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.     

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.     

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.     

层状钙华及其地球化学指标的古气候/环境意义

层状钙华作为高分辨率古气候环境重建记录已被国内外许多学者所关注.钙华的微层厚度、氧碳同位素组成和微量元素的含量都呈现出随季节变化的周期性特点.钙华年层的形成与方解石沉积速率或者微生物生长活性的季节变化有关;氧同位素组成的变化主要受温度和沉积水体的δ18O控制,但蒸发作用(尤其是在干旱区)也有重要影响;钙华的稳定碳同位素...     

Seasonal patterns of carbon chemistry and isotopes in tufa depositing groundwaters of southwestern Japan

Annually laminated carbonates, known as tufas, commonly develop in limestone areas and typically record seasonal patterns of oxygen- and carbon-isotope compositions. δ¹⁸O values are principally controlled by seasonal changes of water temperature, whereas δ¹³C values are the result of complex reactions among the gaseous, liquid, and solid sources of carbon in the system. We examined the processes that cause the seasonal patterns of δ¹³C in groundwater systems at three tufa-depositing sites in southwestern Japan by applying model calculations to geochemical data. Underground inorganic carbon species are exchanged with gaseous CO₂, which is mainly introduced to the underground hydrological system by natural atmospheric ventilation and by diffusion of soil air. These processes control the seasonal pattern of δ¹³C, which is low in summer and high in winter. Among the three sites we investigated, we identified two extreme cases of the degree of carbon exchange between liquid and gaseous phases. For the case with high radiocarbon composition (Δ¹⁴C) and low pCO₂, there was substantial carbon exchange because of a large contribution of atmospheric CO₂ and a small water mass. For the other extreme case, which was characterized by low Δ¹⁴C and high pCO₂, the contribution of atmospheric CO₂ was small and the water mass was relatively large. Our results suggest that at two of the three sites water residence time within the soil profile was longer than 1 year. Our results also suggested a short residence time (less than 1 year) of water in the soil profile at the site with the smallest water mass, which is consistent with large seasonal amplitude of the springwater temperature variations. The Δ¹⁴C value of tufas is closely related to the hydrological conditions in which they are deposited. If the initial Δ¹⁴C value of a tufa-depositing system is stable, ¹⁴C-chronology can be used to date paleo-tufas.     

Modelling δC and δO in the solution layer on stalagmite surfaces

We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO₂ and the buffering effect of the water reservoir are taken into account. Whereas δ¹³C shows a progressive increase to a final constant value, δ¹⁸O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H₂O-CO₂-CaCO₃ solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ¹³C and δ¹⁸O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ¹³C and δ¹⁸O values.     

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.     

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.     

Palaeoenvironmental records in Holocene Spanish tufas: a stable isotope approach in search of reliable climatic archives

Tufa deposits are potential terrestrial archives of palaeoenvironmental and palaeoclimatic information. This study assesses the potential of stable isotopic archives from two closely juxtaposed Holocene tufa sites in SE Spain. The Ruidera site contains deep‐water lacustrine micrites and tufas, whereas the nearby Alcaraz site represents a shallow barrage tufa. Understanding site characteristics is critical to interpreting the stable isotopic variations. These Holocene lacustrine micrites have isotopic compositions consistent with modern European lake shore microbial carbonates, where the isotopic chemistry is strongly influenced by hydrological and residence time effects. All the lacustrine micrite δ¹³C values were influenced by microenvironmental microbial effects to some degree. Because of these effects, stable isotope data from lacustrine microbial micrites and tufas will not normally yield precise information on the isotopic composition of palaeoprecipitation, temperature or vegetation composition of an area. In contrast, Holocene tufas that formed in shallow, fast‐flowing riverine settings may contain valuable palaeoclimatic archives. The tufa deposits must be largely autochthonous, as at Alcaraz, where in situ reed stem encrustations are present. Records of relative change in air temperature and changes in the source of airmasses are potentially resolvable in the δ¹⁸O data. These interpretations can be verified by other independent climatic data where chronology is constrained. Variations in riverine tufa δ¹³C values probably record changes in local vegetation and/or soil respiration. Covariation between δ¹⁸O and δ¹³C values may be intrinsically linked to climatic factors such as aridity. Tentative palaeoclimatic interpretations for the middle Holocene at Alcaraz based on the isotope data suggest warming (or increasing influence of Mediterranean‐sourced precipitation) between approximately 5000–3000 radiocarbon years BP, accompanied by increased aridity. These interpretations are consistent with the sparse independent palaeoclimatic data and climate modelling results for the Holocene of SE Spain. This study supports the growing evidence that well‐chosen tufa sites could yield valuable palaeoclimatic information.     

Stable isotope variations in modern tropical speleothems: Evaluating equilibrium vs. kinetic isotope effects

Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison’s Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ¹⁸O and δ¹³C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified.Carbon isotope values for the majority of modern speleothem samples from Harrison’s Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ¹³C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The ¹³C depletions are likely caused by kinetically driven departures in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions, caused by rapid calcite growth. ¹³C enrichments can be accounted for by Rayleigh distillation of the HCO₃⁻ (aq) reservoir during degassing of ¹³C-depleted CO₂.Modern speleothems from Harrison’s Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in ¹⁸O relative to equilibrium values. δ¹⁸O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ¹³C, δ¹⁸O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO₂ hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO₃⁻ (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in ¹⁸O enrichment in the HCO₃⁻ (aq) reservoir and ultimately in the precipitated CaCO₃.     

Soils at the hyperarid margin: The isotopic composition of soil carbonate from the Atacama Desert, Northern Chile

We evaluate the impact of exceptionally sparse plant cover (0-20%) and rainfall (2-114 mm/yr) on the stable carbon and oxygen composition of soil carbonate along elevation transects in what is among the driest places on the planet, the Atacama Desert in northern Chile. δ¹³C and δ¹⁸O values of carbonates from the Atacama are the highest of any desert in the world. δ¹³C (VPDB) values from soil carbonate range from −8.2‰ at the wettest sites to +7.9‰ at the driest. We measured plant composition and modeled respiration rates required to form these carbonate isotopic values using a modified version of the soil diffusion model of [Cerling (1984) Earth Planet. Sci. Lett.71, 229-240], in which we assumed an exponential form of the soil CO₂ production function, and relatively shallow (20-30 cm) average production depths. Overall, we find that respiration rates are the main predictor of the δ¹³C value of soil carbonate in the Atacama, whereas the fraction C₃ to C₄ biomass at individual sites has a subordinate influence. The high average δ¹³C value (+4.1‰) of carbonate from the driest study sites indicates it formed—perhaps abiotically—in the presence of pure atmospheric CO₂.δ¹⁸O (VPDB) values from soil carbonate range from −5.9‰ at the wettest sites to +7.3‰ at the driest and show much less regular variation with elevation change than δ¹³C values. δ¹⁸O values for soil carbonate predicted from local temperature and δ¹⁸O values of rainfall values suggest that extreme (>80% in some cases) soil dewatering by evaporation occurs at most sites prior to carbonate formation. The effects of evaporation compromise the use of δ¹⁸O values from ancient soil carbonate to reconstruct paleoelevation in such arid settings.     

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.     

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.     

The potential origins and palaeoenvironmental implications of high temporal resolution δO heterogeneity in coral skeletons

δ¹⁸O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ¹⁸O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ¹⁸O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ¹¹B. We model predicted skeletal δ¹⁸O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO₂ to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ¹⁸O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO₂ at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO₂. Seasonal skeletal δ¹⁸O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ¹⁸O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ¹⁸O heterogeneity.     

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.     

Controls on dissolved inorganic carbon and δC in cave waters from DeSoto Caverns: Implications for speleothem δC assessments

Unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time-series δ¹³C records of speleothems. Here we report the results of a 3-year study of total dissolved inorganic carbon [DIC] and δ¹³C_DIC from cave waters at DeSoto Caverns (Southeastern USA) that offer valuable insight on carbon transport and the accompanied isotope fractionations from end-member sources to speleothems.[DIC] and δ¹³C_DIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ¹³C_DIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ¹³C_DIC = −2.49[DIC] + 0.64, r² = 0.84). A shallow pool fed by multiple drips shows a bimodal δ¹³C_DIC distribution with an isotopically heavier mode during winter (−4‰ to −5‰ VPDB) relative to summer months (−9‰ to −10‰ VPDB). A multi-year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry. Coupled cave air winter ventilation/summer stagnation and varying CO₂ fluxes through the soil horizon and epikarst exert the strongest influence on seasonal [DIC] and δ¹³C_DIC variability. Measured values of high [DIC] and low δ¹³C_DIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ¹³C_DIC values during winter/early months indicate kinetically enhanced isotopic fractionations within the cave waters. The kinetically enhanced isotopic fractionation of partitioned between degassed CO₂ and precipitated CaCO₃(1000lnα_{[(CO2-HCO3)+(CaCO3(AR)-HCO3)]/2}) is greater by about a factor of two (−6.7 ± 0.3‰) relative to the same isotopic fractionation under equilibrium conditions (−3.1‰).On the basis of ¹⁴C mass balance and paired ¹⁴C-U/Th measurements we estimate that on average about ∼23% of C delivered annually by the drips to the aragonite stalagmites is derived from ¹⁴C-dead dolomite cap while the remainder of ∼77% is derived from ¹⁴C-live biomass. δ¹³C measurements of aragonite (n = 12) sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite δ¹³C values calculated using the shallow pool summer/early fall data thus confirming the δ¹³C seasonality in both drips and coeval aragonite. δ¹³C values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of −7.1 ± 1.2‰ (n = 81) and a mode of −7‰ to −8‰ that are statistically indistinguishable from the annual mean and mode of all dripwaters. Thus secular time-series δ¹³C records of stalagmites at DeSoto Caverns with resolving power >10⁻¹ year will likely carry the imprints of drip annual means that record climate-driven δ¹³C seasonal biases.     

Controls on ostracod valve geochemistry, Part 1: Variations of environmental parameters in ostracod (micro-)habitats

The variations of environmental conditions (T°, pH, δ¹³C_DIC, [DIC], δ¹⁸O, Mg/Ca, and Sr/Ca) of ostracod habitats were examined to determine the controls of environmental parameters on the chemical and isotopic composition of ostracod valves. Results of a one-year monitoring of environmental parameters at five sites, with depths of between 2 and 70 m, in Lake Geneva indicate that in littoral to sub-littoral zones (2, 5, and 13 m), the chemical composition of bottom water varies seasonally in concert with changes in temperature and photosynthetic activity. An increase of temperature and photosynthetic activity leads to an increase in δ¹³C values of DIC and to precipitation of authigenic calcite, which results in a concomitant increase of Mg/Ca and Sr/Ca ratios of water. In deeper sites (33 and 70 m), the composition of bottom water remains constant throughout the year and isotopic values and trace element contents are similar to those of deep water within the lake. The chemical composition of interstitial pore water also does not reflect seasonal variations but is controlled by calcite dissolution, aerobic respiration, anaerobic respiration with reduction of sulphate and/or nitrate, and methanogenesis that may occur in the sediment pores. Relative influence of each of these factors on the pore water geochemistry depends on sediment thickness and texture, oxygen content in bottom as well as pore water. Variations of chemical compositions of the ostracod valves of this study vary according to the specific ecology of the ostracod species analysed, that is its life-cycle and its (micro-)habitat. Littoral species have compositions that are related to the seasonal variations of temperature, δ¹³C values of DIC, and of Mg/Ca and Sr/Ca ratios of water. In contrast, the compositions of profundal species are largely controlled by variations of pore fluids along sediment depth profiles according to the specific depth preference of the species. The control on the geochemistry of sub-littoral species is a combination of controls for the littoral and profundal species as well as the specific ecology of the species.     

A model for O/O variations in CO2 evolved from goethite during the solid-state α-FeOOH to α-Fe2O3 phase transition

“Plateau” δ¹⁸O values of CO₂ that evolved from the Fe(CO₃)OH component during isothermal vacuum dehydrations (200-230 °C) of 18 natural goethites range from 8.2 to 28.1‰. In contrast, the measured δ¹⁸O values of the goethite structural oxygen range from −11.3 to 1.7‰. The results of this study indicate that the apparent oxygen isotope fractionation factor (¹⁸α_app) between plateau CO₂ and initial goethite is systematically related to the rate of isothermal vacuum dehydration. The nonlinear correlation and the magnitudes of the ¹⁸α_app values are predicted by a relatively simple mass balance model with the following assumptions: (1) the rate of isothermal vacuum dehydration of goethite (for the interval from 0 to ∼60 to 80% loss of structural hydroxyl hydrogen) can be reasonably well represented by first-order kinetics and (2) isotopic exchange between evolving H₂O vapor and solid occurs only in successive, local transition states. The generally good correspondence between the model predictions and the experimental data seems to validate these assumptions. Thus, the ¹⁸O/¹⁶O ratios of the evolved CO₂ can act as probes into the transient processes operating at the molecular level during the solid-state goethite-to-hematite phase transition. For example, the activation energy for the rate constant associated with the transition state, oxygen isotopic exchange between solid and H₂O vapor, is tentatively estimated as 28 ± 11 KJ/mol. Such knowledge may be of consequence in understanding the significance of ¹⁸O/¹⁶O ratios in hematites from some natural environments (e.g., Mars?).Kinetic data and δ¹⁸O values of CO₂ are routinely obtained in the course of measurements of the abundance and δ¹³C values of the Fe(CO₃)OH in goethite. The observed correlation between ¹⁸α_app and dehydration rates suggests that plateau δ¹⁸O values of evolved CO₂ may provide complementary estimates of the δ¹⁸O values of total goethite structural oxygen (O, OH, CO₂) with an overall precision of about ±1‰. However, because of isotopic exchange during the dehydration process, δ¹⁸O values of the evolved CO₂ do not reflect the original δ¹⁸O values of the CO₂ that was occluded as Fe(CO₃)OH in goethite.     

Carbon and oxygen stable isotopes in the middle-upper miocene and lower pliocene carbonates of the Eastern Paratethys (Kerch-Taman Region): Palaeoenvironments and post-sedimentation changes

C and O isotope composition of Middle-Upper Miocene and Lower Pliocene carbonates from Kerch-Taman Region (Eastern Paratethys) have been studied in order to reconstruct palaeoenvironmental variability and post-sedimentation changes. The δ¹³C and δ¹⁸О values of the Upper Sarmatian to Lower Pliocene organogenic carbonates reflect the desalinization of paleobasins, global Late Miocene Cooling, and increase in seasonal temperature fluctuations. Isotopic composition of the Middle Sarmatian organogenic carbonates was strongly influenced by evaporation processes, high bioproductivity, and local submarine methane emissions. Warm climate and low bioproductivity together with unstable hydrological regime during the Late Chokrakian and the Karaganian times influenced the isotope composition of primary carbonates. Calcite shell of Spiratella sp. (δ¹³C =–0.4‰ and δ¹⁸О =–0.4‰) from Tarkhanian sediments was formed in warm marine environment. Dolomitization prevails over other secondary mineralization in the studied carbonate rocks. Two groups of secondary dolomites that are characterized by negative and positive δ¹³C values have been recognized. Lowe δ¹³C values (up to–31.4‰) in dolomites indicate the influence of both dissolved inorganic carbon (DIC) from oxidized organic matter (С_org) and methane. Dolomites with positive δ¹³C values (7.0 and 7.8‰) associat with migration of CO₂- and CH₄-containing saline groundwater.     

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