Oxygen isotope exchange between carbonic acid, bicarbonate, carbonate, and water: A re-examination of the data of McCrea (1950) and an expression for the overall partitioning of oxygen isotopes between the carbonate species and water

doi:10.1016/0016-7037(93)90159-T

Geochimica et Cosmochimica Acta

Volume 57, Issue 15, August 1993, Pages 3815-3818

https://doi.org/10.1016/0016-7037(93)90159-T Get rights and content

Abstract

An examination of McCREA's work (1950) shows that the $^{18} O^{16} O$ ratio of rapidly precipitated calcium carbonate depends upon the pH value of the solution and discloses that the oxygen isotope equilibrium fractionation between the sum of the dissolved carbonate species and water is linearly related to the equilibrium between the carbonate species. This relation permits the calculation of fractionation factors for the individual carbonate species and the expression of an overall fractionation factor in terms of individual factors and the oxygen proportions of the carbonate species. The fractionation factors a_{H₂CO₃-H₂O} = 1.0396, a_{HCO⁻₃-H₂O} = 1.0346, and a_{CO²⁻₃-H₂O} = 1.0183 (25°C) compare well to recent data.

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Cited by (96)

Multi-isotope fingerprints of recent environmental samples from the Baltic coast and their implications for bioarchaeological studies
2023, Science of the Total Environment
Stable isotopes in coastal regions are influenced by the so-called sea spray effect which masks the actual terrestrial isotope fingerprint with a marine isotope signal. The sea spray impact on plants was investigated by analyzing different stable isotope systems (δ¹³C_cellulose, δ¹⁸O_cellulose, δ¹⁸O_sulfate, δ³⁴S_sulfate, δ³⁴S_{total S}, δ³⁴S_{organic S}, ⁸⁷Sr/⁸⁶Sr) in recent environmental samples (plants, soil, water) collected close to the Baltic Sea.
All these isotopic systems are influenced by the sea spray, either by the uptake of ions (HCO₃⁻, SO₄²⁻, Sr²⁺) of marine origin, thus exhibiting a marine isotopic signature, or by biochemical reactions associated with, e.g., salinity stress. A shift towards seawater values is observed for δ¹⁸O_sulfate, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr. Cellulose becomes enriched in ¹³C and ¹⁸O due to sea spray, further enhanced (δ¹³C_cellulose) or mitigated (δ¹⁸O_cellulose) by salinity stress. The effect differs both regionally and seasonally, probably as a result of, e.g., differences in wind strength or prevailing wind direction, as well as between plants collected only few meters apart, in either the open field or at more wind-protected sites, reflecting samples more or less influenced by sea spray.
The stable isotope data of recent environmental samples are compared to previously analyzed archaeological bone samples of animals from the Viking Haithabu and Early Medieval Schleswig sites located close to the Baltic Sea. Potential regions of origin can be predicted based on the magnitude of the (recent) local sea spray effect. This enables the identification of probably non-local individuals.
The insights into sea spray mechanisms, biochemical reactions in plants, as well as seasonal, regional, and small-scale differences in stable isotope data will help to interpret multi-isotope fingerprints at coastal sites. Our study demonstrates the usefulness of environmental samples for bioarchaeological studies. Moreover, the detected seasonal and small-scale differences require adjusted sampling strategies for, e.g., isotopic baselines in coastal areas.
Identification and quantification of the sea spray effect on isotopic systems in α-cellulose (δ13C, δ18O), total sulfur (δ34S), and 87Sr/86Sr of European beach grass (Ammophila arenaria, L.) in a greenhouse experiment
2023, Science of the Total Environment
Citation Excerpt :
Consequently, both carbon and oxygen of marine origin will be metabolized into a variety of plant compounds, including α-cellulose. As marine HCO3− is enriched in both 13C and 18O (see e.g. Craig, 1953, 1954; Hoefs, 2021; Kroopnick, 1985; Mook and Vogel, 1968; Saltzman and Thomas, 2012; Usdowski and Hoefs, 1993; Zeebe, 1999), an uptake of marine HCO3− can explain that α-cellulose of group 2 plants was enriched by up to 6 ‰ in 13C and up to 2.7 ‰ in 18O compared to “control 2”. In the case of the second group, additionally to the sea spray effect, the isotopic signature of plants is affected by NaCl transferred to the plants via sea spray.
The sea spray effect can severely influence the isotopic signature of terrestrial individuals in coastal regions. To further specify this effect, beach grass was grown in a greenhouse under controlled environmental conditions and sprayed with mineral salt solution containing different mineral salts but only traces of NaCl (group 1). Another group of plants was sprayed with salty water from the Schlei inlet and the Baltic Sea, respectively (group 2). Control plants were only sprayed with tap water.
Isotope analyses were conducted on the unwashed and washed plants (δ¹³C_cellulose, δ¹⁸O_cellulose, δ³⁴S_{total S}, ⁸⁷Sr/⁸⁶Sr), soil (δ¹⁸O_sulfate, δ³⁴S_sulfate, ⁸⁷Sr/⁸⁶Sr), and spray as well as irrigation water (δ¹⁸O_sulfate, δ³⁴S_sulfate, ⁸⁷Sr/⁸⁶Sr). Moreover, elemental analyses were performed on the water samples.
The sea spray effect was visible in all isotopic systems under study. The uptake of SO₄²⁻, HCO₃⁻, and Sr²⁺ directly affected plants of group 1, while plants of group 2, sprayed with salty water, additionally showed salinity stress in the case of α-cellulose and total sulfur due to biochemical reactions of the plants. Very high concentrations in HCO₃⁻ or SO₄²⁻ also affected the plants' isotopic signatures. The impact of the sea spray and additional stress reactions were quantified.
Our study is the first experiment creating an artificial sea spray effect in a greenhouse. This experiment for the first time enables the identification and quantification of the sea spray effect in environmental samples. The marine signature taken up by the plants and recorded by the investigated isotopic systems is apparently high and should have an impact on the isotopic fingerprints of animal consumers at the coast, as evidenced for archaeological animals from the Viking Haithabu and the early medieval Schleswig sites located close to the Baltic Sea. This result demonstrates the potential of greenhouse experiments as an isotopic predictor of the past local sea spray effect.
Dual clumped isotope thermometry of coral carbonate
2022, Geochimica et Cosmochimica Acta
The stable (δ¹⁸O and δ¹³C) and clumped (Δ₄₇) isotope compositions of coral carbonate are valuable archives for paleoclimate reconstructions. However, the Δ₄₇-temperature relationships of warm and cold-water corals deviate from that of inorganic carbonate precipitated at equilibrium. Dual clumped isotope thermometry of carbonates (i.e., simultaneous Δ₄₇ and Δ₄₈ measurements on a single carbonate) has the potential to achieve more accurate paleotemperature reconstruction, identifying and correcting for kinetically driven isotopic disequilibrium. Here we present the first extensive dual clumped isotope dataset of coral carbonate, spanning a broad range of cold and warm-water coral species. We confirm that corals are enriched in Δ₄₇ and depleted in Δ₄₈ relative to equilibrium, a pattern corresponding to the mixing of an equilibrium DIC pool with kinetically derived HCO₃^– produced by hydration and hydroxylation of CO₂. Dual clumped isotope measurements of cold-water corals fall on the initial linear portion of model (IsoDIC) predicted departure from equilibrium. The dual clumped isotope composition of cold-water corals, corrected by the model-predicted Δ₄₇/Δ₄₈ offset slope (−0.78), yield accurate reconstruction of coral growth temperature with a precision of <3 °C at the 68% confidence level. In contrast, disequilibrium offsets in the Δ₄₇ and Δ₄₈ of warm-water corals correspond to precipitation from a more equilibrated DIC pool, which we attribute to the action of carbonic anhydrase in the calcifying fluid. It may be possible to correct warm-water coral growth temperatures, using an empirically derived correction (Δ₄₇/ Δ₄₈ offset slope of −0.4). Dual clumped isotope thermometry of coral carbonate opens new possibilities to reconstruct both sea surface temperatures and ocean dynamics of intermediate to deep water masses.
Oxygen isotopes of calcite precipitated at high ionic strength: CaCO<inf>3</inf>-DIC fractionation and carbonic anhydrase inhibition
2022, Geochimica et Cosmochimica Acta
Background electrolytes affect calcite precipitation and dissolution rates and hence have the potential to impact kinetic isotope fractionation between calcite and the dissolved inorganic carbon (DIC) species. We grew inorganic calcite from NaCl-CaCl₂ solutions (T = 25 °C, pH = 8.3, and crystal growth rate = 10^{−6.3 ± 0.3} mol m⁻² s⁻¹) to test for potential ionic strength effects on the oxygen isotope fractionation between calcite and an isotopically equilibrated inorganic carbon pool (α_c/EIC). Calcite was grown in the presence of the enzyme carbonic anhydrase from bovine erythrocytes (bCA) to promote isotopic equilibration of the DIC pool.
No evidence of an ionic strength effect on α_c/EIC was found for NaCl concentrations up to 0.35 M (1000lnα_c/w = 28.0 ± 0.1; n = 7). For experiments conducted with [NaCl] > 0.35 M, the DIC pool could not be maintained in isotopic equilibrium with water due to the inhibitory effect of NaCl on bCA. The use of other types of CA may be required to maintain isotopic equilibration of DIC in solution with ionic strength close to or above that of seawater.
The oxygen isotope results were modeled successfully with an isotopic box model for a CO₂-fed solution that tracks the isotopic composition of each DIC species and CaCO₃. The experimental and modeling results suggest that the efficacy of bCA decreases exponentially with increasing [NaCl]. We quantify the salt effect on the quantity k_cat/K_M, which relates the catalyzed rate constant for CO₂ hydration to the concentration of bCA. The salt effect can be implemented in models of biomineralization with potential to extend our knowledge of oxygen isotope vital effects in marine organisms.
Isotopic fractionation accompanying CO<inf>2</inf> hydroxylation and carbonate precipitation from high pH waters at The Cedars, California, USA
2021, Geochimica et Cosmochimica Acta
Citation Excerpt :
Chen et al (2018) developed a model for oxygen and carbon isotopes that integrates reaction kinetics of the DIC species, carbonate precipitation and fluid mixing - a combination that is necessary to understand alkaline springs like those at The Cedars. This model is informed by extensive experimental and theoretical work on the kinetics and isotope fractionations among DIC species (e.g. Usdowski et al., 1991; Clark et al., 1992; Usdowski and Hoefs, 1993; Zeebe and Wolf-Gladrow, 2001; Beck et al., 2005; Kim et al., 2006; Zeebe, 2014; Sade and Halevy, 2017, 2018) and carbonate minerals (Romanek et al., 1992; Kim et al., 2007; Wolthers et al., 2012; Watkins et al., 2013, 2014). In this section, we present a model adapted from that of Chen et al. (2018), with addition of diffusive effects at the atmosphere-water interface and use it to evaluate the observed C and O isotope variations, while also using the constraints we have on carbonate growth rates and Ca isotope compositions.
The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO₂ and at times via mixing with surface water. These processes lead to distinct carbonate morphologies with “floes” forming at the atmosphere-water interface, “snow” of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO₃ precipitation occurring in waters with low Mg/Ca (<0.01). Precipitation of aragonite is likely promoted by the high pH (11.5–12.0) of pool waters, in agreement with published experiments illustrating the effect of pH on calcium carbonate polymorph selection.
The calcium carbonates exhibit an extreme range and approximately 1:1 covariation in δ¹³C (−9 to −28‰ VPDB) and δ¹⁸O (0 to −20‰ VPDB) that is characteristic of travertine formed in high pH waters. The large isotopic fractionations have previously been attributed to kinetic isotope effects accompanying CO₂ hydroxylation but the controls on the δ¹³C-δ¹⁸O endmembers and slope have not been fully resolved, limiting the use of travertine as a paleoenvironmental archive. The limited areal extent of the springs (∼0.5 km²) and the limited range of water sources and temperatures, combined with our sampling strategy, allow us to place tight constraints on the processes involved in generating the systematic C and O isotope variations.
We develop an isotopic reaction–diffusion model and an isotopic box model for a CO₂-fed solution that tracks the isotopic composition of each dissolved inorganic carbon (DIC) species and CaCO₃. The box model includes four sources or sinks of DIC (atmospheric CO₂, high pH spring water, fresh creek water, and CaCO₃ precipitation). Model parameters are informed by new floe Δ⁴⁴Ca data (−0.75 ± 0.07‰), direct mineral growth rate measurements (4.8 to 8 × 10⁻⁷ mol/m²/s) and by previously published elemental and isotopic data of local water and DIC sources. Model results suggest two processes control the extremes of the array: (1) the isotopically light end member is controlled by the isotopic composition of atmospheric CO₂ and the kinetic isotope fractionation factor (KFF (‰) = (α − 1) × 1000) accompanying CO₂ hydroxylation, estimated here to be −17.1 ± 0.8‰ (vs. CO_2(aq)) for carbon and −7.1 ± 1.1‰ (vs. ‘CO_2(aq) + H₂O’) for oxygen at 17.4 ± 1.0 °C. Combining our results with revised CO₂ hydroxylation KFF values based on previous work suggests consistent KFF values of −17.0 ± 0.3‰ (vs. CO_2(aq)) for carbon and −6.8 ± 0.8‰ for oxygen (vs. ‘CO_2(aq) + H₂O’) over the 17–28 °C temperature range. (2) The isotopically heavy endmember of calcium carbonates at The Cedars reflects the composition of isotopically equilibrated DIC from creek or surface water (mostly $HC O_{3}^{-}$ , pH = 7.8–8.7) that occasionally mixes with the high-pH spring water. The bulk carbonate δ¹³C and δ¹⁸O values of modern and ancient travertines therefore reflect the proportion of calcium carbonate formed by processes (1) and (2), with process (2) dominating the carbonate precipitation budget at The Cedars. These results show that recent advances in understanding kinetic isotope effects allow us to model complicated but common natural processes, and suggest ancient travertine may be used to retrieve past meteoric water δ¹⁸O and atmospheric δ¹³C values. There is evidence that older travertine at The Cedars recorded atmospheric δ¹³C that predates large-scale combustion of fossil fuels.
Implications of new mineral phases in the isotopic composition of Roman lime mortars at the Kom el-Dikka archaeological site in Egypt
2021, Construction and Building Materials
Over time, the carbonated components of lime-based mortars dissolve and recrystallise, inducing calcite cementation in the resulting micro- cracks and pores, favouring self-healing capacity. In such types of mortars, the binder may originally contain gypsum, or, on the other hand, dissolution and precipitation processes of compounds from different sources (soil, construction materials or airborne particles) may derive in the formation of new saline minerals. The uptake of such components may interfere with chemical and physical analysis, hindering the interpretation of the data needed to determine the identification, provenance of raw materials, formulation, and production processes of mortars, carried out in archaeometric investigations.
This article discusses the presence of such mineral phases in the mortars sampled at the Kom el-Dikka archaeological site located in Alexandria, Egypt, and their effect on the findings. A multi-technique approach was undertaken to characterize the ancient mortars and determine their behaviour and evolution, by using the following analytical techniques; polarised optical microscopy (POM), scanning electron microscopy (SEM–EDS), X-ray diffraction (XRD), thermogravimetry (TG), X-ray fluorescence (XRF) and ion chromatography (IC). The results achieved through archaeometric and geochemical investigations show the presence of different mortars at the Kom el-Dikka site. Also, petrological techniques successfully explain the variation in isotopic composition (¹³C and ¹⁸O) patterns mediated by the presence of the saline and carbonate phases.

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Geochimica et Cosmochimica Acta

Abstract

References (14)

The geochemistry of some carbonate ground water in central Pennsylvania

Geochim. Cosmochim. Acta

Carbonate-water isotopic temperature scale

Bull. GSA

Revised carbonate-water isotopic temperature scale

Bull. GSA

The ionization constant of carbonic acid in water and the solubility of carbon dioxide in water and aqueous salt solutions from 0 to 50°C

J. Amer. Chem. Soc.

The Physical Chemistry of Electrolyte Solutions

The ionization constant of HCO⁻₃ from 0 to 50°C

J. Amer. Chem. Soc.

On the isotopic chemistry of carbonates and a paleotemperature scale

J. Chem. Phys.

Cited by (96)

Multi-isotope fingerprints of recent environmental samples from the Baltic coast and their implications for bioarchaeological studies

Identification and quantification of the sea spray effect on isotopic systems in α-cellulose (δ<sup>13</sup>C, δ<sup>18</sup>O), total sulfur (δ<sup>34</sup>S), and <sup>87</sup>Sr/<sup>86</sup>Sr of European beach grass (Ammophila arenaria, L.) in a greenhouse experiment

Dual clumped isotope thermometry of coral carbonate

Oxygen isotopes of calcite precipitated at high ionic strength: CaCO<inf>3</inf>-DIC fractionation and carbonic anhydrase inhibition

Isotopic fractionation accompanying CO<inf>2</inf> hydroxylation and carbonate precipitation from high pH waters at The Cedars, California, USA

Implications of new mineral phases in the isotopic composition of Roman lime mortars at the Kom el-Dikka archaeological site in Egypt

LetterOxygen isotope exchange between carbonic acid, bicarbonate, carbonate, and water: A re-examination of the data of McCrea (1950) and an expression for the overall partitioning of oxygen isotopes between the carbonate species and water

Abstract

Geochim. Cosmochim. Acta

Carbonate-water isotopic temperature scale

Bull. GSA

Revised carbonate-water isotopic temperature scale

Bull. GSA

The ionization constant of carbonic acid in water and the solubility of carbon dioxide in water and aqueous salt solutions from 0 to 50°C

J. Amer. Chem. Soc.

The Physical Chemistry of Electrolyte Solutions

The ionization constant of HCO−3 from 0 to 50°C

J. Amer. Chem. Soc.

On the isotopic chemistry of carbonates and a paleotemperature scale

J. Chem. Phys.

Letter
Oxygen isotope exchange between carbonic acid, bicarbonate, carbonate, and water: A re-examination of the data of McCrea (1950) and an expression for the overall partitioning of oxygen isotopes between the carbonate species and water

The ionization constant of HCO⁻₃ from 0 to 50°C