-impermeable carbonic anhydrase inhibitor. The results show utilization of the added HCO₃^? was only 8% of the total carbon sources in karst lake. The proportion of the HCO₃^? utilization pathway was 52% of total inorganic carbon assimilation. Therefore, in the natural water of the karst area, the microalgae used less bicarbonate that preexisted in the aqueous medium than CO₂ derived from the atmosphere. CAex increased the utilization of inorganic carbon from the atmosphere. The microalgae with CAex had greater carbon sequestration capacity in this karst area.     

Investigation of the accelerated carbonation of a MgO-based binder used to treat contaminated sediment

A MgO-based binder developed to simultaneously solidify/stabilize contaminated sediment and store CO₂ has been described previously. The objectives of the study presented here were to investigate the kinetics of the carbonation reactions of the binder and the extent to which carbonation occurred and to identify the optimal conditions for using the binder. The carbonation reaction was clearly faster and the degree of carbonation higher at CO₂ concentrations of 50 and 100% than in the ambient atmosphere (which contains 0.04% CO₂). A modified unreactive core model adequately described the kinetics. The rate constants were 0.0217–0.319 h^?1 and were proportional to the degree of carbonation. A high degree of carbonation, 93.8%, was achieved at a CO₂ concentration of 100%. The water to sediment ratio strongly affected carbonation, the optimal ratio being around 0.7. The relative humidity did not strongly affect the carbonation performance. The carbonation products were magnesite (MgCO₃) and nesquehonite (MgCO₃·3H₂O). X-ray diffraction analysis showed that brucite (Mg(OH)₂) was not present, suggesting that brucite was very quickly transformed into magnesium carbonates, the presence of which was confirmed by thermal gravimetric analysis. The results indicated that, in 7 d, 1 kg of binder could sequester up to 0.507 kg of CO₂ in a 100% CO₂ atmosphere. The results indicate that the MgO-based binder has great potential to be used to sequester CO₂ under accelerated carbonation conditions.     

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

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

CO<Subscript>2</Subscript> Air–Sea Exchange due to Calcium Carbonate and Organic Matter Storage,and its Implications for the Global Carbon Cycle

Release of CO₂ from surface ocean water owing to precipitation of CaCO₃ and the imbalance between biological production of organic matter and its respiration, and their net removal from surface water to sedimentary storage was studied by means of a quotient θ = (CO₂ flux to the atmosphere)/(CaCO₃ precipitated). θ depends not only on water temperature and atmospheric CO₂ concentration but also on the CaCO₃ and organic carbon masses formed. In CO₂ generation by CaCO₃ precipitation, θ varies from a fraction of 0.44 to 0.79, increasing with decreasing temperature (25 to 5°C), increasing atmospheric CO₂ concentration (195–375 ppmv), and increasing CaCO₃ precipitated mass (up to 45% of the initial DIC concentration in surface water). Primary production and net storage of organic carbon counteracts the CO₂ production by carbonate precipitation and it results in lower CO₂ emissions from the surface layer. When atmospheric CO₂ increases due to the ocean-to-atmosphere flux rather than remaining constant, the amount of CO₂ transferred is a non-linear function of the surface layer thickness because of the back-pressure of the rising atmospheric CO₂. For a surface ocean layer approximated by a 50-m-thick euphotic zone that receives input of inorganic and organic carbon from land, the calculated CO₂ flux to the atmosphere is a function of the CaCO₃ and C_org net storage rates. In general, the carbonate storage rate has been greater than that of organic carbon. The CO₂ flux near the Last Glacial Maximum is 17 to 7×10¹² mol/yr (0.2–0.08 Gt C/yr), reflecting the range of organic carbon storage rates in sediments, and for pre-industrial time it is 38–42×10¹² mol/yr (0.46–0.50 Gt C/yr). Within the imbalanced global carbon cycle, our estimates indicate that prior to anthropogenic emissions of CO₂ to the atmosphere the land organic reservoir was gaining carbon and the surface ocean was losing carbon, calcium, and total alkalinity owing to the CaCO₃ storage and consequent emission of CO₂. These results are in agreement with the conclusions of a number of other investigators. As the CO₂ uptake in mineral weathering is a major flux in the global carbon cycle, the CO₂ weathering pathway that originates in the CO₂ produced by remineralization of soil humus rather than by direct uptake from the atmosphere may reduce the relatively large imbalances of the atmosphere and land organic reservoir at 10²–10⁴-year time scales.     

Contrasting Carbon Dioxide Inputs and Exchange in Three Adjacent New England Estuaries

Four surveys of the adjacent Cocheco, Bellamy, and Oyster estuaries reveal spatial heterogeneity with respect both to river-born carbon dioxide (CO₂) fluxes and CO₂ exchange with the atmosphere (−17 to 51 mmol m⁻² day⁻¹), a finding partially explained by CO₂ inputs from contributing watersheds. Nonuniform nutrient and organic carbon loading from upstream rivers and within the estuaries is considered as a mechanism resulting in the variability between estuaries. Conditions during the surveys included spring river runoff and phytoplankton blooms, drought with baseline river flow, and a historic flood which led to a large CO₂ release to the atmosphere. This study highlights the variability of CO₂ transport and release found between proximate estuaries over a wide range of flow conditions.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

中国南方表层岩溶系统的碳循环及其生态效应

表层岩溶系统因碳酸盐岩－水－CO²(气)三相的化学动态不平衡过程而产生特殊的碳循环环节,参加循环的碳包括碳酸盐岩中的碳、大气和土壤空气CO²部分。中国南方表层岩溶系统的碳循环非常活跃,并敏感地响应岩溶动力因素的变化,从而促进了地球化学过程和生物化学过程的结合,成为大气CO²汇的重要项。中国南方表层岩溶系统的碳循环通过驱动环境的元素迁移,促进土壤有机质的积累,并影响植物所需要的矿物质营养元素的全量和有效态,进而影响岩溶区的植物物种、特有性和作物的发育。     

Human impact on the historical change of CO<Subscript>2</Subscript>degassing flux in River Changjiang

The impact of water quality changes in River Changjiang (formally known as the Yangtze River) on dissolved CO₂ and silicate concentrations and seasonal carbon flux in the past several decades (1960s–2000) was evaluated, based on monitoring data from hydrographic gauge. It was found that dissolved CO₂ and silicate in Changjiang decreased dramatically during this decades, as opposed to a marked increase in nutrient (e.g. NO₃ ^-) concentrations. Our analyses revealed that dissolved CO₂ in Changjiang was over-saturated with the atmosphere CO₂, and its concentration had showed a declining trend since the 1960s, despite that fluvial DIC flux had maintained stable. Analysis results also suggested that the decrease in dissolved CO₂ concentration was attributed to changes on the riverine trophic level and river damming activities in the Changjiang drainage basin. Due to the economic innovation (e.g. agriculture and industry development) across the Changjiang watershed, fertilizers application and river regulations have significantly altered the original state of the river. Its ecosystem and hydrological condition have been evolving toward the "lacustrine/reservoir" autotrophic type prevailing with plankton. Accordingly, average CO₂ diffusing flux to the atmosphere from the river had been reduced by three-fourth from the 1960s to 1990s, with the flux value being down to 14.2 mol.m^-2.yr^-1 in the 1990s. For a rough estimate, approximately 15.3 Mt of carbon was degassed annually into the atmosphere from the entire Changjiang drainage basin in the 1990s.     

CO2全球循环及其同位素示踪研究

极地冰盖气泡研究表明,工业革命前大气圈天然ＣＯ₂浓度约为２８０×１０－６,天然ＣＯ₂浓度变化反映了冰期－间冰期循环这一长期气候变化固有特征。工业革命后,大量人为ＣＯ₂进人大气圈,人为ＣＯ₂收支明显不平衡,一个大于２．６ＧＴＣ／ａ的未知陆地生态汇很可能存在于北半球中纬度地带。土壤、岩溶作用、河流作用、地球化学作用、干旱－半干旱环境等系统以及海洋内部ＣＯ₂循环的同位素示踪研究,可为人为ＣＯ₂未知汇即“ＭｉｓｓｉｎｇＳｉｎｋ”的探求提供线索。     

The role of near-surface cavities in the carbon dioxide cycle of karst areas: evidence from the Carburangeli Cave Natural Reserve (Italy)

Hydrological, chemical and meteorological data collected during the years 2006–2007 at Carburangeli Cave (Italy) have provided new insights on the near-surface cycle of carbon dioxide, particularly concerning the role played by fractures and karst conduits. Carbon dioxide is trapped in the underground atmosphere essentially when its temperature is lower than the outer one. By contrast, convective air circulation disperses all the excess CO₂ in the external environment when the thermal differential is inverted. The network of fractures and karst conduits then works, in the vadose zone, as a re-circulator of CO₂ from the soil to the atmosphere. The total amount of CO₂ fixed in the underground is controlled, during the wet season, by the amount of infiltrating waters, which act as the main carrier of CO₂ in the subsoil. By contrast, during the dry season, gravitational drainage is responsible for the accumulation of carbon dioxide in the underground voids. The quantitative balance demonstrated that the degassed CO₂ amounts are one order of magnitude higher than the dissolved CO₂. In light of this, if the near-surface outgassing processes are not taken into account, CO₂ budgets may be affected by significant errors.     

Carbonation and decarbonation of eclogites: the role of garnet

Carbonates are potentially significant hosts for primordial and subducted carbon in the Earth's mantle. In addition, the coexistence of carbonate with silicates and reduced carbon (diamond or graphite), allows constraints to be placed on the oxidation state of the mantle. Carbonate-silicate-vapor reactions control how carbonate + silicate assemblages may form from carbon-bearing vapor + silicate assemblages with increasing pressure. In olivine-bearing rocks such as peridotite, considered the dominant rock type in the upper mantle, the lowest-pressure carbonate-forming reactions involve olivine (±clinopyroxene) reacting with CO₂ (e.g., Wyllie et al. 1983). In eclogitic rocks, the essential mineral assemblage is omphacitic clinopyroxene + garnet, without olivine. Therefore, alternative carbonate-forming reactions must be sought. The carbonation of clinopyroxene via the reaction dolomite + 2 coesite = diopside + 2 CO₂ was studied experimentally by Luth (1995). The alternative possibility that garnet reacts with CO₂ is explored here by determining the location of the reaction 3 magnesite + kyanite + 2 coesite = pyrope + 3 CO₂ between 5 and 11 GPa in multi-anvil apparatus. At the temperatures ≥1200 °C, carbonation of eclogitic rocks with increasing pressure will proceed initially by reaction with clinopyroxene, because the pyrope-carbonation reaction lies at higher pressures for a given temperature than does the diopside-carbonation reaction. Diluting the pyrope component of garnet and the diopside component of clinopyroxene to levels appropriate for mantle eclogites does not change this conclusion. At lower temperatures, appropriate for “cold” slabs, it is possible that the converse situation will hold, with initial carbonation proceeding via reaction with garnet, but this possibility awaits experimental confirmation. Decarbonation of an eclogite under “normal mantle” geothermal conditions by a decrease in pressure, as in an ascending limb of a mantle convection cell, would be governed by the formation of clinopyroxene + CO₂. At higher pressure than this reaction, any CO₂ produced by the breakdown of magnesite reacting with kyanite and coesite would react with clinopyroxene to produce dolomite + coesite. Release of CO₂ from eclogite into mantle peridotite would form carbonate at sub-solidus conditions and produce a dolomitic carbonate melt if temperatures are above the peridotite-CO₂ solidus. Received: 4 May 1998 / Accepted: 23 December 1998     

Fluid inclusion and stable isotope evidence for the genesis of quartz-scheelite veins, Metaggitsi area, central Chalkidiki Peninsula, N. Greece

Scheelite mineralization accompanied by muscovite and albite, and traces of Mo-stolzite and stolzite occurs in epigenetic quartz vein systems hosted by two-mica gneissic schists, and locally amphibolites, of the Paleozoic or older Vertiskos Formation, in the Metaggitsi area, central Chalkidiki, N Greece. Three types of primary fluid inclusions coexist in quartz and scheelite: type 1, the most abundant, consists of mixed H₂O-CO₂ inclusions with highly variable (20–90 vol.%) CO₂ contents and salinities between 0.2 and 8.3 equivalent weight % NaCl. Densities range from 0.79 to 0.99 g/cc; type 1 inclusions contain also traces (<2 mol%) of CH₄. Type 2 inclusions are nearly 100 vol.% liquid CO_2, with traces of CH₄, and densities between 0.75 and 0.88 g/cc. Type 3 inclusions, the least abundant, contain an aqueous liquid of low salinity (0.5 to 8.5 equivalent weight% NaCl) with 10–30 vol.% H₂O gas infrequently containing also small amounts of CO₂ (<2 mol%); densities range from 0.72 to 0.99 g/cc. The wide range of coexisting fluid inclusion compositions is interpreted as a result of fluid immiscibility during entrapment. Immiscibility is documented by the partitioning of CH₄ and CO₂, into gas-rich (CO₂-rich) type 1 inclusions, and the conformity of end-member compositions trapped in type 1 inclusions to chemical equilibrium fractionation at the minimum measured homogenization temperatures, and calculated homogenization pressures. Minimum measured homogenization temperatures of aqueous and gas-rich type 1 inclusions of 220°–250 °C, either to the H₂O, or to the CO₂ phase, is considered the best estimate of temperature of formation of the veins, and temperature of scheelite deposition. Corresponding fluid pressures were between 1.2 and 2.6 kbar. Oxygen fugacities during mineralization varied from 10⁻³⁵ to 10⁻³¹ bar and were slightly above the synthetic Ni-NiO buffer values. The fluid inclusion data combined with δ¹⁸O water values of 3 to 6 per mil (SMOW) and δ¹³C CO₂₋ fluid of −1.2 to +4.3 per mil (PDB), together with geologic data, indicate generation of mineralizing fluids primarily by late- to post-metamorphic devolatilization reactions. Received: 8 April 1997 / Accepted: 8 July 1997     

Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela

Ultramafic-hosted deposits of magnesite (MgCO₃) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ¹⁸O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ¹³C ranges from −9 to −16‰ PDB within the magnesite and −8 to −10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO₂ and CH₄ which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.     

Greenhouse gases and greenhouse effect

Conventional theory of global warming states that heating of atmosphere occurs as a result of accumulation of CO₂ and CH₄ in atmosphere. The writers show that rising concentration of CO₂ should result in the cooling of climate. The methane accumulation has no essential effect on the Earth’s climate. Even significant releases of the anthropogenic carbon dioxide into the atmosphere do not change average parameters of the Earth’s heat regime and the atmospheric greenhouse effect. Moreover, CO₂ concentration increase in the atmosphere results in rising agricultural productivity and improves the conditions for reforestation. Thus, accumulation of small additional amounts of carbon dioxide and methane in the atmosphere as a result of anthropogenic activities has practically no effect on the Earth’s climate.     

我国南方岩溶区和北方黄土区的大气CO2效应

我国南方岩溶区与北方黄土区都是巨大的碳库。碳酸盐的溶蚀及再结晶是两个碳库与大气ＣＯ^２交换的重要过程。碳的区域平衡是评价化学风化消耗或逸散ＣＯ^２的基础。岩溶区与黄土区在地球化学风化的环境背景、溶蚀过程、产物运移和归宿等差异很大。黄土区化学风化消耗大气ＣＯ^２通量较岩溶区小。目前评价两类地区土壤与大气ＣＯ^２的源汇关系尚不成熟,需要定量认识土壤ＣＯ^２与下伏碳酸盐岩溶蚀或与下伏黄土次生碳酸盐化作用。岩溶区湖泊沉积物中有机质分解产生的ＨＣＯ^３－制约外源及内生碳酸盐溶解和自生碳酸盐形成。     

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     

Is orogenesis a net sink or source of atmospheric CO2?

In global carbon cycle models, orogenesis is often viewed as a sink for atmospheric CO₂, acting on tectonic timescales. However, recent attempts to quantify fluxes for CO₂ produced by metamorphic reactions and released to the atmosphere suggest that these are an order‐of‐magnitude greater than CO₂ uptake by chemical weathering of silicate minerals, and that metamorphic CO₂ is released on millennial timescales. These hypotheses have gained support from both measurements of CO₂ emissions from present‐day orogenic hot springs and chromatographic modelling of carbonation reactions in metamorphic rocks from ancient orogens. In this article I review research that attempts to quantify metamorphic CO₂ release fluxes, focussing specifically on studies conducted in the SW Scottish Highlands.     

Annual volcanic carbon dioxide emission: An estimate from eruption chronologies

Continuing interest in the effects of carbon dioxide on climate has been promoted by the exponentially increasing anthropogenic production of CO₂. Volcanoes are also a major source of carbon dioxide, but their average input to the atmosphere is generally considered minor relative to anthropogenic input. This study examines eruption chronologies to determine a new estimate of the volcanic CO₂ input and to test if temporal fluctuations may be resolved. Employing representative average values of 2.7 g cm⁻³ as density of erupted material, 0.2 wt percent CO₂ in the original melt, 60 percent degassing during eruption, and an average volume of 0.1 km³ for each of the eruptions in the recently published eruption chronology of Hirschboeck (1980), a volcanic input of about 1.5 · 10¹¹ moles CO₂ yr⁻¹ was determined for the period 1800–1969. The period 1800–1899 had a somewhat lower input than 1900–1969, which could well be related more to completeness of observational data than to a real increase in volcanic CO₂. This input is well below man's current CO₂ production of 4–5 · 10¹⁴ moles CO₂ yr⁻¹. The average values above together with specific volumetric estimates were employed to calculate CO₂ input from individual historic eruptions, massive flood basalts, and ash-flow eruptions. Total CO₂ release from the largest of flood basalt and ash-flow sequences was 10¹⁵-10¹⁶ moles of CO₂. The impact of these sources on global atmospheric CO₂ and climate, however, will be limited by the duration and spacing of the major individual eruptive periods in the sequences.     

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.