Equilibrium Oxygen Isotope Fractionation Research Articles

Authigenic quartz reveals the triple oxygen isotope composition and diagenetic temperature of saline brines

Triple oxygen isotope compositions of authigenic minerals are an emerging tool for the reconstruction of fluid temperatures and the fluid isotopic composition. In this study, we analyzed euhedral authigenic quartz crystals from a halite deposit of the Upper Permian Zechstein evaporitic basin for their triple oxygen isotope composition using laser fluorination isotope ratio mass spectrometry. In the triple oxygen isotope space, additional information, such as the triple oxygen isotope composition of the ambient water, provides insights into equilibrium conditions during quartz formation that cannot be identified from δ18O alone. The triple oxygen isotope composition of authigenic quartz shows, that single oxygen isotope (δ18O) thermometry is not applicable for samples from evaporitic environments, where the fluids' δ18O deviates from dynamic oxygen isotope equilibrium. By combining the Craig and Gordon evaporation model with H2O – SiO2 triple oxygen isotope equilibrium fractionation, we reconstruct the formation temperature of authigenic quartz and the triple oxygen isotope composition of the marine-derived saline brine pore fluid in equilibrium with the quartz. We obtain temperatures of 90 to 130 °C that is interpreted as crystallization temperatures of microcrystalline quartz in pore fluid of halite during burial diagenesis. The triple oxygen isotope composition of authigenic quartz from evaporitic environments is suited as a geochemical tracer for fluid oxygen isotope compositions and ancient fluid or diagenetic temperatures.

Oxygen Isotope Fractionation between Carbonate Minerals and Carbonic Acid Systems and Constraints for Environmental Science and Geological Processes

The equilibrium oxygen isotope fractionation factor is widely used in geological thermometry. However, under most natural conditions, the oxygen isotope exchange is rare to reach equilibrium. Especially for the complex water–rock interaction process, the contribution of the H2CO3 solution, CO32− solution, Ca(HCO3)2 solution, and CaCO3 solution to the equilibrium oxygen isotope fractionation factor of this process is poorly understood. In view of this predicament, these key parameters are obtained by ab initio calculations. The results showed that the contributions of different carbonate minerals and different aqueous solutions to the equilibrium oxygen isotope fractionation factor were different. Among all nine carbonate minerals (dolomite, calcite, aragonite, magnesite, siderite, otavite, smithsonite, ankerite, and strontianite), the minerals with the highest and lowest reduced partition function ratios (RPFR) were siderite and strontianite, respectively. At the same time, the RPFR of nitratine, which has the same structure as carbonate, was studied. The RPFRs of the three most widely distributed carbonates in nature (dolomite, calcite, and aragonite) were dolomite > calcite > aragonite. Among the H2CO3 solution, CO32− solution, Ca(HCO3)2 solution, and CaCO3 solution, the H2CO3 solution had the strongest ability to enrich 18O. In addition, the equilibrium oxygen isotope fractionation factors between aqueous solutions and gas phase species (CO2(g), H2O(g), and O2(g), etc.) were calculated systematically. The results showed that the oxygen isotope fractionation factors between solutions and gas phases were often inconsistent with the temperature change direction and that the kinetic effects played a key role. These theoretical parameters obtained in this study will provide key equilibrium oxygen isotope constraints for water-rock interaction processes.

Density functional theory calculations of equilibrium oxygen isotope fractionation between borate minerals and aqueous fluids

Density functional theory calculations of equilibrium oxygen isotope fractionation between borate minerals and aqueous fluids

碳酸物种和氯离子对生物磷灰石磷酸钙成核的影响

Apatite is the principal inorganic component of biological hard tissues such as bone and teeth, and thus is essential to the existence of vertebrate life. Because carbonate species and chloride ions are ubiquitous in the fluids of vertebrate life forms, and these species are known to compete with phosphate species, it is critical to understand the influence of these anions on the nucleation of biological apatite. In this study, the important roles of carbonate and chloride ions in mediating inorganic calcium phosphate (CaP) phase nucleation are revealed both theoretically and experimentally. Theoretical investigations suggest that the Ca-O coordination number is an important descriptor for the nucleation of CaP and the interface interaction of the CaP-additive. Positive surface charges on the outermost Ca2+ ions of CaP clusters could attract carbonate species and Cl− ions, promoting the formation of CaP phase. In the presence of carbonate species and Cl− ions, the crystallization of hydroxyapatite (HA) from its precursor brushite (DCPD) has been observed in our experimental studies. The Cl− ion-doped B-type HA is proposed to be the most likely biological apatite based on equilibrium oxygen isotope fractionation and vibrational spectroscopic analysis. The insight gained here may help rationalize the control of biomineralization, and will guide the synthesis of anion-doped biological functional apatite materials.

Equilibrium hydrogen isotope fractionation between portlandite/brucite and water: Implication from the vibrational spectra at elevated temperature and pressure

Minerals in brucite-type structure, including brucite (Mg(OH)2) and portlandite (Ca(OH)2), have been studied as important analogs of hydrous silicate minerals for their thermodynamic properties, including equilibrium hydrogen and oxygen isotope fractionations between minerals and water at elevated temperatures and pressures. In this study, Raman and Fourier transform infrared (FTIR) spectra were collected at high-temperature (T) and high-pressure (P) conditions on synthetic hydrogenated and deuterated portlandite samples (i.e., Ca(OH)2 and Ca(OD)2), and their isobaric and isothermal mode Grüneisen parameters, as well as anharmonic parameters, were then evaluated. These high-precision vibrational spectra enable the evaluation of thermodynamic properties of portlandite (ΔU, CV, CP and ΔS) up to 427 °C, to which anharmonicity has positive contributions. More importantly, they help to determine the isobaric (at P = 1 bar) β factors of brucite and portlandite for equilibrium D/H fractionation considering anharmonic effects, and the D/H fractionation factor (103∙lnα) between brucite/portlandite and water at high-P,T conditions. The calculated equilibrium fractionation factor (lnαbrucite-water) agrees with experimental results in the temperature range from 300 to 647 K (∼27 to ∼374 °C, the critical point of water) within analytical uncertainties estimated using Monte Carlo method. The Ab initio calculation using DFT theory and VASP program was also carried out to obtain phonon spectra for brucite and portlandite with three-split hydrogen sites and to evaluate the dispersion effect, which is found to be smaller than the statistical uncertainty at high temperatures. Our results show that the internal OH-stretching modes in brucite/portlandite play a dominant role in determining the β values, and the anharmonic OH-stretching potential (xi parameter) contributes significantly to the D/H fractionation factor. Because previous studies show that OH-stretching frequencies generally decrease with increasing mass of cation in the metallic hydroxide having similar crystal structure, our results imply that the deuterium isotope may be preferentially enriched in the hydroxide phase with the light cation bonded to the hydroxyl group, which is also consistent with the observed D/H fractionations among hydrous silicates.

Theoretical estimates of sulfoxyanion triple-oxygen equilibrium isotope effects and their implications

Triple-oxygen isotope (δ18O and Δ′17O) analysis of sulfate is becoming a common tool to assess several biotic and abiotic sulfur-cycle processes, both today and in the geologic past. Multi-step sulfur redox reactions often involve intermediate sulfoxyanions such as sulfite, sulfoxylate, and thiosulfate, which may rapidly exchange oxygen atoms with surrounding water. Process-based reconstructions therefore require knowledge of equilibrium oxygen-isotope fractionation factors (18α and 17α) between water and each individual sulfoxyanion. Despite this importance, there currently exist only limited experimental 18α data and no 17α estimates due to the difficulty of isolating and analyzing short-lived intermediate species. To address this, we theoretically estimate 18α and 17α for a suite of sulfoxyanions—including several sulfate, sulfite, sulfoxylate, and thiosulfate species—using quantum computational chemistry. We determine fractionation factors for sulfoxyanion “water droplets” using the B3LYP/6-31G+(d,p) method; we additionally calculate higher-order method (CCSD/aug-cc-pVTZ and MP2/aug-cc-pVTZ) scaling factors, and we qualitatively estimate the importance of anharmonic zero-point energy (ZPE) corrections using a suite of gaseous sulfoxy compounds. Methodological scaling factors greatly impact 18α predictions, whereas ZPE corrections are likely small (i.e., ⩽1‰) at Earth-surface temperatures; existing experimental data best agree with 18α predictions when including redox state-specific CCSD/aug-cc-pVTZ scaling factors. Theoretical pH- and temperature-specific bulk-solution (i.e., abundance-weighted average of all species) 18α values yield root-mean-square errors for sulfate/water, sulfite/water, and thiosulfate/water equilibrium of 4.5‰ (n=18 experimental conditions), 3.7‰ (n=27), and 2.2‰ (n=3), respectively. However, sulfate- and sulfite-system agreement improves considerably when comparing experimental results only to SO3(OH)−/H2O (RMSE = 1.6‰) and SO2(OH)−/H2O (RMSE = 2.2‰) predictions, rather than bulk solutions. This is particularly true for the sulfite system at high and low pH, when SO2(OH)− is not the dominant species. We discuss potential experimental and theoretical biases that may lead to this apparent improvement. By combining 18α and 17α predictions, we additionally estimate that sulfate, sulfite, sulfoxylate, and thiosulfate species can exhibit Δ′17O values as much as 0.199‰, 0.205‰, 0.101‰, and 0.186‰ more negative than equilibrated water at Earth-surface temperatures (reference line slope = 0.5305). This theoretical framework provides a foundation to interpret experimental and observational triple-oxygen isotope results of several sulfur-cycle processes including pyrite oxidation, microbial metabolisms (e.g., sulfate reduction, thiosulfate disproportionation), and hydrothermal anhydrite precipitation. We highlight this with several examples.

Cassiterite oxygen isotopes in magmatic-hydrothermal systems: in situ microanalysis, fractionation factor, and applications

Tin and tungsten are important metals for the industrializing society. Deciphering the origin and evolution of hydrothermal fluids responsible for their formation is critical to underpin genetic models of ore formation. Traditional approaches obtain isotopic information mainly from bulk analysis of both ore and gangue minerals, or less frequently from in situ analysis of gangue minerals, which either bear inherited complexities and uncertainties or are indirect constraints. Hence, directly obtaining isotopic information from ore minerals such as cassiterite by in situ techniques is warranted. However, this has been hampered by challenges from both analytical and applicational aspects. In this study, we first demonstrate a lack of crystallographic orientation effects during cassiterite ion microprobe oxygen isotope analysis. Along with our newly developed matrix-matched reference material, the Yongde-Cst, which has a recommended δ18O value of 1.36 ± 0.16‰ (VSMOW) as defined by gas source isotope ratio mass spectrometry, in situ oxygen isotope analysis of cassiterite now is possible. We further refine the oxygen isotope fractionation (1000 ln α) for quartz-cassiterite by first-principles calculations, which is given by the equation of 1.259 × 106/T2 + 8.15 × 103/T − 4.72 (T is temperature in Kelvin). The 1000 ln α for quartz-cassiterite has a sensitive response to temperature, and makes cassiterite-quartz an excellent mineral pair in oxygen isotope thermometry, as described by the equation of T (℃) = 2427 × (δ18Oqtz − δ18Ocst)−0.4326 − 492.4. Using the well-established 1000 ln α of quartz-water, 1000 ln α of cassiterite-water is derived as 2.941 × 106/T2 − 11.45 × 103/T + 4.72 (T in Kelvin), which shows a weak response to temperature. This makes cassiterite an ideal mineral from which to derive δ18O of fluids as robust temperature estimates are no longer a prerequisite. We have applied oxygen isotope analysis to cassiterite samples from six Sn(-W) deposits in China. The results show considerable variability in δ18O values both within a single deposit and among studied deposits. Combining the δ18O of cassiterite samples and the equilibrium oxygen isotope fractionation, we find that the δ18O values of ore-forming fluids show a strong magmatic affinity with variable but mostly no to low degree involvements (~0-10%) of meteoric water, hence our results invite a reassessment on the extent and role of meteoric water in Sn-W mineralization. This study demonstrates that in situ oxygen isotope analysis of cassiterite is a promising tool to refine sources of ore-forming fluids, and to decode hydrothermal dynamics controlling tin and tungsten mineralization.

Are oxygen isotope fractionation factors between calcite and water derived from speleothems systematically biased due to prior calcite precipitation (PCP)?

The equilibrium oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) is an important quantity in stable isotope geochemistry and allows in principle to infer temperature variations from carbonate δ18O if carbonate formation occurred in thermodynamic equilibrium. For this reason, many studies intended to determine the value of the oxygen isotope fractionation factor between calcite and water (18αcalcite/H2O) for a wide range of temperatures using modern cave calcite and the corresponding cave drip water or ancient speleothem carbonate and fluid inclusion samples. However, the picture that emerges from all of these studies indicates that speleothem calcite is not formed in thermodynamic equilibrium but under kinetic conditions, provoking a large variability of determined 18αcalcite/H2O values. Here we present a conceptual framework that can explain the variability of 18αcalcite/H2O values obtained by cave studies. Prior calcite precipitation (PCP) is calcite precipitation before cave drip water is dripping from the cave ceiling and impinges on the surface of a stalagmite or watch glass. Prior to the karst water dripping from the cave ceiling, PCP can occur in the karst above the cave as well as on the cave ceiling, the cave walls and on the surface of stalactites. We argue that PCP leads to increasing the δ18O value of the dissolved HCO3− (δ18OHCO3-), resulting in an oxygen isotope disequilibrium of the δ18OHCO3- values with respect to the δ18O value of water (δ18OH2O). The oxygen isotope disequilibrium between HCO3− and H2O is re-equilibrated by oxygen isotope exchange between H2O and HCO3. Depending on the temperature, the re-equilibration time varies from hours to days and is usually much longer than the residence time of the drip water on stalactites, but much shorter than the time required to percolate through the karst. Therefore, while the oxygen isotope equilibrium between HCO3− and H2O is very likely re-established when PCP occurred in the karst, oxygen isotope disequilibrium conditions between HCO3− and H2O still prevail when PCP occurred inside a cave, e.g., on stalactites. If the oxygen isotope disequilibrium conditions between HCO3− and H2O is not re-established, the precipitated calcite will inherit the elevated δ18O value of the HCO3− and not be in oxygen isotope equilibrium with the corresponding drip water. Consequently, if the 18αcalcite/H2O value is calculated from cave calcite samples affected by PCP, the derived value will be systematically biased.

Fractionation of the copper, oxygen and hydrogen isotopes between malachite and aqueous phase

Studies of the equilibrium isotope properties of stable isotopes of minerals have been initiated principally because of their application to the solution of geochemical problems. Therefore, we examined malachite, a common secondary mineral in the oxidation zone of ore deposits. Stable isotope characterization can contribute needed information on the formation of malachite by establishing the isotopic composition of the parental waters. The equilibrium oxygen and hydrogen isotope fractionations between malachite and solution were determined by precipitation experiments over the temperature range from 10 to 65 °C and could be distinguished in two sets of fractionation factors depending on the temperature. For 45–65 °C, the fractionation is expressed as 1000lnαmal-soloxygen=2.87(106/T2)+0.96 and 1000lnαmal-solhydrogen=-1.47(106/T2)-22.3 with temperature (T) in Kelvin. With the application of the fractionation factors of oxygen and hydrogen of malachite onto source water from the meteoric water line, we were able to calculate the “malachite line” which represents the isotopic compositions of malachite that would precipitate from such water. We also examined the copper isotope fractionation factors between solution and malachite from 10 to 65 °C: 1000lnαsol-malcopper=0.033(106/T2)-0.19 with fractionation shift of Δ65Cumalachite-solution=-0.17±0.05 ‰. This fractionation shift implies that chemical reactions without change of the redox state yield only minor copper isotope fractionation. The calculated fractionation factors of oxygen and hydrogen were used to determine the oxygen and hydrogen isotopic composition of the parental waters of natural malachite samples from a number of localities worldwide. With δ18OVSMOW values of +22.1 to +29.5 ‰ and δD values of -132 to -61 ‰ for the natural malachite and δ18OVSMOW values of -14.5 to -7 ‰ and δD values of -107 to -36 ‰ for the parental water together with the Cu isotopes, it is to assume that all investigated malachite samples are supergene samples which formed from meteoric water. Even in massive malachite samples from Ural Mts. (Russia), no signs of other fluids were detected from the isotopic composition.

Mass Dependence of Equilibrium Oxygen Isotope Fractionation in Carbonate, Nitrate, Oxide, Perchlorate, Phosphate, Silicate, and Sulfate Minerals

Research Article| January 01, 2021 Mass Dependence of Equilibrium Oxygen Isotope Fractionation in Carbonate, Nitrate, Oxide, Perchlorate, Phosphate, Silicate, and Sulfate Minerals Edwin A. Schauble; Edwin A. Schauble Department of Earth, Planetary, and Space Sciences, UCLA, Los Angeles, CA 90095-1567, USA * E-mail: schauble@g.ucla.edu Search for other works by this author on: GSW Google Scholar Edward D. Young Edward D. Young Department of Earth, Planetary, and Space Sciences, UCLA, Los Angeles, CA 90095-1567, USA * E-mail: eyoung@epss.ucla.edu Search for other works by this author on: GSW Google Scholar Reviews in Mineralogy and Geochemistry (2021) 86 (1): 137–178. https://doi.org/10.2138/rmg.2021.86.04 Article history first online: 04 Jan 2021 Cite View This Citation Add to Citation Manager Share Icon Share Twitter LinkedIn Tools Icon Tools Get Permissions Search Site Citation Edwin A. Schauble, Edward D. Young; Mass Dependence of Equilibrium Oxygen Isotope Fractionation in Carbonate, Nitrate, Oxide, Perchlorate, Phosphate, Silicate, and Sulfate Minerals. Reviews in Mineralogy and Geochemistry 2021;; 86 (1): 137–178. doi: https://doi.org/10.2138/rmg.2021.86.04 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyReviews in Mineralogy and Geochemistry Search Advanced Search Variation in both 18O/16O and 17O/16O ratios in natural materials can now be measured with unprecedented precision, with a broad range of potential geochemical applications. In this chapter, equilibrium 18O/16O and 17O/16O fractionation factors are calculated for a selection of minerals and molecules, using first-principles density functional theory models to estimate vibrational frequencies, with a particular focus on investigating the potential for detectable signatures of high-temperature equilibrium processes. Reduced partition function ratios as well as mass-fractionation exponents are tabulated versus temperature. The results are compared with previous theoretical... You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

Calibration of carbonate-water triple oxygen isotope fractionation: Seeing through diagenesis in ancient carbonates

High precision triple oxygen isotope measurements of carbonates can better constrain temperatures and oxygen isotope compositions of seawater through geologic time than 18O/16O measurements alone, but lack of a definitive calibration has hindered progress. In this study, we fluorinated both carbonate and water samples to measure quantitatively the triple oxygen isotope composition of each phase. We compared the oxygen isotope fractionation between carbonate and water for different carbonate materials: calcite synthesized with and without carbonic anhydrase, abiogenic calcite from Devils Hole, and extant biogenic calcite and aragonite of marine origin. We found similar 1000lnα18Occ-wt values for all materials and combined the results with the high temperature experimental data of O'Neil et al. (1969), resulting in the following fractionation equation (T in Kelvins) 1000lnα18Occ-wt=2.84(±0.02)×106T2-2.96(±0.19). The calcite triple oxygen isotope values yielded a θ-T relationship of θcc-wt = –1.39(±0.01)/T + 0.5305 whereas the aragonite triple oxygen isotope values yielded a θ-T relationship of θara-wt = –1.53(±0.02)/T + 0.5305. The calcite-water triple oxygen isotope equilibrium fractionation equation for natural samples is Δ17′Occ-Δ17′Owt=2.84(±0.02)×106T2-2.96(±0.19)-1.39(±0.01)T+0.5305-λ. The combined 1000lnα18O and 1000lnα17O relationships can be used to assess equilibrium in ancient samples and to evaluate potential secular changes in the δ18O value of seawater. Most of the Phanerozoic samples analyzed in this study, which were determined to be pristine in previous studies, have undergone some level of diagenesis. Two samples appear to preserve their original oxygen isotope compositions and suggest a cool ocean with a δ18O value similar to the modern ocean. Using a fluid-rock interaction model, we can “see through” the diagenetic process and estimate the triple oxygen isotope composition of the carbonate prior to alteration. In doing so, we show that for the time intervals and sample locations measured in this study, Phanerozoic oceans had a comparable range of oxygen isotope compositions and temperatures as modern seawater.

Simulating speleothem growth in the laboratory: Determination of the stable isotope fractionation (δ13C and δ18O) between H2O, DIC and CaCO3

Here we present novel cave-analogue experiments directly investigating stable carbon and oxygen isotope fractionation between the major involved species of the carbonate system (HCO3−, CO2, CaCO3 and H2O). In these experiments, which were performed under controlled conditions inside a climate box, a thin film of solution flew down an inclined marble or glass plate. After different distances of flow and, thus, residence times on the plate, pH, electrical conductivity, supersaturation with respect to calcite, precipitation rate as well as the δ18O and δ13C values of the dissolved inorganic carbon (DIC) and the precipitated CaCO3 were obtained.Progressive precipitation of CaCO3 along the plate is accompanied by degassing of CO2 and stable isotope fractionation, and the system is driven out of isotope equilibrium. We observe a strong enrichment of the δ13C values with increasing residence time and a smaller enrichment in δ18O. The temporal evolution of the δ18O and δ13C values of both the DIC and the precipitated CaCO3 can be explained by a Rayleigh fractionation model, but the observed enrichment in δ13C values is much larger than expected based on isotope equilibrium fractionation factors.Our setup enables to determine the fractionation between CaCO3 and HCO3−, i.e., εCaCO3/HCO3−. Carbon isotope fractionation, 13εCaCO3/HCO3−, is strongly negative for all experiments and much lower than equilibrium isotope fractionation (0–1‰). In addition, 13εCaCO3/HCO3− decreases with increasing residence time on the plate, and thus decreasing supersaturation with respect to calcite. Thus, isotope fractionation depends on precipitation rate and consequently occurs under kinetic conditions. This is in contrast to previous studies, which found no rate-dependence and no or even a positive carbon isotope fractionation between CaCO3 and HCO3−. Oxygen isotope fractionation, 18εCaCO3/HCO3−, is also negative and dependent on precipitation rate. Since no literature values for 18εCaCO3/HCO3− are available, we calculated 18εCaCO3/HCO3− using equilibrium oxygen isotope fractionation factors between water and calcite and water and HCO3−, respectively. At the beginning of the plate, the fractionation is in agreement with the fractionation calculated using fractionation factors determined in cave systems.The observed fractionation between CaCO3 and water, 1000ln18α, is also in good agreement with the values determined in cave systems and shows a very similar temperature dependence 1000ln18α=16.516±1.267∗103T−26.141±4.356. However, with progressive precipitation of CaCO3 along the plate, the system is forced out of isotope equilibrium with the water, and 1000ln18α increases.The large, negative, rate-dependent isotope fractionations observed in this study suggest that precipitation of speleothem calcite is strongly kinetically controlled and may, thus, have a large effect on speleothem δ18O and δ13C values. Since these values may erroneously be interpreted as reflecting changes in past temperature, precipitation and/or vegetation density, these results have important implications for paleoclimate reconstructions from speleothems.

Triple oxygen isotope fractionation in the DIC-H2O-CO2 system: A numerical framework and its implications

Triple oxygen isotope composition of carbonate minerals reflects the isotope composition of the water from which carbonates precipitate, and is emerging as a promising proxy for constraining past changes in Earth hydroclimate and surface environment. However, quantitative interpretation of this proxy is not straightforward when carbonate minerals do not form under isotope equilibrium with water. For these carbonates, isotope composition of dissolved inorganic carbon (DIC) in the precipitating solution usually exerts the dominant control on their isotope composition. Here we examine the systematics of triple oxygen isotope fractionation in the DIC-H2O-CO2 system by deriving the fundamental equilibrium and kinetic triple oxygen isotope fractionation factors in this system and simulating the evolution of triple oxygen isotope composition of DIC during three common isotope fractionation processes, i.e., DIC-H2O isotope exchange, CO2 degassing and CO2 absorption.We show that under thermodynamic equilibrium dissolved HCO3– and CO32– both exhibit similar Δ′17O as calcite and aragonite (within 10 per meg at 25 °C), with temperature dependences around 0.61 per meg/°C. However, kinetic isotope fractionations associated with CO2 hydration and hydroxylation and their reverse reactions can produce a range of disequilibrium triple oxygen isotope effects in DIC during all three processes we simulated. The magnitudes of these disequilibrium effects vary with both time and the physicochemical conditions of the solution, e.g., temperature, pH and initial composition. Particularly, we predict correlated enrichments in Δ′17O and δ18O of DIC during CO2 degassing but depletions during CO2 absorption. The slopes of these correlations vary mainly as a function of solution pH but not temperature, DIC concentration or air pCO2, yielding values of 8.8 and 12.0 per meg/‰ at pH = 8 and 9, respectively, at 25 °C. Such disequilibrium isotope effects in DIC are expected to be inherited by carbonate minerals that form from these solutions (e.g., speleothem, coral skeleton, and high pH travertine) and, if not accounted for, could lead to inaccurate estimates of the triple oxygen isotope compositions of the parent water and carbonate formation temperatures. Our numerical model provides a quantitative framework for interpreting triple oxygen isotope composition of DIC and for correcting disequilibrium triple oxygen isotope effects in natural carbonates.

Metamorphism and fluid evolution of the Sumdo eclogite, Tibet: Constraints from mineral chemistry, fluid inclusions and oxygen isotopes

The Sumdo metamorphic belt, located in the Lhasa terrane of Tibet, is a key area for unraveling the Paleo-Tethys evolution. In order to identify the fluid evolution in oceanic subduction zones, eclogite from the Sumdo metamorphic belt, has been investigated in a combined study of petrography, mineral chemistry, fluid inclusions and oxygen isotopes. On the basis of petrography and mineral chemistry, two kinds of garnet were distinguished. The core part of Grt-I shows increasing grossular content and contains prograde mineral inclusions, suggesting that it grew during prograde metamorphism, while the rim of Grt-I shows varying grossular and pyrope contents, representing subsequent overgrowth. Grt-II displays a composition comparable with the outermost part of Grt-I, indicating that Grt-II grew at the peak or initial retrograde stage. Garnet trace element zoning patterns and P-T estimates suggest that the Sumdo eclogite experienced a heating stage during an initial exhumation after the peak metamorphic event.Based on textural criteria and host minerals, three types of fluid inclusions were distinguished: Type-I are primary NaCl dominated intermediate to high-salinity (10–22 wt% NaCl) fluid inclusions hosted by omphacite, which were most likely released during dehydration of the subducting oceanic crust and reflect the composition of eclogite-facies fluids; Type-II are defined as primary low-salinity (1–6 wt% NaCl) fluid inclusions hosted by epidote/clinozoisite, representing fluids that evolved towards low-salinity during uplift; Type-III are secondary low-salinity (0–7 wt% NaCl) fluid inclusions hosted by matrix quartz (i.e., minerals other than the mineral inclusions) and rarely by omphacite and must have formed at a very late stage. In addition, the eclogite displays δ18O values (δ18O = +5.0 to +8.9‰) similar to its protolith, low-temperature altered oceanic crust (δ18O = +4.9 to +12.7‰). The equilibrium oxygen isotope fractionations (Δ18OQtz-Min) between quartz and garnet/omphacite suggest isotopic equilibrium and a closed fluid system during eclogite facies metamorphism. Our data indicate that the Sumdo eclogite experienced “hot” exhumation, during which large amounts of fluids were released by dehydration. Fluids in the Sumdo eclogite were typically aqueous fluids of varying salinities and now preserved as fluid inclusions in HP metamorphic minerals. In comparison with continental subduction zones, we confirm previous conclusion that the fluid regime in oceanic subduction zones is relatively simple (i.e. mainly NaCl bearing brines) with seawater-altered slabs as the dominant source.

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32− pool (αc/CO32-), and (b) CO32− and water (αCO32-/w), as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32− pool and water. When the CO32− pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1–2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32− and water leads to strong (>2‰) positive or negative pH and growth rate effects on αCO32-/w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3−, CO2, H2O and/or OH−. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on αCO32-/w and is expected to deviate from the commonly accepted value (−0.22±0.02‰/°C between 0 and 30°C; Kim and O’Neil, 1997) when the CO32− pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading to a relatively constant foraminifer calcite δ18O-temperature relationship (−0.21±0.01‰/°C). The lower average coral δ18O data relative to foraminifers and other calcifiers is best explained by the precipitation of internal DIC derived from hydrated CO2 in a high-pH calcifying fluid and minimal subsequent DIC-H2O isotopic equilibration. This leads to a reduced and variable coral aragonite δ18O-temperature relationship (−0.11 to −0.22‰/°C). Together, the model presented here reconciles observations of oxygen isotope fractionation over a range of CaCO3-DIC-H2O systems.

A refined method for calculating paleotemperatures from linear correlations in bamboo coral carbon and oxygen isotopes

AbstractBamboo corals represent an emerging paleoclimate archive with the potential to record variability at intermediate depths throughout much of the global ocean. Realizing this potential has been complicated by biologically mediated vital effects, which are evident in linear correlations of skeletal carbon (δ13C) and oxygen (δ18O) isotope composition. Previous efforts to develop a bamboo coral δ18O paleothermometer by accounting for such vital effects have not been completely successful as they still rely on empirical calibrations that are offset from the temperature dependence of abiogenic experiments. Here we describe an approach that better corrects for bamboo coral vital effects and allows paleotemperatures to be calculated directly from the abiogenic temperature dependence. The success of the method lies in calculating apparent equilibrium carbon and oxygen isotope fractionation at the temperature, pH, and growth rate of each coral, as well as in the use of model II regressions. Rigorous propagation of uncertainty suggests typical errors of ±2–3°C, but in select cases errors as low as ±0.98°C can be achieved for densely sampled and strongly correlated data sets. This lower limit approaches the value attributed to uncertainty in pH and growth rate estimates alone, as predicted by a series of pseudoproxy experiments. The incorporation of isotopically light metabolic CO2 appears to be negligible in most Pacific corals, but may be significant in Atlantic specimens, potentially requiring an additional correction. The success of the method therefore hinges on how well complex environmental systems and biomineralization strategies are constrained, with the most reliable temperatures occurring when calcifying fluid pH, growth rate, and incorporation of metabolic carbon into skeletal calcite are constrained using multiple geochemical proxies.

Oxygen isotope fractionation in the portlandite–water and brucite–water systems from 125 to 450 °C, 50 MPa

Equilibrium oxygen isotope fractionation factors were determined for the portlandite–water and brucite–water systems from 125 to 425°C, 50MPa using the partial exchange technique. Reagent grade cryptocrystalline Ca(OH)2 and amorphous Mg(OH)2 were reacted with three waters having different initial δ18O compositions. Isotope exchange occurred via recrystallization with exchange varying from 40% to 95% at 200 to 425°C, respectively. Equilibrium 18O brucite–water fractionation factors (103lnα) increase from −4.7±3.5‰ at 200°C to −3.5±2.5‰ at 425°C. These data connect smoothly with previous experimental calibrations at lower and higher temperatures to define a single function valid from 15 to 450°C, as follows:103lnαbrucite-water=4.39×106T2-16.95×103T+11.19where T is temperature in Kelvin. These results confirm the existence of a broad minimum in the fractionation factor for brucite at ∼250°C. The equilibrium 18O fractionation factor for portlandite–water varies from −11.1±2.7‰ at 125°C to −6.6±0.1‰ at 425°C, and can be described by the following function:103lnαportlandite-water=5.61×106T2-26.29×103T+19.72where T is temperature in Kelvin. These experimental results indicate that brucite favors 18O relative to portlandite with brucite–portlandite fractionation decreasing from 8‰ to 3‰ from 125 to 425°C. A significant temperature dependent cation mass effect is therefore indicated for cation–OH bonds in hydroxide minerals. The observed fractionation is consistent with quantum theory which predicts that bonds with less massive cations have higher vibrational frequencies and will display a relative affinity for 18O to stabilize the structure. Brucite–portlandite 18O fractionation predicted using the increment method is extremely small, opposite in sign (−0.1‰ to −0.2‰), and shows very little dependence on temperature, in poor agreement with the experimental calibration. This indicates that the method does not adequately account for the effect of cation mass on 18O fractionation within hydroxide minerals. It is suggested that cation-specific parameters within the increment method could be fit to the experimental calibrations reported here to improve prediction of fractionation factors for hydroxides and hydroxyl-bearing aluminosilicates, particularly at low temperate where the cation-mass effect is more significant.

Precise calibration of equilibrium oxygen isotope fractionations between dissolved phosphate and water from 3 to 37 °C

The stable oxygen isotope composition of orthophosphate (δ18OPO4) is a widely used (paleo)temperature indicator and more recently, a useful tracer of phosphorus-cycling. In natural aqueous systems (e.g., oceans, rivers, soil/ground water) the largest reactive phosphorus pool is dissolved inorganic phosphate. Here, we present a new experimentally-determined equation for thermodynamic equilibrium O-isotope fractionations between dissolved phosphate and water, catalyzed by the enzyme inorganic pyrophosphatase (PPase) between 3 and 37°C;1000lnα(PO4-H2O)=14.43(±0.39)1000/T(K)-26.54(±1.33)r2=0.99The new equation is slightly offset by +0.5 to +0.7‰ from recent empirically-determined fractionations based on biogenic apatite, with both based on modern cf-irms TC/EA analysis of Ag3PO4. Dissolved phosphate–water fractionations are offset by +0.9 to +2.3‰ from the earlier empirical relation for biogenic phosphate–water fractionation determined using fluorination of BiPO4. The equation presented here is thus, specific to equilibrium fractions between dissolved phosphate and water and appropriate for use in recent/future oxygen isotope studies of dissolved phosphate using similar cf-irms TC/EA analytical methods.

Oxygen isotope fractionation in travertine-depositing pools at Baishuitai, Yunnan, SW China: Effects of deposition rates

Travertine δ18O values can be used to reconstruct paleo-temperatures if the oxygen isotope fractionation factors between travertine and water are accurately understood. For this purpose, the δ18O values of pool travertine and its parent water, and the deposition rates of the calcite were investigated at Baishuitai (Yunnan, SW China) over the course of the full hydrological year, April 23 2006–April 25 2007. The results show that the travertine–water isotope fractionation factors are close to the commonly accepted equilibrium line of Kim and O’Neil (1997). This differs from the results obtained by Yan et al. (2012) who found that the oxygen isotope fractionation factors in the travertine-depositing pools were close to the line suggested as equilibrium relationship by Coplen (2007). The average calcite deposition rate (2.30mgcm−2d−1) in the present study is six times larger than that (0.38mgcm−2d−1) in Yan et al. (2012). If slower calcite precipitation leads to equilibrium oxygen isotopic fractionation, then the results of this study support the results of Coplen (2007) that indicate that the equilibrium fractionation factor may be greater than the commonly accepted one derived by Kim and O’Neil (1997). The relationship between oxygen isotope fractionation factor and calcite deposition rate in our study also agrees with the results of Dietzel et al. (2009) who found that the kinetic-isotope effect favors preferential incorporation of 16O in solid calcite as the calcite deposition rate increases. There was a threshold for calcite precipitation rate control on oxygen isotopic equilibrium. In our case of travertine-depositing pools, when the calcite deposition rate was lower than 0.38mgcm−2d−1, oxygen isotopic equilibrium between calcite and water was attained. Therefore, calcite deposition rate is a potentially important consideration when using δ18O in natural carbonates as a proxy for terrestrial and ocean temperature.

The oxygen isotope equilibrium fractionation between sulfite species and water

Sulfite is an important sulfoxy intermediate in oxidative and reductive sulfur cycling in the marine and terrestrial environment. Different aqueous sulfite species exist, such as dissolved sulfur dioxide (SO2), bisulfite (HSO3−), pyrosulfite (S2O52−) and sulfite sensu stricto (SO32−), whereas their relative abundance in solution depends on the concentration and the pH. Conversion of one species into another is rapid and involves in many cases incorporation of oxygen from, or release of oxygen to, water (e.g. SO2+H2O↔HSO3−+H+), resulting in rapid oxygen isotope exchange between sulfite species and water. Consequently, the oxygen isotope composition of sulfite is strongly influenced by the oxygen isotope composition of water. Since sulfate does not exchange oxygen isotopes with water under most earth surface conditions, it can preserve the sulfite oxygen isotope signature that it inherits via oxidative and reductive sulfur cycling. Therefore, interpretation of δ18OSO42- values strongly hinges on the oxygen isotope equilibrium fractionation between sulfite and water which is poorly constrained. This is in large part due to technical difficulties in extraction of sulfite from solution for oxygen isotope analysis.To overcome these challenges, anoxic isotope equilibration experiments were performed with dissolved sodium sulfite in solutions with distinct oxygen isotope signatures. Sulfite was precipitated using two different agents, barium chloride and silver nitrate. The experiments were performed at 22°C and varying pH of 1.5, 6.3, 6.6, and 9.7 to investigate how changes in sulfite speciation affect the oxygen isotope equilibrium fractionation between sulfite and water.From the experiments at pH 1.5 where SO2 is the dominant sulfite species, a rough estimate of 37.0‰ was determined for the oxygen isotope equilibrium fractionation factor between aqueous SO2 and water (εSO2↔H2OEQ). The oxygen isotope equilibrium fractionation between the aqueous phases is much larger than the known oxygen isotope equilibrium fractionation between gaseous SO2 and water vapor, probably because of a stronger association with water molecules. At pH values of 6.3–9.7 a more firm estimate for the oxygen isotope equilibrium fractionation between HSO3−, SO32− and water (εSO32-↔H2OEQ) of 15.2±0.7‰ was obtained.Our results provide new insights into the oxygen isotope fractionation during reductive and oxidative sulfur cycling. They demonstrate that isotope exchange between sulfite and water during dissimilatory sulfate reduction (DSR) alone is too small to be responsible for the apparent oxygen isotope equilibrium fractionation between sulfate and water mediated by DSR. Our estimates also provide a basis for tracing and quantifying the transformation of sulfoxy intermediates during the oxidation of reduced sulfur compounds to sulfate.