3.4.1. Oxygen Isotope Fractionation between Different Carbonate Minerals
The study of oxygen isotopes between carbonate minerals has always been the focus of researchers [
32]. Carbonate minerals are the most common minerals in nature. The scientific consensus is that two associated carbonate minerals are a good system for measuring geological temperature [
33,
34]. The basis of a geothermometer is to accurately obtain the equilibrium isotope fractionation factors between two associated minerals. Unfortunately, until now, there has been no consensus on the magnitude of equilibrium isotope fractionation factors between carbonate minerals [
34]. In this part, the dolomite-calcite system is selected as an example to illustrate the oxygen isotope effect between carbonate minerals. The data of oxygen isotope fractionation between other carbonate minerals can also be obtained in sequence according to this method.
Figure 7 shows the comparison of our calculation results with previous theoretical and experimental results.
Figure 7 makes it clear that the differences between all theoretical and experimental results (including those not listed) are considerable. In particular, the differences between the four different theoretical calculations are even more obvious [
4,
8,
21]. Compared with other theoretical calculation results, the results of this study are in better agreement with the experimental values, especially when the temperature exceeds 100 °C. There are a lot of experimental studies on oxygen isotope fractionation among carbonate minerals, such as the works of Northrop and Clayton, Clayton et al., and the relevant data reported in Chacko and Deines’s work, etc. [
8,
35,
36]. Those who are interested can refer to the relevant data. Sheppard and Schwarcz investigated the fractionation of oxygen isotopes in coexisting metamorphic calcite and dolomite by measuring natural samples [
37]. Their experimental results show that the oxygen isotope fractionation factor between dolomite and calcite has a temperature function relationship of
(
) in the temperature range of 100–600 °C. Matthews and Katz experimentally studied the oxygen isotope fractionation during the dolomitization of calcium carbonate at 252, 265, 274, 285, and 295 °C [
32]. Although their experimental data were limited (only five data points), they were able to illustrate the oxygen isotope fractionation characteristics of the two carbonate minerals at temperatures ranging from 252 to 295 °C (see
Figure 7). Our theoretical calculation results are slightly greater than their experimental results and better than other theoretical results reported by predecessors. This difference may result from their choice of experimental method, especially the choice of experimental solution concentrations and the Mg/Ca ratio. In the experiment of Matthews and Katz, an Mg/Ca ratio of 0.26 was selected, and increasing or decreasing Mg/Ca ratios may affect the final determination of oxygen isotope fractionation between carbonate minerals [
32].
Zheng systematically calculated the oxygen isotope fractionation factors of carbonate minerals and sulfate minerals by an increment method [
4]. As can be seen from
Figure 7, the research results of Zheng are significantly different from the results of this study, Schauble et al. and Chacko and Deines [
4,
8,
21]. The increment method has been proved by many studies to be unsuitable for the study of various solid mineral systems [
8,
22]. Chacko and Deines’s work give a range that is determined by different Mg/(Mg + Ca) ratios. Those who are interested can see
Figure 7 in this article for more details [
8].
3.4.2. Oxygen Isotope Fractionation Factors between Carbonate Minerals and Aqueous Solutions
The oxygen isotope fractionation factors between carbonate minerals and different aqueous solutions were systematically studied. Taking an H
2CO
3 aqueous solution as an example, in the theoretical calculation, its gas phase molecular form is H
2CO
3(g), while the aqueous solution species is H
2CO
3·nH
2O (in this study H
2CO
3·30H
2O was used). The purpose of this operation is to investigate the contribution of these different species to the oxygen isotope effects of carbonate dissolution and precipitation on a molecular basis. For the sake of discussion, oxygen isotope fractionation factors between three carbonate minerals (calcite, aragonite, and dolomite) and aqueous solutions are used as research objects. The oxygen isotope fractionation effect between other carbonate minerals and aqueous solutions can also be obtained through the same treatment process. As shown in
Figure 8, the abilities of aqueous solutions to enrich heavy oxygen isotope (
18O), with respect to the three carbonate minerals, were different. The overall change trend of oxygen isotope fractionation factors for these three systems was dolomite-aqueous solutions > calcite-aqueous solutions > aragonite-aqueous solutions (
Figure 8A). This change order is consistent with the RPFRs of dolomite, calcite, and aragonite. In terms of oxygen isotope fractionation factors between carbonate minerals and CO
32− solutions, these three minerals were more enriched with
18O than the CO
32− solution. Among them, dolomite had the strongest ability to enrich heavy oxygen isotopes (
18O). Taking the equilibrium oxygen isotope fractionation factors at 25 °C as an example, the 1000lnα
s for systems of dolomite-CO
32− solution, calcite-CO
32− solution, and aragonite-CO
32− solution were 9.43, 5.79, and 2.90, respectively. The experimental results and published isotope fractionation data demonstrated that CO
32− contributed significantly to the equilibrium oxygen isotope fractionation factors of carbonate minerals [
38]. Devriendt et al.’s results show that
(C stands for CaCO
3) is 1.00542 at the temperature of 33.7 °C [
11]. If you convert that to 1000lnα, it is equal to 5.42. This value is close to the oxygen isotope fractionation factor of a calcite-CO
32− solution (5.79) but is quite different from the dolomite-CO
32− solution (9.43) and aragonite-CO
32− solution (2.90) systems. Therefore, it is essential to accurately determine the species of carbonate when calculating the oxygen isotope fractionation factor between carbonate and CO
32− solutions. See
Table 4 for the oxygen isotope fractionation factors at other temperatures.
Bicarbonate ions (HCO
3−) also play an important role in the water–rock interaction between carbonate minerals and water. In the process of water–rock interactions, HCO
3− plays a crucial role as the controlling factor that determines the species balance of an aqueous solution [
38]. The concentration of HCO
3− in aqueous solutions is controlled by multiple factors, such as pH, temperature, salinity, etc. [
11]. When the pH value of the solution is low, or the concentration of carbon dioxide (CO
2) in the surrounding atmosphere is high, the water–rock interaction process will move in the direction of the formation of HCO
3−, that is, the dissolution of carbonate minerals will occur. Compared with the aqueous solution of HCO
3−, the three carbonate minerals differed greatly in their ability to enrich heavy oxygen isotopes (
18O). Dolomite was more enriched with
18O than the HCO
3− solution, while for calcite and aragonite, the HCO
3− solution was more enriched with
18O (
Figure 8B). Similarly, the oxygen isotope fractionation factors of the dolomite-HCO
3− solution, calcite-HCO
3- solution, and aragonite-HCO
3− solution at 25 °C were 2.99, −0.63, and −3.53, respectively. Devriendt et al. conducted a systematic experimental study on the oxygen isotope fractionation of the CaCO
3-DIC-H
2O system [
11]. Their work found that the oxygen isotope fractionation factor between carbonate-HCO
3− solutions is kinetically controlled. When considering equilibrium oxygen isotope fractionation, among the three carbonate minerals aragonite is the most depleted in
18O compared to HCO
3− solutions. The oxygen isotope fractionation factors of these three systems under other temperature conditions can also be obtained from
Table 4.
Calcium carbonate (CaCO
3) is in an aqueous solution, usually in the form of precipitation [
29,
39,
40]. It is well known that calcium carbonate is insoluble in water, but it also has a solubility product constant Ksp, that is, the precipitation equilibrium constant, although this value is very small. When precipitation reaches the equilibrium state of precipitation-dissolution in solution, the concentration of each ion remains unchanged, and the product of the power of the ion concentration is a constant, which is called the solubility product constant. Although the solubility of calcium carbonate in aqueous solution is very low, the oxygen isotope fractionation factors between a calcium carbonate solution and minerals are systematically studied. The three carbonate minerals also differ in their ability to enrich
18O relative to CaCO
3 solutions (
Figure 8C). Dolomite and calcite are more enriched in heavy oxygen isotopes than CaCO
3 solutions, while aragonite is depleted in heavy oxygen isotopes compared with CaCO
3 solutions. At 25 °C, the oxygen isotope fractionation factors of dolomite-CaCO
3 solution, calcite-CaCO
3 solution, and aragonite-CaCO
3 solution are 5.36, 1.72, and −1.16, respectively. Oxygen isotope fractionation factors at other temperatures are also given in detail in
Table 4.
Carbonic acid (H
2CO
3) is a binary weak acid with the formula H
2CO
3 and has a relatively small ionization constant. Therefore, in the natural water body (seawater, surface water, or groundwater), there will also be an H
2CO
3 aqueous solution in the form of H
2CO
3 molecules. The existence of an H
2CO
3 solution has a crucial effect on the balance of the CO
2 concentration [
11] between water and the atmosphere, and the concentration of HCO
3− in an aqueous solution. Its existence, in fact, plays the role of a buffer. In turn, it will affect the water–rock interaction between the carbonate minerals and water. Compared with other aqueous solutions, an H
2CO
3 aqueous solution has a stronger ability to enrich heavy oxygen isotopes (
Figure 8D). Dolomite, calcite, and aragonite are all depleted heavy oxygen isotopes relative to the H
2CO
3 aqueous solution. At 25 °C, the oxygen isotope fractionation factors of the dolomite-H
2CO
3 solution, calcite-H
2CO
3 solution, and aragonite-H
2CO
3 solution are −9.56, −13.19, and −16.09 respectively. In this chemical reaction process, the phenomenon of heavy oxygen isotope loss of solid minerals, relative to a carbonic acid aqueous solution, is very obvious. Even at higher temperatures, such as 500 °C, the oxygen isotope fractionation factors can still reach −3.68, −4.29, and −4.63. Please refer to
Table 4 for oxygen isotope fractionation factors at other temperatures.
3.4.3. Oxygen Isotope Fractionation between Aqueous Solutions and Gas Phases
The oxygen isotope fractionation factors between aqueous solutions (such as CO
32− solutions, Ca(HCO
3)
2 solutions, CaCO
3 solutions, and H
2CO
3 solutions) and oxygen-bearing gas phases (CO
2(g), CO(g), O
2(g), and H
2O(g)) were systematically studied. The oxygen isotope fractionation factors between aqueous solutions and gas phases as a function of temperature are shown in
Figure 9. The results showed that, in most cases, the CO
2(g) had a stronger ability to enrich heavy oxygen isotoped (
18O) than aqueous solutions. Only under low-temperature conditions (0–50 °C) should the H
2CO
3 solution be slightly enriched with heavy oxygen isotopes (
18O) (
Figure 9A). At about 50 °C, the enrichment sequence of heavy oxygen isotopes (
18O) for the oxygen isotope fractionation factors between H
2CO
3 aqueous solutions and CO
2 was reversed. At 25 °C, the oxygen isotope fractionation factors of the H
2CO
3 solution-CO
2(g), CO
32− solution-CO
2(g), Ca(HCO
3)
2 solution-CO
2(g), and aqueous CaCO
3 solution-CO
2(g) were 0.77, −18.21, −11.77 and −14.14, respectively. With the exception of the H
2CO
3 solution, the CO
32− solution, Ca(HCO
3)
2 solution, and aqueous CaCO
3 solution have a significant depletion of heavy oxygen isotopes (
18O) relative to CO
2(g). These depletions are still very obvious even at higher temperature conditions, such as 500 °C; this series of values can still reach −2.16, −7.63, −6.08, and −6.80 (‰) (See
Table 5). Another conclusion can be drawn from
Figure 9A, that is, the oxygen isotope fractionation factors between aqueous solution species and CO
2(g) did not completely decrease gradually with the decrease in temperature. In general, except for the CO
32− solution-CO
2(g) system, oxygen isotope fractionation factors decreased first and then increased with the increase in temperature. It is just that the temperature conditions that changed were different for different systems. Oxygen isotope fractionation factors between aqueous solutions and CO
2(g) at other temperatures can be obtained from
Table 5.
For oxygen isotope fractionation factors between aqueous solutions and H
2O(g), the content of H
2O(g) in the atmosphere is relatively small, but most of the H
2O(g) exists in the troposphere, and the relationship between the surface layers is very close. Almost all weather events in the troposphere are related to H
2O(g). The oxygen isotope fractionation between the carbonic acid aqueous solution systems and H
2O(g) is shown in
Figure 9B. The H
2CO
3 solution, Ca(HCO
3)
2 solution, CaCO
3 solution, and CO
32− solution were all more enriched with heavy oxygen isotopes (
18O) than H
2O(g). Among them, the H
2CO
3 solution had the strongest ability to enrich heavy oxygen isotopes relative to H
2O(g). At 25 °C, the oxygen isotope fractionation factors between the H
2CO
3 solution, Ca(HCO
3)
2 solution, CaCO
3 solution, CO
32− solution, and H
2O(g) were 50.77, 38.22, 35.85, and 31.78, respectively. Data for oxygen isotope fractionation at other temperatures are shown in
Table 5. The oxygen isotope fractionation factors of all systems decreased linearly with the increase in temperature.
Carbon monoxide and oxygen are also important oxygen carriers in the atmosphere. Oxygen isotope fractionation between aqueous solutions and these two gases has also been studied in detail. The relationship between the fractionation factors and temperature is shown in
Figure 9C,D. The oxygen isotope fractionation factor between aqueous solutions and O
2(g) decreased gradually with the increase in temperature. The isotope fractionation factor between H
2CO
3 solution and oxygen was the largest one. At 25 °C, The oxygen isotope fractionation factors of the H
2CO
3 solution-O
2(g), CO
32− solution-O
2(g), Ca(HCO
3)
2 solution-O
2(g), and CaCO
3 solution-O
2(g) were 32.74, 13.75, 20.18 and 17.81, respectively. The uniform pattern of change was that aqueous solutions were more enriched with heavy isotopes than O
2(g). The oxygen isotope fractionation between the solutions and CO
2(g) did not show a consistent decrease with the increase in temperature but would reverse when the temperature rises to a certain value. Compared with CO
2(g), except for the H
2CO
3 solution which is more enriched with heavy isotope, the other solutions showed different degrees of heavy oxygen isotope depletion.
3.4.4. Oxygen Isotope Fractionation between Aqueous Solutions
In the aqueous carbonate system, the isotope exchange reactions are shown in Formula (3). When constructing the molecular clusters and calculating the harmonic vibration frequencies, only one oxygen atom exchange reaction is considered. The oxygen isotope exchange reaction between the Ca(HCO
3)
2 solution and the CO
32− solution occurs with the exchange of only one oxygen atom, as shown in the Formula (3). There have been many previous experimental studies on carbonic acid systems, such as Beck’s work [
7]. In the work of Beck, oxygen isotope fractionation in the carbonic acid system at 15, 25, and 40 °C was systematically studied [
7]. In the work of McCrea, the temperature variation of oxygen fractionation in the exchange reactions between dissolved carbonate and water and between calcite and water was investigated theoretically and experimentally [
19]. At 25 °C, the oxygen isotope fractionation factor between the Ca(HCO
3)
2 solution and the CO
32− solution was 6.43 (
Table 6), and the results obtained by recalculating Beck et al. and McCrea were 6.81 and 6.28 [
7,
19], respectively. The data obtained in this study are in good agreement with the previous studies. For the oxygen isotope fractionation factors between the H
2CO
3 solution and the CO
32− solution, and between the H
2CO
3 solution and the Ca(HCO
3)
2 solution, the results of this study were 18.99 and 12.55, respectively. The work by Beck et al. showed corresponding figures of 16.30 and 9.49, respectively. Our calculations were larger than the data from Beck et al. [
7]. The reason for this gap may be that we use the structure H
2CO
3 when calculating the carbonic H
2CO
3 solution, while in the laboratory, they use CO
2 (aq). CO
2 is easily soluble in water, and the real existence structure should be in the form of H
2CO
3 and CO
2 molecules. This work showed that the H
2CO
3 solution had the highest ability to enrich
18O among all solutions (
Figure 10).