Response to the Comment by J. Horita and R.N. Clayton on “The studies of oxygen isotope fractionation between calcium carbonates and water at low temperatures”

The apparent inconsistency in calcite-water fractionation does occur between the arithmetic combination of Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2003) An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures. Geochim. Cosmochim. Acta67, 387-399] and the experimental determination of Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2005) Effect of polymorphic transition on oxygen isotope fractionation between aragonite, calcite and water: a low-temperature experimental study. Am. Mineral90, 1121-1130]. To resolve this issue is to acknowledge whether or not the isotope salt effect of dissolved minerals would occur on oxygen isotope exchange between water and the minerals of interest. The question is whether or not a term of mineral-water interaction should be taken into account when calculating mineral-water 10³ln α factors by an arithmetic combination between theoretical 10³ln β factors for mineral and water, respectively. The hydrothermal experiments of Hu and Clayton [Hu G.-X., and Clayton R.N. (2003) Oxygen isotope salt effects at high pressure and high temperature, and the calibration of oxygen isotope geothermometers. Geochim. Cosmochim. Acta67, 3227-3246] demonstrate the absence of isotope salt effect on the oxygen isotope fractionation between calcite and water, and this abnormal behavior reasonably explains the so-called inconsistency in the calcite-water fractionations of Zhou and Zheng (2003, 2005). We argue that the mineral-water correction is still necessary for calculation of fractionations in mineral-water systems. New experimental data for oxygen isotope fractionations involving dolomite and cerussite are consistent with the calculations of Zheng [Zheng Y.-F. (1999a) Oxygen isotope fractionation in carbonate and sulfate minerals. Geochem. J.33, 109-126], but also shed light on the assumptions used in modifying the increment method. We argue that the modified increment method has developed into a theoretical mean of predictive power for calculation of oxygen isotope fractionation factors for crystalline minerals of geochemical interest.     

On the Direction and Magnitude of Oxygen Isotope Fractionation Between Calcite and Aragonite at Thermodynamic Equilibrium

Oxygen isotope fractionation factors between calcium carbonates and water have been applied to ancient marine geochemistry principally for the purpose of geothermometry. The problem was encountered, however, with respect to the direction and magnitude of oxygen isotope fractionation between calcite and aragonite at thermodynamic equilibrium. This basically involves sound understanding of both thermodynamics and kinetics of oxygen isotope fractionation between inorganically precipitated carbonate and water at low temperatures. Thus the crucial issues are to acknowledge the processes of chemical reaction and isotopic exchange during precipitation of CaCO₃ minerals in solution, the kinetic mechanism of isotope equilibrium or disequilibrium, the effect of polymorphic transition from metastable aragonite to stable calcite under hydrous or anhydrous conditions, and the presence or absence of isotope salt effect on oxygen isotope exchange between carbonate and water in response to the hydrous or anhydrous conditions at thermodynamic equilibrium. Because good agreements exist in carbonate–water oxygen isotope fractionation factors between theoretical calculations and experimental determinations, it is encouraging to applying the thermodynamic and kinetic data to isotopic paleothermometry and geochemical tracing.     

碳酸盐矿物氧同位素分馏的理论研究

应用增量方法系统地计算了碳酸盐矿物的同位素分馏系数，得到不同结构和成分的碳酸盐矿物的18O富集顺序为：菱铁矿〉铁白云石〉菱镁矿≥白云石≥方解石〉文石〉菱锶矿〉白铅矿〉碳钡矿。在0℃～1200℃范围内获得了一组内部一致的碳酸盐－水体系的理论分馏系数，这些计算结果与已知的实验和／或经验数据之间存在良好的一致性，因此本文对碳酸盐矿物氧同位素分馏系数的理论校准不仅可应用于共生矿物组合形成温度的确定，而且能够应用于其形成机理的示踪。 计算结果表明，白云石的氧同位素分馏行为与方解石相似，在25℃下白云石与方解石之间的平衡分馏为0.56‰ 。理论预测文石相对于方解石显著地亏损 δ18O，在25℃时方解石与文石之问的平衡分馏为4.47‰ 。文石向方解石的同质多相转变可能是通过一种没有同位素再造的惰性氧结构单元[CO3]2- 进行的，即只涉及Ca2+ 与[C03]2- 基团之间键的断裂和再组台而未出现[CO3]2- 基团内部C－O键的断裂和再组合。结果在自然界和实验室实验中，文石中氧同位索配分的温度关系能够传递副方解石中来。这种在同质多相转变形成方解石过程中的氧同位素继承性对于了解白云石－方解石－水体系分馏的难题至关重要。理论预测也能够用来解释对方解石分馏的经验估算与实验测定之间的分歧。     

碳酸钙-水体系氧同位素分馏系数的低温实验研究

碳酸钙是古气候和沉积岩稳定同位素地球化学研究中最常用的矿物 ,因此对碳酸钙水体系氧同位素分馏系数的实验校准已成为稳定同位素地球化学诞生以来的热点和前沿课题。但由于碳酸钙在自然界存在 3种同质多象变体 (方解石、文石和六方方解石 ) ,使人们对碳酸钙矿物与水之间氧同位素分馏系数的实验测定结果存在较大差别 ,当应用到同位素地质测温时 ,会给出显著不同的温度值。正确选用合理的方解石水或文石水体系分馏曲线 ,对低温和环境地球化学研究和应用具有重要价值。文章系统总结和评述了碳酸钙水体系氧同位素分馏系数实验校准的历史、方法和结果 ,对前人在表达方式上的不一致进行了统一 ,对氧同位素分馏的盐效应、动力氧同位素分馏效应和同质多象转变过程中的氧同位素继承性进行了讨论。通过对前人大量实验数据的系统处理并与理论计算相比较 ,推荐了热力学上平衡的方解石水体系氧同位素分馏方程 ,而对于文石水体系 ,理论计算结果尚有待于实验证实。     

Oxygen isotope fractionation between synthetic aragonite and water: Influence of temperature and Mg concentration

Aragonite was precipitated in the laboratory at 0, 5, 10, 25, and 40 °C to determine the temperature dependence of the equilibrium oxygen isotope fractionation between aragonite and water. Forced CO₂ degassing, passive CO₂ degassing, and constant addition methods were employed to precipitate aragonite from supersaturated solutions, but the resulting aragonite-water oxygen isotope fractionation was independent of the precipitation method. In addition, under the experimental conditions of this study, the effect of precipitation rate on the oxygen isotope fractionation between aragonite and water was almost within the analytical error of ±∼0.13‰ and thus insignificant. Because the presence of Mg²⁺ ions is required to nucleate and precipitate aragonite from Na-Ca-Cl-HCO₃ solutions under these experimental conditions, the influence of the total Mg²⁺ concentration (up to ∼0.9 molal) on the aragonite-water oxygen isotope fractionation was examined at 25 °C. No significant Mg²⁺ ion effect, or oxygen isotope salt effect, was detected up to 100 mmolal total Mg²⁺ but a noticeable isotope salt effect was observed at ∼0.9 molal total Mg²⁺.On the basis of results of the laboratory synthesis experiments, a new expression for the aragonite-water fractionation is proposed over the temperature range of 0-40 °C:

1000lnα_{aragonite-water}=17.88±0.13(10³/T)-31.14±0.46     

Calcium isotope fractionation in calcite and aragonite

Calcium isotope fractionation was measured on skeletal aragonite and calcite from different marine biota and on inorganic calcite. Precipitation temperatures ranged from 0 to 28°C. Calcium isotope fractionation shows a temperature dependence in accordance with previous observations: 1000 · ln(α_cc) = −1.4 + 0.021 · T (°C) for calcite and 1000 · ln(α_ar) = −1.9 + 0.017 · T (°C) for aragonite. Within uncertainty the temperature slopes are identical for the two polymorphs. However, at all temperatures calcium isotopes are more fractionated in aragonite than in calcite. The offset in δ^44/40Ca is about 0.6‰. The underlying mechanism for this offset may be related to the different coordination numbers and bond strengths of the calcium ions in calcite and aragonite crystals, or to different Ca reaction behavior at the solid-liquid interface. Recently, the observed temperature dependence of the Ca isotope fractionation was explained quantitatively by the temperature control on precipitation rates of calcium carbonates in an experimental setting (Lemarchand et al., 2004). We show that this mechanism can in principle also be applied to CaCO₃ precipitation in natural environments in normal marine settings. Following this model, Ca isotope fractionation in marine Ca carbonates is primarily controlled by precipitation rates. On the other hand the larger Ca isotope fractionation of aragonite compared to calcite can not be explained by different precipitation rates. The rate control model of Ca isotope fractionation predicts a strong dependence of the Ca isotopic composition of carbonates on ambient CO₃²⁻ concentration. While this model is in general accordance with our observations in marine carbonates, cultured specimens of the planktic foraminifer Orbulina universa show no dependence of Ca-isotope fractionation on the ambient CO₃²⁻ concentration. The latter observation implies that the carbonate chemistry in the calcifying vesicles of the foraminifer is independent from the ambient carbonate ion concentration of the surrounding water.     

Calibration of the calcite-water oxygen-isotope geothermometer at Devils Hole, Nevada, a natural laboratory

The δ¹⁸O of ground water (−13.54 ± 0.05 ‰) and inorganically precipitated Holocene vein calcite (+14.56 ± 0.03 ‰) from Devils Hole cave #2 in southcentral Nevada yield an oxygen isotopic fractionation factor between calcite and water at 33.7 °C of 1.02849 ± 0.00013 (1000 ln α_{calcite-water} = 28.09 ± 0.13). Using the commonly accepted value of ∂(α_{calcite-water})/∂T of −0.00020 K⁻¹, this corresponds to a 1000 ln α_{calcite-water} value at 25 °C of 29.80, which differs substantially from the current accepted value of 28.3. Use of previously published oxygen isotopic fractionation factors would yield a calcite precipitation temperature in Devils Hole that is 8 °C lower than the measured ground water temperature. Alternatively, previously published fractionation factors would yield a δ¹⁸O of water, from which the calcite precipitated, that is too negative by 1.5 ‰ using a temperature of 33.7 °C. Several lines of evidence indicate that the geochemical environment of Devils Hole has been remarkably constant for at least 10 ka. Accordingly, a re-evaluation of calcite-water oxygen isotopic fractionation factor may be in order.Assuming the Devils Hole oxygen isotopic value of α_{calcite-water} represents thermodynamic equilibrium, many marine carbonates are precipitated with a δ¹⁸O value that is too low, apparently due to a kinetic isotopic fractionation that preferentially enriches ¹⁶O in the solid carbonate over ¹⁸O, feigning oxygen isotopic equilibrium.     

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:

     

Stable isotope fractionation between mollusc shells and marine waters from Martinique Island

Forty-nine aragonitic and calcitic shells from 14 species of marine tropical molluscs (Bivalvia, Gastropoda, Polyplacophora) and ambient waters from Martinique have been analyzed for their carbon and oxygen isotope compositions. Mineralogy of shells was systematically determined by Raman spectroscopy that reveals composite shell structures and early processes of diagenetic alteration. In mangrove, brackish waters result from the mixing between 89±1% of seawater and 11±1% of freshwater, a hydrological budget quantified by both oxygen isotope and salinity mass balance calculations. Mollusc shells from the mangrove environment (S=31‰; δ¹⁸O=0.5‰) are characterized by mean δ¹³C values (−1.2‰) lower than those (+2.6‰) living in the open sea (S=35‰; δ¹⁸O=1‰). These low carbon isotope compositions result from the oxidation of organic matter into bicarbonate ions used in the building of mollusc shells. The oxygen isotope compositions of the studied mollusc species are mainly controlled by the temperature and composition of seawater whereas the role of the so-called “vital effects” is negligible. Contrasting with carbon isotopes, variability in the δ¹⁸O values among and within species of mollusc shells is very low (1σ=0.15) for a given littoral environment. Using ambient temperatures of seawater (28-30 °C), oxygen isotope fractionations between all studied living species and environmental waters match those extrapolated from the fractionation equation established for molluscs by Grossman and Ku [Chem. Geol., Isot. Geosci. Sect. 59 (1986) 59] in the range 3-20 °C. By analyzing calcite and aragonite layers from the same shell or by comparing shells from different species living in the same environment, there is no evidence that oxygen isotope fractionation between aragonite and water differs from that between calcite and water. On the basis of these results, we conclude that the oxygen isotope compositions of shells from most fossil mollusc species are suitable to estimate past seawater temperatures at any paleolatitude.     

文石-水体系氧同位素分馏系数的低温实验研究

采用缓慢分解法和“两步法”的附晶生长法,在低温(0℃～70℃)下实验合成纯文石型碳酸 钙矿物,以XRD和SEM技术对合成矿物的相组成和形貌进行了鉴定。将XRD与SEM及氧同位素分 析技术相结合,研究了文石的生成速率与氧同位素分馏之间关系。对0℃、25℃和50℃条件 下采用缓慢分解法合成的文石进行SEM观察发现,随着温度升高,矿物生成速率加快,氧同 位素分馏逐渐趋于不平衡,导致50℃条件下获得的文石-水体系氧同位素分馏是一种不平衡 分馏,而0℃和25℃条件下获得的低值代表平衡分馏。将0℃和25℃以下采用缓慢分解法获得 的文石-水体系分馏低值与采用“两步法”的附晶生长法在50℃和70℃条件下获得的文石- 水体系平衡分馏数据相结合,得到0℃～70℃范围内文石-水体系氧同位素平衡分馏方程为 ：103lnα=20.41×103T－41.42。这个实验结果不仅与增量方法理论计算结 果一致,而且与前人低温实验获得的文石或文石与方解石混合相碳酸钙-水体系,以及生物 成因文石-水体系的氧同位素分馏结果相近。这是首次根据实验确定的无机成因文石-水体 系热力学平衡氧同位素分馏系数,因此对于无机成因文石在古沉积环境和古气候研究中的应 用具有重要参考价值。     

Large fractionation of calcium isotopes during cave-analogue calcium carbonate growth

We have measured δ^44/42Ca of laboratory-precipitated calcite grown in an experimental setup that closely replicates stalagmite formation. Calcium solutions were dripped onto two different substrates in tightly-controlled conditions and calcite precipitated due to rapid CO₂ degassing. With seeded glass slides as the substrate, we observe a Ca isotope ratio in the calcite which is ∼0.5‰ per amu lower than that in the growth solution. This fractionation is generally almost twice that observed in previously published calcite growth experiments and indicates a large kinetic effect on Ca isotopes in the stalagmite growth environment. The precipitate forming near the spot where the drip lands shows slightly greater solution-to-precipitate fractionation than calcite further from the drip reflecting a decrease in this kinetic fractionation as precipitation continues. We interpret these results in the context of the model of Fantle and DePaolo (2007) which involves surface entrapment of light Ca isotopes to decrease calcite δ^44/42Ca, and depletion of Ca from the solution in the direct vicinity of the growing calcite to increase calcite δ^44/42Ca. In the stalagmite setting, the second of these effects is minimized so that calcite Ca isotope ratios are unusually light. This interpretation suggests that stalagmite Ca isotope ratios should decrease with the saturation state of the drip water (i.e. with the growth rate of calcite). Ca isotopes might therefore allow reconstruction of surface entrapment of trace metals and isotopes more generally and might, for instance, allow an assessment of the appropriate relationship between oxygen isotope fractionation and temperature for periods of past growth in stalagmites.     

Oxygen isotope salt effects at high pressure and high temperature and the calibration of oxygen isotope geothermometers

The influence of NaCl, CaCl₂, and dissolved minerals on the oxygen isotope fractionation in mineral-water systems at high pressure and high temperature was studied experimentally. The salt effects of NaCl (up to 37 molal) and 5-molal CaCl₂ on the oxygen isotope fractionation between quartz and water and between calcite and water were measured at 5 and 15 kbar at temperatures from 300 to 750°C. CaCl₂ has a larger influence than NaCl on the isotopic fractionation between quartz and water. Although NaCl systematically changes the isotopic fractionation between quartz and water, it has no influence on the isotopic fractionation between calcite and water. This difference in the apparent oxygen isotope salt effects of NaCl must relate to the use of different minerals as reference phases. The term oxygen isotope salt effect is expanded here to encompass the effects of dissolved minerals on the fractionations between minerals and aqueous fluids. The oxygen isotope salt effects of dissolved quartz, calcite, and phlogopite at 15 kbar and 750°C were measured in the three-phase systems quartz-calcite-water and phlogopite-calcite-water. Under these conditions, the oxygen isotope salt effects of the three dissolved minerals range from ∼0.7 to 2.1‰. In both three-phase hydrothermal systems, the equilibrium fractionation factors between the pairs of minerals are the same as those obtained by anhydrous direct exchange between each pair of minerals, proving that the use of carbonate as exchange medium provides correct isotopic fractionations for a mineral pair.When the oxygen isotope salt effects of two minerals are different, the use of water as an indirect exchange medium will give erroneous fractionations between the two minerals. The isotope salt effect of a dissolved mineral is also the main reason for the observation that the experimentally calibrated oxygen isotope fractionations between a mineral and water are systematically 1.5 to 2‰ more positive than the results of theoretical calculations. Dissolved minerals greatly affect the isotopic fractionation in mineral-water systems at high pressure and high temperature. If the presence of a solute changes the solubility of a mineral, the real oxygen isotope salt effect of the solute at high pressure and high temperature cannot be correctly derived by using the mineral as reference phase.     

Oxygen isotope fractionation in synthetic magnesian calcite

Mg-bearing calcite was precipitated at 25°C in closed system free-drift experiments from solutions containing NaHCO₃, CaCl₂ and MgCl₂. The chemical and isotope composition of the solution and precipitate were investigated during time course experiments of 24-h duration. Monohydrocalcite and calcite precipitated early in the experiments (<8 h), while Mg-calcite was the predominant precipitate (>95%) thereafter. Solid collected at the end of the experiments displayed compositional zoning from pure calcite in crystal cores to up to 23 mol% MgCO₃ in the rims. Smaller excursions in Mg were superimposed on this chemical record, which is characteristic of oscillatory zoning observed in synthetic and natural solid-solution carbonates of differing solubility. Magnesium also altered the predominant morphology of crystals over time from the {104} to {100} and {110} growth forms.The oxygen isotope fractionation factor for the magnesian-calcite-water system (as 10³lnα_Mg-cl-H2O) displayed a strong dependence on the mol% MgCO₃ in the solid phase, but quantification of the relationship was difficult due to the heterogeneous nature of the precipitate. Considering only the Mg-content and δ¹⁸O values for the bulk solid, 10³lnα_Mg-cl-H2O increased at a rate of 0.17 ± 0.02 per mol% MgCO₃; this value is a factor of three higher than the single previous estimate (Tarutani T., Clayton R.N., and Mayeda T. K. (1969) The effect of polymorphims and magnesium substitution on oxygen isotope fractionation between calcium carbonate and water. Geochim. Cosmochim. Acta 33, 987-996). Nevertheless, extrapolation of our relationship to the pure calcite end member yielded a value of 27.9 ± 0.02, which is similar in magnitude to published values for the calcite-water system. Although no kinetic effect was observed on 10³lnα_Mg-cl-H2O for precipitation rates that ranged from 10^3.21 to 10^4.60 μmol · m⁻² · h⁻¹, it was impossible to disentangle the potential effect(s) of precipitation rate and Mg-content on 10³lnα_Mg-cl-H2O due to the heterogeneous nature of the solid.The results of this study suggest that paleotemperatures inferred from the δ¹⁸O values of high magnesian calcite (>10 mol% MgCO₃) may be significantly underestimated. Also, the results underscore the need for additional experiments to accurately characterize the effect of Mg coprecipitation on the isotope systematics of calcite from a chemically homogeneous precipitate or a heterogeneous material that is analyzed at the scale of chemical and isotopic zonation.     

Carbon and oxygen isotope fractionation in non-marine ostracods: results from a ‘natural culture’ environment

Carbon and oxygen isotope analysis of ostracods living in the near-constant conditions of spring-fed ponds in southern England allowed accurate determination of the ostracod’s calcite-water ¹³C/¹²C and ¹⁸O/¹⁶O fractionations. The ¹³C/¹²C fractionations of two species, Candona candida and Pseudocandona rostrata, correspond to values expected for isotopic equilibrium with the pond’s dissolved inorganic carbon at the measured temperature (11°C) and pH (6.9), whilst those of a third species, Herpetocypris reptans, would represent equilibrium at a slightly higher pH (7.1).The ¹⁸O/¹⁶O fractionations confirm two previous studies in being larger, by up to 3‰, than those ‘traditionally’ regarded as representing equilibrium. When the measured fractionations are considered in the context of more recent work, however, they can be explained in terms of equilibrium if the process of calcite formation at the ostracod lamella occurs at a relatively low pH (≤7) irrespective of the pH of the surrounding water. The pH of calcite formation, and therefore the calcite-water ¹⁸O/¹⁶O fractionation, may be species and stage (adult versus juvenile) specific, and related to the rate of calcification.     

Kinetic mechanism of oxygen isotope disequilibrium in precipitated witherite and aragonite at low temperatures: an experimental study

To study what dictates oxygen isotope equilibrium fractionation between inorganic carbonate and water during carbonate precipitation from aqueous solutions, a direct precipitation approach was used to synthesize witherite, and an overgrowth technique was used to synthesize aragonite. The experiments were conducted at 50 and 70°C by one- and two-step approaches, respectively, with a difference in the time of oxygen isotope exchange between dissolved carbonate and water before carbonate precipitation. The two-step approach involved sufficient time to achieve oxygen isotope equilibrium between dissolved carbonate and water, whereas the one-step approach did not. The measured witherite-water fractionations are systematically lower than the aragonite-water fractionations regardless of exchange time between dissolved carbonate and water, pointing to cation effect on oxygen isotope partitioning between the barium and calcium carbonates when precipitating them from the solutions. The two-step approach experiments provide the equilibrium fractionations between the precipitated carbonates and water, whereas the one-step experiments do not. The present experiments show that approaching equilibrium oxygen isotope fractionation between precipitated carbonate and water proceeds via the following two processes:

1.

Oxygen isotope exchange between [CO₃]²⁻ and H₂O:

(1)     

Experimental study of the aragonite to calcite transition in aqueous solution

The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca²⁺]:[CO₃²⁻] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in ¹⁸O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of ¹⁸O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the ¹⁸O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C¹⁶O₃²⁻]_aq and [H₂¹⁸O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.     

Mechanisms of equilibrium and kinetic oxygen isotope effects in synthetic aragonite at 25 °C

Aragonite was precipitated in the laboratory at 25 °C in isotopic equilibrium with Na-Ca-Mg-Cl-CO₃ solutions at two different pH values (i.e., pH = ∼8.2 and ∼10.8) by the constant addition method. On the basis of the oxygen isotope composition of the aragonite precipitates, it was demonstrated that the equilibrium aragonite-water fractionation factor is independent of the pH of the parent solution and equal to:

1000lnα_{(aragonite-H2O)}=29.12±0.09     

Element partitioning during precipitation of aragonite from seawater: A framework for understanding paleoproxies

This study presents the results from precipitation experiments carried out to investigate the partitioning of the alkaline earth cations Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ between abiogenic aragonite and seawater as a function of temperature. Experiments were carried out at 5 to 75 °C, using the protocol of Kinsman and Holland [Kinsman, D.J.J., Holland, H.D., 1969. The coprecipitation of cations with CaCO₃ IV. The coprecipitation of Sr²⁺ with aragonite between 16 and 96 °C. Geochim. Cosmochim. Acta33, 1-17.] The concentrations of Mg Sr and Ba were determined in the fluid from each experiment by inductively coupled plasma-mass spectrometry, and in individual aragonite grains by secondary ion mass spectrometry. The experimentally produced aragonite grains are enriched in trace components (“impurities”) relative to the concentrations expected from crystal-fluid equilibrium, indicating that kinetic processes are controlling element distribution. Our data are not consistent with fractionations produced kinetically in a boundary layer adjacent to the growing crystal because Sr²⁺, a compatible element, is enriched rather than depleted in the aragonite. Element compatibilities, and the systematic change in partitioning with temperature, can be explained by the process of surface entrapment proposed by Watson and Liang [Watson, E.B., Liang, Y., 1995. A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am. Mineral.80, 1179-1187] and Watson [Watson, E.B., 1996. Surface enrichment and trace-element uptake during crystal growth. Geochim. Cosmochim. Acta60, 5013-5020; Watson, E.B., 2004. A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals. Geochim. Cosmochim. Acta68, 1473-1488]. This process is thought to operate in regimes where the competition between crystal growth rate and diffusivity in the near-surface region limits the extent to which the solid can achieve partitioning equilibrium with the fluid. A comparison of the skeletal composition of Diploria labyrinthiformis (brain coral) collected on Bermuda with results from precipitation calculations carried out using our experimentally determined partition coefficients indicate that the fluid from which coral skeleton precipitates has a Sr/Ca ratio comparable to that of seawater, but is depleted in Mg and Ba, and that there are seasonal fluctuations in the mass fraction of aragonite precipitated from the calcifying fluid (“precipitation efficiency”). The combined effects of surface entrapment during aragonite growth and seasonal fluctuations in “precipitation efficiency” likely forms the basis for the temperature information recorded in the aragonite skeletons of Scleractinian corals.     

Theoretical calculation of oxygen isotope fractionation factors in carbonate systems

Using established methods of statistical mechanical calculation and a recent compilation of vibrational frequency data, we have computed oxygen isotope reduced partition function ratios (β values) for a large number of carbonate minerals. The oxygen isotope β values of carbonates are inversely correlated to both the mass and radius of the cation bonded to the carbonate anion but neither correlation is good enough to be used as a precise and accurate predictor of β values. There is an approximately 0.6% relative increase in the β values of aragonite per 10 kbar increase in pressure. These estimates of the pressure effect on β values are broadly similar to those deduced previously for calcite using the methods of mineral physics. In comparing the β values of our study with those derived recently from first-principles lattice dynamics calculations, we find near-perfect agreement for calcite and witherite (<0.3% deviation), reasonable agreement for dolomite (<0.9% deviation) and somewhat poorer agreement for aragonite and magnesite (1.5-2% deviation). In the system for which we have the most robust constraints, CO₂-calcite, there is excellent agreement between our calculations and experimental data over a broad range of temperatures (0-900 °C). Similarly, there is good to excellent correspondence between calculation and experiment for most other low to moderate atomic mass carbonate minerals (aragonite to strontianite). The agreement is not as good for high atomic mass carbonates (witherite, cerussite, otavite). In the case of witherite and cerussite, the discrepancy may be due, in part, to our calculation methodology, which does not account for the effect of cation mass on the magnitude of vibrational frequency shifts associated with heavy isotope substitution. However, the calculations also reveal an incompatibility between the high- and low-temperature experimental datasets for witherite and cerussite. Specifically, the shapes of fractionation factor versus 1/T² curves in the calcite-witherite and calcite-cerussite systems do not conform to the robust constraints on the basic shape of these curves provided by theory. This suggests that either the high- or low-temperature datasets for both minerals is in error. Dolomite-calcite fractionation factors derived from our calculations fall within the wide range of fractionations for this system given by previous experimental and natural sample studies. However, our compilation of available low-temperature (25-80 °C) experimental data reveal an unusual temperature dependence of fractionations in this system; namely, the data indicate an increase in the magnitude of fractionations between dolomite (or proto-dolomite) and calcite with increasing temperature. Such a trend is incompatible with theory, which stipulates that fractionations between carbonate minerals must decrease monotonically with increasing temperature. We propose that the anomalous temperature dependence seen in the low-temperature experimental data reflect changes in the crystallinity and degree of cation ordering of the dolomite phase over this temperature interval and the effect these changes have on the vibrational frequencies of dolomite. Similar effects may be present in natural systems at low-temperature and must be considered in applying experimental or theoretical fractionation data to these systems. In nearly all cases, carbonate mineral-calcite fractionation factors given by the present calculations are in as good or better agreement with experimental data than are fractionations derived from semi-empirical bond strength methods.     

Isotopic fractionations associated with phosphoric acid digestion of carbonate minerals: Insights from first-principles theoretical modeling and clumped isotope measurements

Phosphoric acid digestion has been used for oxygen- and carbon-isotope analysis of carbonate minerals since 1950, and was recently established as a method for carbonate ‘clumped isotope’ analysis. The CO₂ recovered from this reaction has an oxygen isotope composition substantially different from reactant carbonate, by an amount that varies with temperature of reaction and carbonate chemistry. Here, we present a theoretical model of the kinetic isotope effects associated with phosphoric acid digestion of carbonates, based on structural arguments that the key step in the reaction is disproportionation of H₂CO₃ reaction intermediary. We test that model against previous experimental constraints on the magnitudes and temperature dependences of these oxygen isotope fractionations, and against new experimental determinations of the fractionation of ¹³C-¹⁸O-containing isotopologues (‘clumped’ isotopic species). Our model predicts that the isotope fractionations associated with phosphoric acid digestion of carbonates at 25 °C are 10.72‰, 0.220‰, 0.137‰, 0.593‰ for, respectively, ¹⁸O/¹⁶O ratios (1000 lnα^∗) and three indices that measure proportions of multiply-substituted isotopologues . We also predict that oxygen isotope fractionations follow the mass dependence exponent, λ of 0.5281 (where ). These predictions compare favorably to independent experimental constraints for phosphoric acid digestion of calcite, including our new data for fractionations of ¹³C-¹⁸O bonds (the measured change in Δ₄₇ = 0.23‰) during phosphoric acid digestion of calcite at 25 °C.We have also attempted to evaluate the effect of carbonate cation compositions on phosphoric acid digestion fractionations using cluster models in which disproportionating H₂CO₃ interacts with adjacent cations. These models underestimate the magnitude of isotope fractionations and so must be regarded as unsucsessful, but do reproduce the general trend of variations and temperature dependences of oxygen isotope acid digestion fractionations among different carbonate minerals. We suggest these results present a useful starting point for future, more sophisticated models of the reacting carbonate/acid interface. Examinations of these theoretical predictions and available experimental data suggest cation radius is the most important factor governing the variations of isotope fractionation among different carbonate minerals. We predict a negative correlation between acid digestion fractionation of oxygen isotopes and of ¹³C-¹⁸O doubly-substituted isotopologues, and use this relationship to estimate the acid digestion fractionation of for different carbonate minerals. Combined with previous theoretical evaluations of ¹³C-¹⁸O clumping effects in carbonate minerals, this enables us to predict the temperature calibration relationship for different carbonate clumped isotope thermometers (witherite, calcite, aragonite, dolomite and magnesite), and to compare these predictions with available experimental determinations. The success of our models in capturing several of the features of isotope fractionation during acid digestion supports our hypothesis that phosphoric acid digestion of carbonate minerals involves disproportionation of transition state structures containing H₂CO₃.