Equilibrium Isotope Fractionation Research Articles

Radiocarbon and Stable Carbon Isotope Constraints on the Propagation of Vent CO 2 to Fluid in the Acidic Kueishantao Shallow Water Hydrothermal System

We report radiocarbon and stable carbon isotope measurements from vent gas (CO2(g)), dissolved inorganic carbon (DIC), and particulate organic carbon (POC), from two vents of the Kueishantao (KST) shallow-water hydrothermal system, offshore northeast Taiwan. The purpose of this research is to investigate how magmatic-sourced carbon enters various carbon pools in the hydrothermal system. We utilize a precipitation method to eliminate sulfur compounds from CO2 samples to facilitate Accelerator Mass Spectrometry (AMS) analysis, and evaluate radiocarbon background levels during processing to characterize hydrothermal-sourced CO2 that contains negligible radiocarbon. The result shows that both CO2(g) and DIC in the fluids below two vent orifices fall within a narrow range of fraction of modern carbon (F14C) from 0.013 to 0.136 and δ13C from −8.3‰ to −5.1‰. The F14C values correspond to approximately 90% magmatic-sourced carbon in CO2(g) and DIC. A combination of equilibrium and kinetic isotopic fractionation can adequately explain relatively high CO2(g) δ13C to DIC, beneath vent orifices. Above the vent orifices, DIC becomes enriched in both 14C and 13C as a result of physical mixing with ambient seawater. POC F14C values confirm a significant magmatic carbon contribution into the POC pool within the KST system, with rapid hydrothermal circulation. Our results identify the physiochemical processes responsible for magmatic carbon migration from CO2(g) into the DIC pool, and demonstrate how a dual carbon isotope approach can serve as an effective tool in understanding carbon flow in high temperature-low pH hydrothermal systems.

Determination of the equilibrium magnesium isotope fractionation factors between brucite and aqueous inorganic and organic species

Magnesium (Mg) is a major element in seawater, rock-forming minerals, and biological systems. Stable Mg isotopes fractionate during silicate weathering and carbonate mineralization, and hence are a promising tool to trace these processes. Magnesium can be present in natural aqueous solutions as a number of distinct inorganic and organic complexes including MgHCO3+, MgCO30, MgSO40, Mg(OH)+, Mg(citrate)− and Mg(EDTA)2−, in addition to Mg(H2O)62+ commonly referred to as Mg2+. The formation of these species can significantly alter the fractionation of Mg isotopes between minerals and natural fluids. To quantify these effects, isotope exchange experiments were performed at bulk chemical equilibrium between brucite and aqueous solutions containing different organic (citrate, EDTA) and inorganic (SO4−) ligands at 25 °C. The ‘three isotope’ method was used to determine the equilibrium Mg isotope fractionation factors Δeq26Mg between brucite and several major aqueous magnesium species. The experimentally measured equilibrium Mg isotope fractionation factor between brucite and aqueous Mg2+ was found to be Δeq26Mgbrucite-Mg2+ = -0.35 ± 0.39‰. First-principle calculations to retvieve the brucite β-factor were performed consistently with the calculations of Pinilla et al. (2015) for Mg2+(aq) β-factor. The combination of both studies yield values of Δeq26Mgbrucite-Mg2+ between +0.3 and +0.8 ± 1.0‰, which is the lowest theoretical estimate of this constant obtained to date. An average value Δeq26Mgbrucite-MgSO40 = 0.48 ± 0.16‰ was retrieved from the experiments for the isotope fractionation between brucite and aqueous MgSO40. Mg isotope equilibrium fractionation factors between brucite and aqueous Mg(citrate)− and between brucite and aqueous Mg(EDTA)2− retrieved from the experiments performed in the presence of these organic ligands are Δeq26Mgbrucite-Mg(citrate)− = 0.35 ± 0.21, and Δeq26Mgbrucite-Mg(EDTA)2− = 2.41 ± 0.20‰.The experimental values determined in this study for Δeq26Mgbrucite-Mg2+ agree with the experimental values reported by Li et al. (2014). There is also an excellent agreement between the experimental values of this study and Li et al. (2014) with the density functional theory (DFT) estimates from Schott et al. (2016) for Δeq26MgMg2+-Mg(EDTA)2−. In contrast, the Mg isotope fractionation factor measured in this study between aqueous Mg2+ and both aqueous Mg sulphate or citrate species is significantly smaller than predictions from the ab initio calculations reported by Schott et al. (2016). The results of the present study confirm that the mineral-fluid equilibrium fractionation of Mg isotopes is strongly dependent on the identity of the inorganic or organic ligands present in the aqueous fluid and the nature of the complexes, (e.g. inner-sphere versus outer-sphere complexes), formed by magnesium with these ligands. Therefore, Mg speciation in natural fluids and the structure of aqueous Mg complexes have to be known for an accurate interpretation of Mg isotopic signatures in natural environments.

Equilibrium fractionation of triple-oxygen and hydrogen isotopes between ice and water

The triple-oxygen isotopic fractionation associated with freezing is a fundamental property of water, knowledge of which is essential for reconstructions of the hydrological cycle from the triple-oxygen isotopic composition of natural materials. We constrained this isotopic fractionation, in freshwater and seawater, in a series of freezing experiments over a range of temperatures and freezing rates. The freshwater freezing experiments with the lowest freezing rates, which we consider closest to isotopic equilibrium, yield 18O/16O, 17O/16O and 2H/1H fractionations of 2.82±0.12‰, 1.49 ± 0.07‰ and 20.05 ± 0.72‰, respectively. The slowest-freezing seawater experiments yield 18O/16O, 17O/16O and 2H/1H fractionations of 2.92 ± 0.08‰, 1.55 ± 0.03‰ and 21.18 ± 1.85‰, respectively. The 18O/16O and 2H/1H fractionation estimates in freshwater and seawater are within error of each other and in broad agreement with past estimates. Our newly determined 17O/16O fractionations constrain the triple-oxygen mass dependence of water freezing to be ≈0.528, but with large uncertainty. If this mass dependence is accurate, then ice formation and melting processes in the hydrological cycle are expected to generate variability that is on the Global Meteoric Water Line.

Mineralogy and fluid chemistry controls on lithium isotope fractionation during clay adsorption

Our current understanding of controls on δ7Li variability and fractionation mechanisms is limited, complicating the interpretation of chemical weathering. The role of clay adsorption in Li isotope fractionation during chemical weathering has been confirmed. However, clay assemblage and fluid chemistry are not simple and often variable in weathering settings, potentially modulating Li isotope fractionation on Earth's surface. Here, this research investigated the patterns and processes of Li isotope fractionation during adsorption on kaolinite and smectite with fluid chemistry of 0.001 M NaCl, 0.5 M NaCl, and 0.001 M Na2HPO4. Specifically, the time-dependent experiments with the reaction period up to 15 days revealed that the steady state can be achieved within one day under neutral conditions. The concentration-dependent (initial Li concentration of 2 to 1000 μM) experiments confirmed the accumulation of Li+ in smectite interlayers and adsorption of Li+ only at the external surfaces of kaolinite. Using 0.5 M NaCl solution and the desorption experiments, we hypothesize that outer-sphere Li may exist in the interlayer sites, which can be replaced by excess Na+. In comparison, inner-sphere Li+ (unexchangeable) potentially dominates at the edge surface of clays. The presence of Na2HPO4 increases the binding capacity for Li+ adsorption, in particular for kaolinite. In all cases, 6Li is enriched on clay surfaces and interlayer spaces, consistent with field observations. Fluid chemistry may affect the degree of clay Li adsorption but exerted negligible impacts on isotope fractionation. For kaolinite, a wide variation (up to 30 ‰) in isotopic fractionation between adsorbed and aqueous Li (Δ7Liaq-ad) exists, conforming to a kinetic fractionation mechanism with a constant fractionation factor αad-aq of ~0.992. By contrast, the isotopic fractionation between Li adsorbed on smectite and Li+ left in solutions keeps constant (Δ7Liaq-ad of ~5 ‰), likely following an equilibrium isotope fractionation law with an αad-aq of ~0.995.

Ca-isotopes as a robust tracer of magmatic differentiation

The large mass difference (∼10%) between the two most abundant isotopes of calcium, 40Ca and 44Ca, gives Ca great potential in tracking mass-dependent fractionation during magmatic processes. Resolvable Ca-isotope fractionation during fractional crystallization of magma, particularly by feldspar in evolved melts, has been theoretically inferred but not robustly tested in nature. To further explore the effects of magmatic differentiation on Ca-isotope systematics, we studied the late-Permian alkaline igneous suite of the Øyangen Caldera, Oslo Rift, Norway, consisting of volcanic and intrusive units ranging from basanitic to rhyolitic compositions. Major and trace element variations and modeling demonstrate that the main series of samples (N=21), including basanites, ring-dyke syenites, and central-dome syenites, likely documents a co-genetic and closed-system fractional crystallization sequence. Our data show minimal δ44/40Ca variation (<0.05‰) in the intermediate magma and a marked increase in δ44/40Ca in the felsic magma of the Øyangen Caldera (from 0.62±0.02‰ to 1.15±0.03‰ relative to Ca standard, SRM915a). The systematic increase is best explained by equilibrium isotopic fractionation dominated by alkali feldspar in the fractionating mineral assemblage. This is further supported by strong correlations between δ44/40Ca, CaO, and Eu/Eu* in the main-series samples. Implementing a Monte Carlo approach, isotopic modeling of the liquid line of descent using Rayleigh fractionation is highly consistent with the observed Ca-isotope evolution. For the first time, we confirm prominent Ca stable isotope fractionation in felsic-stage differentiation of alkaline magma and constrain the isotope fractionation factors of plagioclase and K-feldspar. Integrated with extant estimations on mineral fractionation factors from the literature, our results suggest increasing fractionation effects of rock-forming minerals with decreasing Ca content. The affirmation of significant Ca-isotope fractionation in alkaline magma by feldspar empowers the application of Ca as a versatile tracer of crustal evolution, allowing further tests in other magmatic conditions across various planetary objects.

Evaluation of the properties of dolomitization fluids and diagenetic alterations of mg/Ca ratios in carbonate rocks in the cambrian series-2 to miaolingian strata in Central Uplift Belt, Tarim Basin: Constraints from halogens, REEs and isotope geochemistry

The nature of the dolomitization fluids and the diagenetic alterations on carbonate Mg/Ca ratios in Cambrian series-2 to Miaolingian strata in Central Uplift Belt, Tarim Basin are interpreted on the basis of petrography, geochemistry (trace elements, halogens, REEs, O–C–Sr isotopes) and fluid inclusion microthermometry. Based on petrographic examination, two types of less stoichiometric dolomites: dolomicrites (DM), very fine-to fine-crystalline planar-e(s) dolomite (D1) formed at near-surface to shallow-burial settings, and two types of more stochiometric dolomites (fine-to medium-crystalline planar-e(s) dolomite (D2) and medium-to coarse-crystalline.nonplanar-a dolomite (D3)) formed at deep-burial setting are identified. Medium-to coarse-crystalline, nonplanar-a saddle dolomite cement (DC), and early-stage calcite cement (ESCAL) and later-stage calcite cement (LSCAL) are identified. The DM, D1, D2, and D3 samples display positive Cerium anomalies (δCe) and negative Europium anomalies (δEu), and the DC display positive δCe and positive δEu. They show micritic-bladed and blocky calcite-like REE patterns, suggesting their dolomitizing fluids inherited the seawater or seawater-like REE signatures of their precursor carbonate materials at the time of crystal growth. No correlations exist between δ13C, δ18O, 87Sr/86Sr, Mg/Ca, and Mn/Sr which were tools used to evaluate the diagenetic history of the carbonates, coupled with the high Mg/Ca ratios (0.64–0.85), Mn/Sr ratios, and more depleted δ18O, δ13C values of D2, D3, and DC. This suggests that the dolomites were altered by high-temperatures or their isotopic difference may be the result of equilibrium isotopic fractionation. The increasing trend in Cl/(Ca + Mg), I/(Ca + Mg), and Br/(Ca + Mg) ratios in the D2, D3, and DC with dolomite content >50 wt% can be explained by the presence of evaporite (salt) derived from seawater or sedimentary pore waters as fluid interaction with sedimentary materials in the studied strata. The comparable isotopic (δ18O, δ13C and 87Sr/86Sr) values between DM, D1, D2, D3, DC, and coeval Early Paleozoic seawater value, coupled with the relatively high homogenization temperature (Th) and salinity levels in D2, D3, and DC, indicates that their diagenetic fluids were derived from radiogenic 87Sr-enrich coeval seawater with hypersaline signatures in deep-burial settings. The dolomitization model shows that the precipitation of dolomicrites was by evaporative seepage-reflux dolomitization at near-surface burial settings. Evaporative seawater dolomitization supported by 87Sr/86Sr, δ13C values and calculated water oxygen isotope ratio was probably responsible for the D1 during shallow-burial, and D2 and D3 with irregular overgrowth rims were formed during deep-burial dolomitization. The average range of the Th values of DC is 148.2–193.4 °C; mostly overlapping with the estimated ambient temperature (65 °C–180 °C, at a depth >4000 m) for the studied strata, indicates that the growth of DC in fractures may have resulted from upward and laterally squeezed higher-temperature saline-enriched basinal fluids conveyed by geothermal convective-advective fluid flows or squeegee fluid flows at depth resulting in geothermal dolomitization.

The factors controlling equilibrium inter-mineral Ca isotope fractionation: Insights from first-principles calculations

Equilibrium isotope fractionation factors are crucial to quantitatively interpreting Ca isotope data of natural samples. Recent studies have revealed significant equilibrium Ca isotope fractionation between minerals, but the controlling factors remain poorly understood. Using density functional theory, this study calculates the reduced partition function ratios (RPFRs) among amphiboles (richterite and tremolite), sorosilicates (akermanite and gehlenite), K-bearing carbonates (butschliite), Na-bearing diopside (jadeite), and other Ca-bearing minerals (fluorapatite, anhydrite, CaTiO3 perovskite, and fluorite) at 0 GPa. The RPFRs of diopside and anorthite over a pressure range from 0 to 5 GPa are calculated to investigate the pressure effect. The effect of force constant, bond length, coordination number, anion type, solid solution composition, and pressure on RPFRs are discussed by compiling the literature data. The RPFRs show good correlations with the force constant and bond length but have no clear correlation with the coordination number. This suggests that the bond length is more reliable than the coordination number for roughly predicting the signs and magnitudes of inter-mineral isotope fractionation. Na-bearing clinopyroxene (e.g., jadeite) has similar RPFR with Na-free clinopyroxene, suggesting that the jadeite effect should be insignificant in natural samples. The RPFR of anorthite is lower than that of diopside at low pressure, and the two minerals both show a positive correlation between RPFR and pressure. Notably, the heavy Ca isotope enrichment between these two minerals can be reversed at high pressure (>3 GPa at 1000 K) because anorthite’s RPFR changes more sharply with increasing pressure than that of diopside. However, such a reverse may not occur in Earth's modern crust due to the stability of anorthite at lower pressures. Combining the theoretical predictions of amphibole and plagioclase and natural sample observation on granitoids, we infer that the RPFR of granitic magma may be lower than that of basaltic magma.

Diagenetic nutrient supplies to the Proterozoic biosphere archived in divergent nitrogen isotopic ratios between kerogen and silicate minerals.

Nitrogen isotopes and abundances in sedimentary rocks have become an important tool for reconstructing biogeochemical cycles in ancient ecosystems. There are two archives of nitrogen in the rock record, namely kerogen‐bound amines and silicate‐bound ammonium, and it is well documented that the isotopic ratios of these two archives can be offset from one another. This offset has been observed to increase with metamorphic grade, suggesting that it may be related to the bonding environment in differing nitrogen host phases and associated equilibrium isotope fractionation. However, theoretical bounds for this effect have not been established, and it remains possible that some isotopic offsets predate metamorphism. In support of this hypothesis, we report an unexpectedly large isotopic offset of 4–5‰ in siltstones of very low metamorphic grade from the late Mesoproterozoic Diabaig Formation in NW Scotland (1.0 Ga). Carbon to nitrogen ratios of bulk rocks are 2–3 times lower than in other Mesoproterozoic sections. The rocks also contain early‐formed phosphate concretions and display wrinkled surfaces on bedding planes, indicative of fossilised microbial mats. Collectively, these data are most parsimoniously interpreted as evidence of diagenetic ammonium release from microbial mats into porewaters, followed by partial oxidation to nitrite or nitrate at the sediment–water interface. This process would render residual ammonium in clays isotopically heavy, while the resulting nitrite or nitrate would be relatively lighter and captured in new biomass, leading to the observed isotopic divergence. The same diagenetic degradation pathway likely also liberated phosphate that was trapped within concretions. Diagenetic release of nutrients is known to occur in modern settings, and our data suggest that nitrogen isotopes may be a way to track this local sedimentary nutrient source in past environments. Lastly, we speculate that diagenetic nutrient recycling within Proterozoic microbial mats may have created a favourable niche for eukaryotic organisms in shallow waters.

Iron isotope systematics during igneous differentiation in lavas from Kīlauea and Mauna Loa, Hawai'i

The Big Island of Hawai'i is currently the most active site of magmatic activity in the Hawaiian chain of volcanoes that are associated with a mantle plume in the Pacific Ocean. Mantle source variability and magmatic processes have both been proposed to significantly affect lava chemistry on the Big Island, which is most prominently illustrated in a radiogenic isotope dichotomy of the so-called ‘Kea’ and ‘Loa’ trends. Here, we present stable Fe isotopes (δ57Fe), complemented by radiogenic 176Hf/177Hf, in lavas from the Puʻu ʻŌʻō vent on the East Rift Zone of Kīlauea (Kea trend) and from the Southwest Rift Zone from Mauna Loa (Loa trend). In Hf isotopic space, lavas range from εHf = +8 to +13, with Puʻu ʻŌʻō samples aligning with published values of lavas from the ‘Kea-trend’ in SrHf isotope space, whereas Mauna Loa basalts and picrites presented here coincide with values of the Loa-trend. The Puʻu ʻŌʻō lavas have average δ57Fe of +0.15 ‰ and an average of MgO ~ 7 wt%. Mauna Loa basalts and picrites show on average lighter δ57Fe of +0.06 ‰ but higher MgO ~ 16 wt%. Combined, in a global OIB comparison, the Hawaiian samples have among the lowest δ57Fe reported to date. Both Puʻu ʻŌʻō and Mauna Loa lavas lie on a trend of decreasing δ57Fe with increasing MgO that is ascribed to olivine fractionation and accumulation. Geochemical indices of partial melting (e.g., (Gd/Yb)PM, TiO2) do not align with Fe isotopic signatures, whether corrected for crystal fractionation or not, and can thus not explain the heavy Fe isotopic signatures observed here. Likewise, a lack of co-variations of radiogenic isotopes with Fe isotopes do not support source inheritance from enriched, crustal-like plume components as the dominant process to explain the Fe isotopic signatures. On a three‑iron isotope plot, it appears that kinetic in combination or in exchange with equilibrium fractionation of stable isotopes can account for Fe isotopes lighter than δ57Fe < +0.15 ‰. An inherently heavy Fe isotope signature (> 0.15 ‰) is required to explain some of the high values measured here for which no geochemical proxy can be identified. Assuming fast recharge into the plumbing systems feeding Puʻu ʻŌʻō and Mauna Loa lavas with no presumed homogenisation in subsurface magma chambers, we surmise that the Hawaiian samples are reflecting lavas that experienced a combination of kinetic and equilibrium processes, which ultimately lead to a seemingly random distribution of Fe isotopes. The exposure to different magmatic processes, e.g., re-charging events, and the missing covariation between MgO vs δ57Fe argue for an open magma chamber underneath Puʻu ʻŌʻō and Mauna Loa, masking processes that influence Fe isotopes, i.e., source inheritance or melting degree. From our new stable Fe isotope data, we show that lavas, which travel through a plumbing system, can undergo multiple fractionation processes.

Magnetite geochemistry and iron isotope signature of disseminated and massive mineralization in the Kalatongke magmatic Cu[sbnd]Ni sulfide deposit, northwest China

Magnetite is a common accessory mineral and an indicator to magma evolution and sulfide fractional crystallization in magmatic NiCu sulfide deposits. The Kalatongke magmatic sulfide deposit at the southern margin of the Central Asian Orogenic Belt is composed of 11 mafic intrusions. The sulfide orebodies (Y1, Y1 deep, and Y2) are hosted by three small mafic intrusions, and magnetite is common in all mineralized samples. Based on ilmenite exsolution texture, composition, and type of mineralization, three types of magnetite are identified, (1) primary Fe-rich magma-related magnetite (type 1), (2) sulfide liquid-related magnetite (type 2), and (3) hydrothermal magnetite (type 3). We speculate that Fe isotope equilibrium fractionation between early or co-crystallized light 54Fe-enriched sulfide and magnetite may account for the ultra-high magnetite δ56Fe value (0.70‰ to 1.35 ‰) in the magmatic magnetite (types 1 and 2). Enriched compatible elements in type 1 magnetite (TiO2 = 1.52 wt% to 7.89 wt%, V = 775 ppm to 2420 ppm, Cr = 2697 ppm to 14,658 ppm, and Ni contents = 478 ppm to 1256 ppm), reflect the characteristics of primary Fe-rich magmatic magnetite crystallized at relatively high temperature and low oxygen fugacity. Type 2 magnetite in massive ores has Ni (762 ppm to 1769 ppm) and δ56Fe (0.89 ‰ to 1.10 ‰) values similar to type 1 magnetite, but significantly lower TiO2, V and Cr contents (TiO2 = 0.07 to 3.72 wt%, V = 61 to 2314 ppm, Cr = 5 to 2937 ppm), indicating co-crystallization with an evolved sulfide liquid across a wide span of temperature and oxygen fugacity. Type 3 magnetite is of hydrothermal fluid origin, with low δ56Fe (0.29 ‰ to 0.41 ‰) and Ni (177 ppm to 377 ppm).Magnetite composition and Fe isotope signatures at the Kalatongke magmatic sulfide deposit can reveal the genesis of magnetite and the evolution of the melt and sulfide. The Y1 orebody was completely crystallized over a short period of time, while the Y1 deep and Y2 east orebodies underwent a protracted evolution during which magnetite co-crystallized from primitive Fe-rich melt, Fe-rich evolved melt and Cu-rich intermediate sulfide solution. Magnetite and sulfide in the Y2 west massive orebody likely formed last. The compatibility of both lithophile and chalcophile elements, combined with Fe isotopes in magnetite, makes magnetite a good indicator of silicate and sulfide melt evolution.

Nickel Isotope Fractionation As an Indicator of Ni Sulfide Precipitation Associated with Microbially Mediated Sulfate Reduction.

Microbially mediated sulfate reduction is a promising cost-effective and sustainable process utilized in permeable reactive barriers (PRB) and constructed wetlands to treat mine wastewater. Laboratory batch experiments were performed to evaluate nickel (Ni) isotope fractionation associated with precipitation of Ni-sulfides in the presence of the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricansT (DSM-642). Precipitates were collected anaerobically and characterized by synchrotron powder X-ray diffraction (PXRD), scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDS), and transmission electron microscopy (TEM). Solid-phase analyses showed that the precipitates associated with bacteria attached to the serum bottle walls were characterized by enhanced size and crystallinity. Lighter Ni isotopes were preferentially concentrated in the solid phase, whereas the solution was enriched in heavier Ni isotopes compared to the input solution. This fractionation pattern was consistent with closed-system equilibrium isotope fractionation, yielding a fractionation factor of Δ60Nisolid-aq = -1.99‰. The Ni isotope fractionation measured in this study indicates multiple Ni reaction mechanisms occurring in the complex SRB-Ni system. The results from this study offer insights into Ni isotope fractionation during interaction with SRB and provide a foundation for the characterization and development of Ni stable isotopes as tracers in environmental applications.

Resolving impact volatilization and condensation from target rock mixing and hydrothermal overprinting within the Chicxulub impact structure

This work presents isotopic data for the non-traditional isotope systems Fe, Cu, and Zn on a set of Chicxulub impactites and target lithologies with the aim of better documenting the dynamic processes taking place during hypervelocity impact events, as well as those affecting impact structures during the post-impact phase. The focus lies on material from the recent IODP-ICDP Expedition 364 Hole M0077A drill core obtained from the offshore Chicxulub peak ring. Two ejecta blanket samples from the UNAM 5 and 7 cores were used to compare the crater lithologies with those outside of the impact structure. The datasets of bulk Fe, Cu, and Zn isotope ratios are coupled with petrographic observations and bulk major and trace element compositions to disentangle equilibrium isotope fractionation effects from kinetic processes. The observed Fe and Cu isotopic signatures, with δ56/54Fe ranging from −0.95‰ to 0.58‰ and δ65/63Cu from −0.73‰ to 0.14‰, mostly reflect felsic, mafic, and carbonate target lithology mixing and secondary sulfide mineral formation, the latter associated to the extensive and long-lived (>105 years) hydrothermal system within Chicxulub structure. On the other hand, the stable Zn isotope ratios provide evidence for volatility-governed isotopic fractionation. The heavier Zn isotopic compositions observed for the uppermost part of the impactite sequence and a metamorphic clast (δ66/64Zn of up to 0.80‰ and 0.87‰, respectively) relative to most basement lithologies and impact melt rock units indicate partial vaporization of Zn, comparable to what has been observed for Cretaceous-Paleogene boundary layer sediments around the world, as well as for tektites from various strewn fields. In contrast to previous work, our data indicate that an isotopically light Zn reservoir (δ66/64Zn down to −0.49‰), of which the existence has previously been suggested based on mass balance considerations, may reside within the upper impact melt rock (UIM) unit. This observation is restricted to a few UIM samples only and cannot be extended to other target or impact melt rock units. Light isotopic signatures of moderately volatile elements in tektites and microtektites have previously been linked to (back-)condensation under distinct kinetic regimes. Although some of the signatures observed may have been partially overprinted during post-impact processes, our bulk data confirm impact volatilization and condensation of Zn, which may be even more pronounced at the microscale, with variable degrees of mixing between isotopically distinct reservoirs, not only at proximal to distal ejecta sites, but also within the lithologies associated with the Chicxulub impact crater.

Improved volume variable cluster model method for crystal-lattice optimization: effect on isotope fractionation factor

The isotopic fractionation factor and element partition coefficient can be calculated only after the geometric optimization of the molecular clusters is completed. Optimization directly affects the accuracy of some parameters, such as the average bond length, molecular volume, harmonic vibrational frequency, and other thermodynamic parameters. Here, we used the improved volume variable cluster model (VVCM) method to optimize the molecular clusters of a typical oxide, quartz. We documented the average bond length and relative volume change. Finally, we extracted the harmonic vibrational frequencies and calculated the equilibrium fractionation factor of the silicon and oxygen isotopes. Given its performance in geometrical optimization and isotope fractionation factor calculation, we further applied the improved VVCM method to calculate isotope equilibrium fractionation factors of Cd and Zn between the hydroxide (Zn–Al layered double hydroxide), carbonate (cadmium-containing calcite) and their aqueous solutions under superficial conditions. We summarized a detailed procedure and used it to re-evaluate published theoretical results for cadmium-containing hydroxyapatite, emphasizing the relative volume change for all clusters and confirming the optimal point charge arrangement (PCA). The results showed that the average bond length and isotope fractionation factor are consistent with those published in previous studies, and the relative volume changes are considerably lower than the results calculated using the periodic boundary method. Specifically, the average Si–O bond length of quartz was 1.63 Å, and the relative volume change of quartz centered on silicon atoms was − 0.39%. The average Zn–O bond length in the Zn–Al-layered double hydroxide was 2.10 Å, with a relative volume change of 1.96%. Cadmium-containing calcite had an average Cd–O bond length of 2.28 Å, with a relative volume change of 0.45%. At 298 K, the equilibrium fractionation factors between quartz, Zn–Al-layered double hydroxide, cadmium-containing calcite, and their corresponding aqueous solutions were Delta ^{30/28} {text{Si}}_{{{text{Qtz-H}}_{4} {text{SiO}}_{4} }} = 2.20{permil} , Delta^{18/16} {text{O}}_{ {text{Qtz}}{-} ( {text{H}}_{2} {text{O}} )_{text{n}}} = 36.05{permil}, Delta^{66/64} {text{Zn}}_{ {text{Zn}} {-} {text{Al LDH-Zn}} ( {text{H}}_{2} {text{O}} )_{text{n}}^{2+}} = 1.12{permil} and Delta^{114/110} {text{Cd}}_{ {text{(Cd--Cal)-Cd}} ( {text{H}}_{2} {text{O}} )_ {text{n}}^{2 +} } = - 0.26{permil} respectively. These results strongly support the reliability of the improved VVCM method for geometric optimization of molecular clusters.

A unified method for measuring noble gas isotope ratios in air, water, and volcanic gases via dynamic mass spectrometry

We describe a new method for the purification, transfer, and analysis of heavy noble gas isotope ratios in water, air, or volcanic gas samples using a dynamic dual-inlet isotope-ratio mass spectrometer (IRMS). IRMS noble gas analysis offers the potential for orders-of-magnitude higher precision than traditional (static) noble gas mass spectrometry. However, due to both inherent IRMS requirements and challenges associated with sample collection and purification, measuring noble gases via IRMS has typically been limited to samples with an air-like elemental composition. Our new method allows for highly accurate and precise measurements of Ar, Kr, and Xe isotope ratios via IRMS, independent of sample composition, thereby opening the door to air, water, or volcanic gas analyses all made with the same technique. This approach exploits the fact that purified heavy noble gas samples are dominated by 40Ar, such that matching 40Ar ion beams between sample and reference gas streams results in pressure balancing. We further introduce new techniques for precisely quantifying and correcting for (i) Kr and Xe isotope non-linearity and matrix effects, (ii) interference of the low energy 40Ar tail on 36Ar and 38Ar ion beams, and (iii) the impact of short-term background fluctuations on trace Xe isotope measurements. We also present results from adsorption-desorption experiments with multiple adsorbent materials across a range of temperatures. For adsorption on silica gel, we find small equilibrium isotopic fractionation of Kr (εeq = −0.37 ± 0.04‰ amu−1, ±2 SE) and Xe (εeq = −0.06 ± 0.02‰ amu−1, ±2 SE) that may be relevant to studies of terrestrial Xe isotope signatures. We demonstrate that adsorption and desorption of heavy noble gases on silica gel at 77 K and 303 K, respectively, is highly reproducible and thus constitutes a viable and efficient method for transferring gases without reliance on cryostats or liquid helium.

Testing the isotopic equilibrium fractionation on active speleothem based on cave monitoring

Testing the isotopic equilibrium fractionation on active speleothem based on cave monitoring

Density functional theory calculations of nitrogen and oxygen equilibrium isotope fractionations in NO3−–NO2−–H2O aqueous system reveal inverse kinetic isotope effects during nitrite oxidation

Nitrate and nitrite play key roles in the nitrogen cycle on Earth's surface. The isotope fractionation during nitrate reduction on enzymatic level involves multiple steps, including transfer of free NO3− to the activate site on nitrate reductase and NO2− equilibration with ambient water. However, the isotope fractionation factors of 15N and 18O among NO3−, NO2−, and H2O molecules in aqueous phases are poorly constrained. It strongly impedes the understanding of the involved processes and using stable isotopes to quantitatively examine the biogeochemical nitrogen cycle. In this contribution, we employ the density functional theory method with the Urey-Bigeleisen-Goeppert-Mayer model to predict the nitrogen and oxygen equilibrium isotope fractionation factors of NO3−, NO2−, and H2O molecules in gaseous and aqueous phases. Our calculation results show that the solvent effect has a large influence on equilibrium isotope fractionation for oxygen in water (+10.1‰ between liquid and vapor water at 25 °C), which is different to the little solvent effects on both oxygen and nitrogen in nitrate and nitrite. The calculated temperature-dependent equilibrium isotope fractionations between nitrogen of NO3− and NO2−, and oxygen of H2O and NO2− are consistent with previous laboratory experiments. Our results confirm that the oxygen equilibrium isotope fractionations between NO3− and NO2− should be +9.4‰ at 25 °C. Integrating the new results and previously reported kinetic isotope effects of nitrate reduction, we demonstrate inverse kinetic isotope effects for both nitrogen (+15.4‰) and oxygen (+5.2‰) during nitrite oxidation, which falls in the range of previous experiments. The new results enable us to use both nitrogen and oxygen isotopes as a bonded isotope tool to quantitatively assess the nitrogen cycle in low-temperature environments.

Near-zero 33S and 36S anomalies in Pitcairn basalts suggest Proterozoic sediments in the EM-1 mantle plume

Volcanic rocks erupted among Pitcairn seamounts sample a mantle plume that exhibits an extreme Enriched Mantle-1 signature. The origin of this peculiar mantle endmember remains contentious, and could involve the recycling of marine sediments of Archean or Proterozoic ages, delaminated units from the lower continental crust, or metasomatized peridotites from a lithospheric mantle. Here, we report the sulfur multi-isotopic signature (32S, 33S, 34S, 36S) of 15 fresh submarine basaltic glasses from three Pitcairn seamounts. We observe evidence for magmatic degassing of sulfur from melts erupted ∼2,000 meters below seawater level (mbsl). Sulfur concentrations are correlated with eruption depth, and range between 1300 ppm S (collected ∼ 2,500 mbsl) and 600 ppm S (∼2,000 mbsl). The δ34S values can be accounted for under equilibrium isotope fractionation during degassing, with αgas-melt between 1.0020 and 1.0001 and starting δ34S values between −0.9‰ and +0.6‰. The δ34S estimates are similar or higher than MORB signatures, suggesting the contribution of recycled sulfur with a ∼ 1‰ 34S enrichment compared to the Pacific upper mantle. The Δ33S and Δ36S signatures average at +0.024±0.007‰ and +0.02±0.07‰ vs. CDT, respectively (all 1σ). Only Δ33S is statistically different from MORB, by +0.02‰. The Δ33S enrichment is invariant across degassing and sulfide segregation. We suggest it reflects a mantle source enrichment rather than a high-temperature fractionation of S in the basalts. Despite the small magnitude of the 33S-36S variations, our data require a substantial amount of recycled sulfur overwhelm the Pitcairn mantle source. We show that models involving metasomatized peridotites, lower crust units, or Archean sediments, may be viable, but are restricted to narrow sets of circumstances. Instead, scenarios involving the contribution of Proterozoic marine sediments appear to be the most parsimonious explanation for the EM-1 signature at Pitcairn.

Isotopic responses of magnesium to two types of dissolution-reprecipitation processes for the growth of the double-carbonate mineral norsethite

Abstract An important mechanism of carbonate mineral growth is dissolution-reprecipitation, including the transformation of amorphous precursor to crystalline carbonates, and coarsening (ripening) of fine carbonate crystals. However, the mechanistic details of cation exchange associated with carbonate mineral growth via a dissolution-reprecipitation process are still not well understood. In this study, we used Mg isotopes to probe the exchange of Mg between aqueous solutions and norsethite [BaMg(CO3)2] by systematic synthesis experiments. Norsethite is a model double carbonate, with a general formula of AB(CO3)2, where A and B stand for two different divalent ions. Formation of norsethite is comprised of three stages, including: (1) precipitation of barium-magnesium (Ba-Mg) amorphous carbonate; (2) transformation of Ba-Mg amorphous carbonate to nano-crystalline norsethite by fast dissolution-reprecipitation; and (3) coarsening (ripening) of nano-norsethite by slow dissolution-reprecipitation. Magnesium isotopes displayed distinct fractionation behaviors in each of the three stages. The Mg isotope fractionation factors (∆26Mgsolid-aq) associated with precipitation of Ba-Mg amorphous carbonate were slightly negative and temperature-dependent, from –0.83‰ at 30 °C to –0.53‰ at 70 °C. During the transformation of Ba-Mg amorphous carbonate to nano-crystalline norsethite, isotopically light Mg isotopes were further enriched in the solid phase, with apparent ∆26Mgsolid-aq decreasing to –2.12‰ at 30 °C and –1.56‰ at 70 °C. In the ripening stage, norsethite became isotopically heavier, with ∆26Mgsolid-aq increasing up to –1.95‰ at 30 °C and –1.17‰ at 70 °C. The experimental results show that non-equilibrium isotope fractionation occurred during the transformation of amorphous carbonate to nano-crystalline norsethite (i.e., fast dissolution-reprecipitation). By contrast, the subsequent ripening of the norsethite led to the evolution toward isotopic equilibrium of the system by slower exchange with a longer reaction time (i.e., slow dissolution-reprecipitation). Moreover, our first-principles calculation results indicate that the equilibrium isotope fractionation was approached, but not attained, even after 276 days of recrystallization at temperatures below 70 °C. In short, this study has identified two different types of dissolution-reprecipitation process during the carbonate mineral growth and highlights the importance of understanding formation mechanism and post-depositional history of carbonate in interpreting the isotopic data of carbonate minerals.

Effect of growth rate and pH on Li isotope fractionation during its incorporation in calcite

Lithium isotope compositions were determined for synthetic calcite and fluid, reported in Füger et al. (2019). Calcite was precipitated at 25 °C, and mineral growth rate and pH varied within the range of 10−8.1 ≤ rp (mol m−2 s−1) ≤ 10−7.2 and 6.3 ≤ pH ≤ 9.5, respectively. At pH = 8.25 ± 0.15, the Δ7Licalcite-fluid = δ7Licalcite - δ7Lifluid value of −2.76 ± 0.22‰ (n = 4) was yielded when calcite growth rate was lower than ∼ 10−7.7 (mol m−2 s−1). As calcite growth rate increased, Δ7Licalcite-fluid values progressively decreased to about −4.5‰. The dependence of Li isotope fractionation on calcite growth rate is described by the surface reaction kinetic model developed by DePaolo (2011). In this model the equilibrium and kinetic isotope fractionation factors obtain values of −2.7 ± 0.1‰ and −8.8 ± 0.1‰, respectively. In addition, for experiments performed under similar surface-normalized growth rate of 10−7.7±0.2 (mol m−2 s−1) a significant decrease in Δ7Licalcite-fluid from pH 9.5 to 6.3 was observed. These variations of Δ7Licalcite-fluid as a function of pH for experiments performed under low degrees of solution saturation with respect to calcite point towards the incorporation of two or more Li-bearing species in the solid phase. Thus, the Li isotope composition of the solid reflects the abundance of these species, which depends on solution pH and fluid composition.Overall the results of this study suggest that both calcite growth rate and pH are parameters that can significantly affect the measured Li isotope fractionation between calcite and fluid. The high sensitivity of Δ7Licalcite-fluid to calcite growth rate observed in this study suggests that a high variability of δ7Licalcite in natural samples, such as foraminifera, brachiopods, and speleothems can be expected in natural environments. The implications for the potential use of elemental and isotope fractionation of Li during calcite formation are discussed in the light of reconstruction of paleo-environmental conditions.

Unprecedently large 37Cl/35Cl equilibrium isotopic fractionation on nano-confinement of chloride anion

Confinement can result in unusual properties leading to new, exciting discoveries in the nano-realm. One such consequence of confinement at the nanoscale is extremally large isotopic fractionation, especially at sub-van der Waals distances. Herein, on the example of chlorine isotope effects, we show that at conditions of nanoencapsulation these effects may reach values by far larger than observed for the bulk environment, which in the case of nanotubes can lead to practical applications (e.g., in isotopic enrichment) and needs to be considered in analytical procedures that employ nanomaterials.