Equilibrium Isotope Exchange Research Articles

Composition effects on equilibrium oxygen isotope fractionation factors between garnets and quartz/calcite/olivine: Implication from vibration frequencies of garnets at high temperatures and high pressures

Garnet-group minerals, with their wide range of compositions, play a significant role in Earth's crust and upper mantle, participating in various petrological and geochemical processes. Oxygen isotope fractionation factors between garnets and other minerals hold crucial implications in these contexts. In this work, vibration frequencies were measured via Raman spectra on five garnet mineral samples in the pyrope-almandine-spessartine ternary system and four synthetic pyrope-grossular solid solutions at temperatures up to 1000 °C and pressures up to 17 GPa. Isobaric (γiP) and isothermal (γiT) mode Grüneisen, as well as anharmonic (ai) parameters, were determined for the observed modes. Our study shows that the vibration bands tend to shift to lower frequencies with increasing temperature and to higher frequencies with increasing pressure. Moreover, the anharmonic correction has been found to contribute positively to equilibrium oxygen isotope fractionation β factors in garnets, typically within 0.5 ‰ above 1000 K. The 103∙lnβ(T) factors calculated from vibration spectra (considering Г points only) align closely with those from theoretical calculations (including all frequencies in the Brillouin zone). Contributions from phonon dispersion (including none-Г points) are typically smaller than the uncertainties propagated from frequency measurements. Additionally, the pressure effect on the oxygen isotope fractionation in garnet, evaluated from the isothermal Grüneisen parameters, is found to be insignificant under crustal and upper mantle conditions, consistent with thermodynamic expectations. Using published oxygen isotope fractionation β factors for quartz and calcite, the equilibrium oxygen isotope fractionation factors (103∙lnα) are calculated between garnets of diverse compositions and any of these phases as functions of temperature, pressure and fraction of garnet endmembers. Considering composition effects helps to reduce the discrepancies among experimental and empirical calibrations of oxygen isotope fractionation factors between garnet and quartz. As an example application, oxygen isotope fractionation factors 103∙lnα(P, T) between garnets and forsterite were calculated under upper mantle conditions. Our findings suggest that these fractionation factors are predominantly dependent on temperature and garnet compositions, with minor influence from pressure. Compared with our calculated fractionation factors between garnet and olivine, the oxygen isotope exchange equilibrium may have been reached in some in kimberlite and mantle xenolith samples between garnet and olivine. However, in other samples, the fractionation factors cannot be explained solely by the composition effect, likely due to metasomatism. Our results underscore the importance of considering garnet compositions when interpreting their oxygen isotope compositions.

Electron correlation effects on uranium isotope fractionation in U(VI)-U(VI) and U(IV)-U(VI) equilibrium isotopic exchange systems.

Uranium isotope fractionation has been extensively investigated in the fields of nuclear engineering and geochemical studies, yet the underlying mechanisms remain unclear. This study assessed isotope fractionations in U(VI)-U(VI) and U(IV)-U(VI) systems by employing various relativistic electron correlation methods to explore the effect of electron correlation and to realize accurate calculations of isotope fractionation coefficients (ε). The nuclear volume term, ln Knv, the major term in ε, was estimated using the exact two-component relativistic Hamiltonian in conjunction with either HF, DFT(B3LYP), MP2, CCSD, CCSD(T), FSCCSD, CASPT2, or RASPT2 approaches for small molecular models with high symmetry. In contrast, chemical species studied in prior experimental work had moderate sizes and were asymmetrical. In such cases, electron correlation calculations other than DFT calculations were not possible and so only the HF and B3LYP approaches were employed. For closed-shell U(VI)-U(VI) systems, the MP2, CCSD and CCSD(T) methods yielded similar ln Knv values that were intermediate between those for the HF and B3LYP methods. Comparisons with experimental results for U(VI)-U(VI) systems showed that the B3LYP calculations gave results closer to the experimental data than the HF calculations. Because of the open-shell structure of U(IV), multireference methods involving the FSCCSD, CASPT2 and RASPT2 techniques were used for U(IV)-U(VI) systems, but these calculations exhibited instability. The average-of-configuration HF method showed better agreement with the experimental ε values for U(IV)-U(VI) systems than the B3LYP method. Overall, electron correlation improved the description of ε for the U(VI)-U(VI) systems but challenges remain with regard to open-shell U(IV) calculations because an energy accuracy of 10-6-10-7Eh is required for ln Knv calculations.

Application of gas chromatography-stable isotope mass spectrometry to determine the oxygen isotope ratio of water in concentrated fruit juice

In this study, we developed a method to determine the authenticity of concentrated fruit juice using the δ18O ratio of water. We utilized the gas chromatography-isotope ratio mass spectrometry (GC-IRMS) technique along with the offline isotope exchange equilibrium method to pretreat and measure the oxygen isotopes in water in concentrated apple juice. This innovative approach uses anhydrous ethanol as a solvent to dissolve concentrated juices, thereby facilitating a more comprehensive reaction between the water in the sample and the CO2 standard gas. Additionally, the reaction vessel exhibits excellent air tightness, ensuring rapid equilibrium time and enabling accurate determination of δ18O in the water content of concentrated juice. The reaction vessel had excellent air tightness and rapid equilibration time, enabling accurate measurement of δ18O of water in concentrated fruit juice. The reaction vessel used had excellent air tightness and rapid equilibration time, ensuring accurate measurement of the δ18O of water in concentrated fruit juice. We analyzed 40 samples of concentrated apple juice and found that the range of δ18O values in the water of concentrated apple juice was between 1.29 ‰ and 7.59 ‰. Additionally, we used prepared sucrose syrup as a simulated sample and found that the δ18O distribution range was between −10.43 ‰ and −10.53 ‰. Furthermore, we conducted adulteration simulation experiments on randomly selected real samples and discovered a linear negative correlation between the adulteration ratio and the δ18O value of water in the samples.

Temperature dependence of hydrogen isotope effect in LaNi5-H(D) system

To study inverse effect of hydrogen isotopes in LaNi5 for hydrogen isotope separation at ambient temperature, temperature dependence of hydrogen isotope effect in LaNi5－H(D) system was investigated in the temperature range -70 °C to 3 °C. Isotherms of hydrogen isotopes were tested in an automated Sieverts apparatus with a thermostat, and pressure differences were studied between H2 and D2. Isotope exchange process was carried out and H2－HD－D2 equilibrium was judged by online chromatography, separation factors were calculated to investigate the thermodynamic isotope effect. In the H2, D2 isotherms, average time interval (0.5h) between each equilibrium point was relatively short due to high precision temperature control. From the plateau pressures at a constant hydrogen (or deuterium) concentration in LaNi5 (2D or 2H atoms/mole of LaNi5) the partial molar enthalpies, ⊿H, and entropies, ⊿S of formation were calculated. ⊿H and ⊿S kept good accordance with the values from references, which indicated good performance of the Sieverts apparatus. The isotope exchange equilibrium was reached within 1h. The results showed that ratio between H2 pressure and D2 pressure, r(H－D) = P(D2)/P(H2), dropped as temperature decreased and the inverse effect was found (r(H－D)<1.0) below -5 °C according to the absorption branch of isotherms, whereas the effect was estimated to appear below 60 °C from the desorption branch. The separation factor of the H2－HD－D2 mixture, decreased as temperature increased and the inverse effect happened below -20 °C. The inverse effect was affected by the isotherm hysteresis and HD existence.

DFT analysis of nitrogen isotopic reduction partition function ratios in proton exchange equilibria of glutamic acid species in water and its application to the estimation of nitrogen isotope fractionation.

L-Glutamic acid (Glu) plays a pivotal role in amino acid metabolism in living organisms. Theoretical knowledge of how metabolism propagates the nitrogen isotope composition (δ15N) is essential for elucidating the mechanism of amino acid metabolism in vivo. In this paper, to estimate the nitrogen isotope fractionation involving Glu and its protonated/deprotonated species, their nitrogen isotopic reduction partition function ratios (RPFRs) were calculated at the apfd/6-311+G(2d,p) level of theory by the SCRF method. The results show that the RPFR values of the eight possible Glu species at 25 °C are: cation > zwitterion with α-COOH and γ-COO- > zwitterion with α-COO- and γ-COOH > anion with -NH3+ ≫ uncharged molecule > anion with -NH2 and γ-COO- > anion with -NH2 and α-COO- > di-anion. Several correlations between RPFR and bond distances were found. Most importantly, it was found that the shorter the distance of the (C-)N⋯H(-O) hydrogen bond (HB), the greater the RPFR value for that species. This correlation indicates that the tri-coordinate nitrogen atom of the amino group may take on the character of the tetra-coordinate nitrogen atom to some extent by forming a HB of this type. The nitrogen isotope exchange equilibrium between Glu and glycine/serine was evaluated at a typical physiological pH of 7.4. Calculations suggest that the equilibrium constant for the former is an increasing function of temperature from 0 to 100 °C, while the latter is a decreasing function of temperature over the same temperature range.

Temperature dependence of isotopic fractionation in the CO2 -O2 isotope exchange reaction.

RationaleOxygen isotope exchange between O2 and CO2 in the presence of heated platinum (Pt) is an established technique for determining the δ 17O value of CO2. However, there is not yet a consensus on the associated fractionation factors at the steady state.MethodsWe determined experimentally the steady‐state α 17 and α 18 fractionation factors for Pt‐catalyzed CO2‐O2 oxygen isotope exchange at temperatures ranging from 500 to 1200°C. For comparison, the theoretical α 18 equilibrium exchange values reported by Richet et al. (1997) have been updated using the direct sum method for CO2 and the corresponding α 17 values were determined. Finally, we examined whether the steady‐state fractionation factors depend on the isotopic composition of the reactants, by using CO2 and O2 differing in δ18O value from −66 ‰ to +4 ‰.ResultsThe experimentally determined steady‐state fractionation factors α 17 and α 18 are lower than those obtained from the updated theoretical calculations (of CO2‐O2 isotope exchange under equilibrium conditions) by 0.0024 ± 0.0001 and 0.0048 ± 0.0002, respectively. The offset is not due to scale incompatibilities between isotope measurements of O2 and CO2 nor to the neglect of non‐Born‐Oppenheimer effects in the calculations. There is a crossover temperature at which enrichment in the minor isotopes switches from CO2 to O2. The direct sum evaluation yields a θ value of ~0.54, i.e. higher than the canonical range maximum for a mass‐dependent fractionation process.ConclusionsUpdated theoretical values of α 18 for equilibrium isotope exchange are lower than those derived from previous work by Richet et al. (1997). The direct sum evaluation for CO2 yields θ values higher than the canonical range maximum for mass‐dependent fractionation processes. This demonstrates the need to include anharmonic effects in the calculation and definition of mass‐dependent fractionation processes for poly‐atomic molecules. The discrepancy between the theory and the experimental α 17 and α 18 values may be due to thermal diffusion associated with the temperature gradient in the reactor.

Sampling Volcanic Plume Using a Drone-Borne SelPS for Remotely Determined Stable Isotopic Compositions of Fumarolic Carbon Dioxide

Both chemical and isotopic compositions of concentrated volcanic plumes are highly useful in evaluating the present status of active volcanoes. Monitoring their temporal changes is useful for forecasting volcanic eruptions as well. Recently, we developed a drone-borne automatic volcanic plume sampler, called SelPS, wherein an output signal from a sulfur dioxide (SO2) sensor triggered a pump to collect plume samples when the SO2 concentration exceeded a predefined threshold. In this study, we added a radio transmission function to the sampler, which enabled our operator to monitor real-time SO2 concentration during flights and thus obtain more concentrated volcanic plume samples through precise adjustment of the hovering position. We attached the improved SelPS to a drone at Nakadake crater, Aso volcano (Japan), and successfully obtained volcanic plume samples ejected from the crater more concentrated than those obtained by using previous version of SelPS in 2019. Additionally, we found a significant linear correlation between the reciprocal of the concentration and isotopic ratios for the 2H/1H ratios of H2, 18O/16O ratios of CO2, and 13C/12C ratios of CO2 within the plume samples. Based on the isotopic ratios of fumarolic H2 (δ2H = −239 ± 6‰) and fumarolic CO2 (δ13C = −3.58 ± 0.85‰ and δ18O = +22.01 ± 0.68‰) determined from the linear correlations, we estimated the apparent equilibrium temperatures (AETs) with magmatic H2O simultaneously and precisely for the first time in erupting volcanoes, assuming hydrogen isotope exchange equilibrium between H2 and H2O (AETD = 629 ± 32°C) and oxygen isotope exchange equilibrium between CO2 and H2O (AET18O = 266 ± 65°C). We found that the AET18O was significantly lower than the AETD in the crater. While the temperature of the magmatic gases was originally 600°C or more, most of the gases cooled just beneath the crater to temperatures around the boiling point of water. The improved SelPS enable us to determine both AETD and AET18O in eruptive volcanoes, wherein fumaroles are inaccessible. Simultaneous and precise determination of both the AET18O and AETD can provide novel information on each volcano, such as the physicochemical conditions of magma degassing and the development of fluid circulation systems beneath each volcano.

A density functional theory (DFT) study on reduced partition function ratios of oxygen species adsorbed on a Pt19 cluster and oxygen isotope effects

ABSTRACT A density functional theory (DFT) computation on oxygen species adsorbed on platinum (Pt) catalyst surfaces has been carried out to elucidate oxygen isotope fractionation observed at the cathode of a polymer electrolyte membrane fuel cell (PEMFC). The Pt(111) catalyst surface was modelled by a Pt19 cluster, and O, OH, OHH, OO, OOH, OHOH and HOHOH were assumed to be the oxygen species adsorbed on the Pt(111) surface. The oxygen isotope reduced partition function ratios (RPFRs) of the adsorbed species were calculated using the vibrational frequencies obtained by normal mode analyses performed on the optimized structures. Various oxygen isotope exchange equilibria among the adsorbed oxygen species and oxygen and water molecules in the gas phase were examined using their RPFRs. Experimental observation that the lighter 16O is enriched in water molecules exhausted from the cathode is explainable in a satisfactory manner by assuming oxygen isotope exchange equilibria of O2 molecule with O, OH, OO and OOH adsorbed on the Pt(111) surface that appear in the first half of the conversion reaction from O2 to H2O and those of H2O molecule with the adsorbed oxygen species, OHH, OHOH and HOHOH, formed in the latter half of the conversion reaction.

Controls on stable isotopic characteristics of water vapour over Thailand

AbstractThis study examined the weekly water vapour isotopic composition (δ18Ov) in Thailand. The water vapour was cryogenically collected from eight sites across the country. Two observational samples were collected over one 24‐h period each week (a daytime and a night‐time sample), from September 2013 to September 2014. The primary aim was to investigate the environmental factors influencing water vapour isotopes. The results revealed differences in water vapour isotopic values between day and night samples. Three periods of depleted δ18Ov were associated with large‐scale convective systems in September, December, and May. The statistical relationship between the climate variables and water vapour isotopes indicated that the amount of precipitation and relative humidity were the primary controls on both diurnal and seasonal isotopic variability. The temperature did not affect the δ18Ov, mainly because the atmospheric processes are a function of vertical convection rather than temperature in tropical regions. The water vapour deuterium excess (d‐excess) showed greater variability in 2013 than in 2014. The d‐excess variation reflected the differences in convection occurring in the day and night. In addition, the vapour phase data were combined with the local meteoric water line to identify the local water vapour line and the interaction between the isotopic composition of water vapour and liquid water. The water vapour isotopic patterns paralleled the precipitation isotopes on rainy days because of equilibrium isotopic exchange. Water vapour and precipitation were isotopically similar under low humidity but showed greater differences from each other under wetter conditions. The study results provide insight into water vapour isotopic characteristics in tropical regions and constrain the role of large‐scale atmospheric processes relative to isotopic variability of water vapour in Thailand and nearby countries.

Insights into Primary Ion Exchange between Ion-Selective Membranes and Solution. From Altering Natural Isotope Ratios to Isotope Dilution Inductively Coupled Plasma Mass Spectrometry Studies.

Although ion-selective electrodes have been routinely used for decades now, there are still gaps in experimental evidence regarding how these sensors operate. This especially applies to the exchange of primary ions occurring for systems already containing analyte ions from the pretreatment step. Herein, for the first time, we present an insight into this process looking at the effect of altered ratios of naturally occurring analyte isotopes and achieving isotopic equilibrium. Benefiting from the same chemical properties of all isotopes of analyte ions and spatial resolution offered by laser ablation and inductively coupled plasma mass spectrometry, obtaining insights into primary ion diffusion in the preconditioned membrane is possible. For systems that have reached isotopic equilibrium in the membrane through ion exchange and between the membrane phase and the sample, quantification of primary ions in the membrane is possible using an isotope dilution approach for a heterogeneous system (membrane–liquid sample). Experimental results obtained for silver-selective membrane show that the primary ion diffusion coefficient in the preconditioned membrane is close to (6 ± 1) × 10–9 cm2/s, being somewhat lower compared to the previously reported values for other cations. Diffusion of ions in the membrane is the rate limiting step in achieving isotopic exchange equilibrium between the ion-selective membrane phase and sample solution. On the contrary to previous reports, quantification of silver present in the membrane clearly shows that contact of the membrane with silver nitrate solution of concentration 10–3 M leads to pronounced accumulation of silver ions in the membrane, reaching almost 150% of ion exchanger amount. The magnitude of this effect increases for higher concentration of the electrolyte in the solution.

Quantifying the nitrogen isotope effects during photochemical equilibrium between NO and NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;: implications for &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;15&amp;lt;/sup&amp;gt;N in tropospheric reactive nitrogen

Abstract. Nitrogen isotope fractionations between nitrogen oxides (NO and NO2) play a significant role in determining the nitrogen isotopic compositions (δ15N) of atmospheric reactive nitrogen. Both the equilibrium isotopic exchange between NO and NO2 molecules and the isotope effects occurring during the NOx photochemical cycle are important, but both are not well constrained. The nighttime and daytime isotopic fractionations between NO and NO2 in an atmospheric simulation chamber at atmospherically relevant NOx levels were measured. Then, the impact of NOx level and NO2 photolysis rate on the combined isotopic fractionation (equilibrium isotopic exchange and photochemical cycle) between NO and NO2 was calculated. It was found that the isotope effects occurring during the NOx photochemical cycle can be described using a single fractionation factor, designated the Leighton cycle isotope effect (LCIE). The results showed that at room temperature, the fractionation factor of nitrogen isotopic exchange is 1.0289±0.0019, and the fractionation factor of LCIE (when O3 solely controls the oxidation from NO to NO2) is 0.990±0.005. The measured LCIE factor showed good agreement with previous field measurements, suggesting that it could be applied in an ambient environment, although future work is needed to assess the isotopic fractionation factors of NO+RO2/HO2→NO2. The results were used to model the NO–NO2 isotopic fractionations under several NOx conditions. The model suggested that isotopic exchange was the dominant factor when NOx&gt;20 nmol mol−1, while LCIE was more important at low NOx concentrations (&lt;1 nmol mol−1) and high rates of NO2 photolysis. These findings provided a useful tool to quantify the isotopic fractionations between tropospheric NO and NO2, which can be applied in future field observations and atmospheric chemistry models.

Equilibrium fractionation and isotope exchange kinetics between aqueous Se(IV) and Se(VI)

The selenium (Se) isotope system has been proposed as a redox proxy in environmental and paleoceanographic studies. However, Se isotope exchange among various Se species can potentially interfere with redox-related isotope signatures, and is still poorly understood. In this work, we investigated Se isotope exchange kinetics and equilibrium fractionations between aqueous Se(IV) and Se(VI) under various experimental conditions. At pH = 7, low-Se concentration experiments (0.026 mM Se(IV) and 0.026 mM Se(VI)) at 25 °C, 38 °C and 60 °C were conducted for 900 days, while high-Se concentrations (0.13 mM Se (IV) and 0.14 mM Se(VI); 1.3 mM Se(IV) and 1.4 mM Se(VI)) at 60 °C were conducted for 1547 days. All experiments did not reach isotopic equilibrium, with observed Se isotope fractionations <0.20‰. Adding an electronic shuttle (Anthraquinone-2, 6-disulfonate) did not increase the isotope exchange rate. These results show that under the experimental conditions examined, the isotope exchange reaction between aqueous Se(IV) and Se(VI) is extremely slow.The exchange kinetics between Se(IV) and Se(VI) were also investigated using a 82Se tracer. The exchange rates (R) at 0.13 mM Se(IV) and 0.13 mM Se(VI) at 25 °C, 38 °C and 60 °C were determined to be ≤6.34 × 10−10 M day−1, ≤1.12 × 10−09 M day−1 and ≤1.17 × 10−09 M day−1, respectively. Using the upper bound for the isotope exchange rate at 25 °C and theoretically calculated equilibrium fractionations, and assuming a first order isotope exchange reaction between Se(IV) and Se(VI) by analogy to the sulfur system, the timescale of isotope exchange between aqueous Se (IV) and Se (VI) in a natural lake (Sweitzer Lake, Colorado, USA) was estimated. The minimum half-time (t1/2, time to reach 50% isotopic equilibrium) and the minimum time for detectable isotope exchange (tmin) are ≥440,000 and ≥18,000 years, respectively. In the modern oceans, t1/2 and tmin are ≥51 million and ≥3.6 million years, respectively. These timescales are much longer than the residence time of Se in Sweizer Lake (2.4 years) and the modern ocean (26,000 years). Therefore, when using Se isotopes to trace the biogeochemical cycle of Se in lakes and oceans, the effect caused by isotope exchange between aqueous Se(IV) -Se(VI) systems is insignificant.

Fluid geochemistry of the Cuopu high temperature geothermal system in the eastern Himalayan syntaxis with implication on its genesis

High-temperature geothermal fluids dissolve constituents pertinent to water-rock interaction and magmatic volatile absorption, resulting in high total dissolved solid (TDS) values. However, this study focuses on the hydrochemical evolution of the low-salinity HCO3–Na type high-temperature geothermal fluid in Cuopu, eastern Himalayas. The geothermal water is recharged by local precipitation and glacier water from surrounding mountains. The TDS values are below 834 mg/L and the constituents are mainly products of the water-carbon dioxide-rock interactions lacking magmatic volatile dissolved in the fluid. The geothermal water reaches an almost complete chemical equilibrium with the feldspar or plagioclase-enriched reservoir rock in a reducing condition. The reservoir temperature is between 175 °C–200 °C, while the temperature could reach up to 400 °C in the deep crustas indicated by the carbon isotopic exchange equilibrium between CO2 and CH4. The infiltrated glacier water was heated during its circulation within the hot thickened crust and continued dissolving the crustal metamorphic gas, such as radiogenic helium and limestone metamorphic CO2, until the junction of the two sets of faults provided an ascending channel for it. Upon rising along the conduit, the geothermal water mixed with cold groundwater to different degrees. Approximately 0.015 mol/L CO2 escaped from the geothermal fluid when it scattered as bubbling hot springs on the surface of the anisotropic porous Quaternary sediments. Such kind ofhydrochemical evolution of lowsalinity alkaline HCO3–Na type water represents a typical formation mechanism of the high-temperature geothermal systems along the Himalayas.

H2 Kinetic Isotope Fractionation Superimposed by Equilibrium Isotope Fractionation During Hydrogenase Activity of D. vulgaris Strain Miyazaki.

We determined 2H stable isotope fractionation at natural abundances associated with hydrogenase activity by whole cells of Desulfovibrio vulgaris strain Miyazaki F expressing a NiFe(Se) hydrogenase. Inhibition of sulfate reduction by molybdate inhibited the overall oxidation of hydrogen but still facilitated an equilibrium isotope exchange reaction with water. The theoretical equilibrium isotope exchange δ2H-values of the chemical exchange reaction were identical to the hydrogenase reaction, as confirmed using three isotopically different waters with δ2H-values of – 62, +461, and + 1533‰. Expected kinetic isotope fractionation of hydrogen oxidation by non-inhibited cells was also superimposed by an equilibrium isotope exchange. The isotope effects were solely catalyzed biotically as hydrogen isotope signatures did not change in control experiments without cells of D. vulgaris Miyazaki.

Copper, zinc, chromium and osmium isotopic compositions of the Teplá-Barrandian unit black shales and implications for the composition and oxygenation of the Neoproterozoic-Cambrian ocean

Two Neoproterozoic-Cambrian shale suites that consist of normal (NBS) and metal-rich (HMBS) black shales from the Teplá-Barrandian Unit, Bohemian Massif (Czech Republic) are studied in terms of their Cu, Zn, Cr and Re–Os isotopic compositions to improve our knowledge of elemental and isotopic mass balance of these elements in Earth's oceans in the past and the extent of surface oxygenation at the Neoproterozoic–Cambrian boundary. The rock compositions indicate that the inputs of Cu and Zn have been controlled by variable proportions of metal-rich authigenic and low-metal terrigenous sources, the latter having exceptionally low δ65Cu and partially δ66Zn. In this respect, our data confirm previous studies conclusions that organic-rich sediments with high a terrigenous flux play an important role in the sinking of light Zn in the oceans and provide new evidence that these types of rocks also represent the currently unidentified burial of very light Cu in the ocean. The chromium isotopic composition reveals a complex history of Cr uptake and fractionation through the dominant Cr input from different terrigenous sources with variable δ53Cr followed by Cr fractionation that was controlled by redox states (NBS). On the other hand, mixing and/or continuous equilibrium isotopic exchange between seawater and hydrothermal Cr was the dominant process for the HMBS. The Re–Os contents of the NBS were controlled by hydrogenous components, which yield a poorly defined Re–Os age for the least disturbed samples of 555 ± 60 Ma, indicating an open-system behavior, while the HMBS Re–Os composition was largely influenced by hydrothermal fluids during deposition. The calculated authigenic δ65Cu, which is similar to that in the present-day ocean, and highly positive δ53Cr values of the HMBS suggest high levels of surface oxygenation during the Neoproterozoic–Cambrian transition. Furthermore, the authigenic δ66Zn, which is indistinguishable from that in the present-day ocean, may imply a constant Zn isotopic composition of the oceans from the Neoproterozoic because of the well-balanced cycle of phosphates, which were strongly adsorbed by Fe-hydroxides. The radiogenic nature of the initial 187Os/188Os (~0.6), although with a high associated error, seems to not confirm previous indications of an abrupt increase of seawater 187Os/188Os during the late Neoproterozoic due to the large-scale radiogenic Os flux into the ocean.

Isotope Fractionation of Nitrate During Volatilization in Snow: A Field Investigation in Antarctica

AbstractSeveral postdepositional processes impact snow nitrate; however, only the isotopic effects of nitrate photolysis have been quantified. Here we discuss results from experiments in field Antarctic snow investigating isotopic fractionation of nitrate due to volatilization. At −35 °C, concentration and isotopic composition of nitrate remained constant during the 16‐day experiment. At −24 °C, 7.5% of nitrate was lost, synchronous with 1.5‰ decrease in δ18O and a constant δ15N. At −4 °C, 38% of nitrate was lost, and δ15N and δ18O decreased by 3.1 and 1.8‰, respectively. Results at −4 °C yield calculated fractionation constants close to theoretical estimates including equilibrium isotopic exchange between nitric acid and nitrate and the desorption of nitric acid from water in quasi‐liquid layers. This suggests that isotopic fractionation associated with nitrate volatilization across most of Antarctica, especially at sites with temperatures &lt;−24 °C, should be minor, but the isotopic effects at warmer sites should be considered in interpreting archived nitrate records.

Evaluating the Roles of Rainout and Post-Condensation Processes in a Landfalling Atmospheric River with Stable Isotopes in Precipitation and Water Vapor

Atmospheric rivers (ARs), and frontal systems more broadly, tend to exhibit prominent “V” shapes in time series of stable isotopes in precipitation. Despite the magnitude and widespread nature of these “V” shapes, debate persists as to whether these shifts are driven by changes in the degree of rainout, which we determine using the Rayleigh distillation of stable isotopes, or by post-condensation processes such as below-cloud evaporation and equilibrium isotope exchange between hydrometeors and surrounding vapor. Here, we present paired precipitation and water vapor isotope time series records from the 5–7 March 2016, AR in Bodega Bay, CA. The stable isotope composition of surface vapor along with independent meteorological constraints such as temperature and relative humidity reveal that rainout and post-condensation processes dominate during different portions of the event. We find that Rayleigh distillation controls during peak AR conditions (with peak rainout of 55%) while post-condensation processes have their greatest effect during periods of decreased precipitation on the margins of the event. These results and analyses inform critical questions regarding the temporal evolution of AR events and the physical processes that control them at local scales.

Theoretical Phase Resolved Ammonia–Ammonium Nitrogen Equilibrium Isotope Exchange Fractionations: Applications for Tracking Atmospheric Ammonia Gas-to-Particle Conversion

Nitrogen (N) equilibrium isotope fractionation (15α) involving gaseous, dissolved, and solid phases of ammonia (NH3) and ammonium (NH4+) (e.g., NH3(g)–NH3(aq)–NH4+(aq)–NH4+(s)) represents a fundamental chemical process that has important implications for understanding the environmental dynamics involving NHx (NH3 + NH4+). However, recent literature disagrees with early experimental results from Urey and co-workers, suggesting the need for an update on theoretical estimates. Here, we have calculated theoretical 15α values for NH4+(g)/NH3(g), NH3(aq)/NH3(g), NH4+(aq)/NH3(g), NH4+(aq)/NH3(aq), and NH4+(s)/NH3(g) using HF/6-31G(d) and B3LYP/6-31G(d) levels of theory. Overall, our theoretical calculated values matched experimental data reported by Urey and co-workers, with best agreement obtained at the HF/6-31G(d) level of theory with solvent effect accounted for using water cluster calculations. Our calculated results have important implications for tracing NH3 gas-to-particle phase conversions that may have...

Inter-laboratory test for oxygen and hydrogen stable isotope analyses of geothermal fluids: Assessment of reservoir fluid compositions.

Knowledge of the accuracy and precision for oxygen (δ18 O values) and hydrogen (δ2 H values) stable isotope analyses of geothermal fluid samples is important to understand geothermal reservoir processes, such as partial boiling-condensation and encroachment of cold and reinjected waters. The challenging aspects of the analytical techniques for this specific matrix include memory effects and higher scatter of delta values with increasing total dissolved solids (TDS) concentrations, deterioration of Pt-catalysts by dissolved/gaseous H2 S for hydrogen isotope equilibration measurements and isotope salt effects that offset isotope ratios determined by gas equilibration techniques. An inter-laboratory comparison exercise for the determination of the δ18 O and δ2 H values of nine geothermal fluid samples was conducted among eleven laboratories from eight countries (CeMIEGeo2017). The delta values were measured by dual inlet isotope ratio mass spectrometry (DI-IRMS), continuous flow IRMS (CF-IRMS) and/or laser absorption spectroscopy (LAS). Moreover, five of these laboratories analyzed an additional sample set at least one month after the analysis period of the first set. Statistical evaluation of all the results was performed to obtain the expected isotope ratios of each sample, which were then subsequently used in deep reservoir fluid composition calculations. The overall analytical precisions of the measurements were ± 0.2‰ for δ18 O values and ± 2.0‰ for δ2 H values within the 95% confidence interval. The measured and calculated δ18 O and δ2 H values of water sampled at the weir box, separator and wellhead of geothermal wells suggest the existence of hydrogen and oxygen isotope-exchange equilibrium between the liquid and vapor phases at all sampling points in the well. Thus, both procedures for calculating the isotopic compositions of the deep geothermal reservoir fluid - using either the analytical data of the liquid phase at the weir box together with those of vapor at the separator or the analytical data of liquid and vapor phases at the separator -are equally valid.

Rates and multiple sulfur isotope fractionations associated with the oxidation of sulfide by oxygen in aqueous solution

Sulfide oxidation is a major component of the global sulfur cycle that requires consideration in isotope-based models of aquatic and sedimentary systems, but the isotope fractionations based on analyses of all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) have yet to be documented for abiological sulfide oxidation processes. We present experimental determinations of the reaction rates and sulfur isotope fractionations associated with the oxidation of aqueous sulfide (principally HS−) by molecular oxygen (‘autoxidation’) in high pH (≈9.8), low ionic strength carbonate/bicarbonate buffered solutions as a function of temperature (5–45 °C) and trace metal catalysis (ferrous iron, added [Fe2+] ∼50–150 nM). Rates and isotope fractionations are quantified via the analysis of sulfide as a function of reaction progress over relatively low extents of reaction (ca. 33–47%). The oxidation of sulfide at pH = 9.8 and 25 °C without any catalyst added is associated with a computed second order rate constant (k) of lnk = 3.49 ± 0.38 (k in M−1 hr−1; 2 s.d., quadruple experiments) and major sulfur isotope discrimination of 34εP-R = −5.85 ± 0.43‰ (2 s.d., duplicate experiments) that are both consistent with previous studies, and a corresponding minor sulfur isotope fractionation relationship of 33/34θ = 0.509 ± 0.004 that translates to Δ33SP-R = 0.033 ± 0.018‰ (2 s.d.). The dependence of 34εP-R on reaction rate due to either temperature or ferrous iron catalysis over the ranges we have studied is small (<∼1‰ in 34εP-R) and similar values for 33/34θ and Δ33SP-R are obtained for all conditions studied (e.g., mean of all 7 experiments: 33/34θ = 0.5082 ± 0.0031 and Δ33SP-R = 0.037 ± 0.014‰; 2 s.d.). These results indicate that the process of sulfide autoxidation has a mass dependence that is resolvable from the expectations of typical equilibrium isotope exchange. Values for 36/34θ and Δ36SP-R may also exhibit deviations from typical equilibrium isotope exchange but are not resolved under all conditions studied. The shift in values of 33/34θ and Δ33S (and potentially 36/34θ and Δ36S) is consistent with the hypotheses that kinetic isotope effects can be associated with different mass laws than equilibrium processes or with reversibility occurring in the initial parts of the reaction network leading to oxidation products, but both hypotheses will likely require further investigation. We provide an example of how our experimentally calibrated ‘signature’ for sulfide autoxidation may be identified in natural data using the previously published δ34S and Δ33S values of dissolved sulfide in proximity to the oxic-sulfidic interface in the water column of the Cariaco Basin. The observation that the autoxidation of aqueous sulfide in high pH media is associated with a non-zero Δ33SP-R will influence how chemical oxidation processes are treated in environmental and global scale models of the sulfur cycle based on multiple sulfur isotopes.