Li Isotope Research Articles

Extreme lithium isotope fractionation in quartz from the Stewart pegmatite

Pegmatites are magmatic bodies consisting of centimeter to meter sized crystals and can sometimes be a source for critical economic resources such as lithium (Li). Determining the chemistry and kinetics involved in pegmatite formation may be important for understanding the element enrichment process. Here, we analyzed the Li isotope compositions of quartz crystals from the Stewart pegmatite in southern California, USA. We find large Li isotopic fractionations: >40‰ between different crystals and >20‰ from core to rim in a single crystal. Two mechanisms for these extreme fractionations were considered: rapid crystal growth rate and Rayleigh fractionation. We find that although rapid crystal growth rate (1–10 m/day) can explain elemental variations, rapid growth alone is unable to explain the most extreme isotopic fractionations. Rayleigh fractionation can account for the largest isotopic fractionations if 96–99.9% of the Li is removed from the system through crystallization of lepidolite and spodumene, but alone cannot explain the observed elemental variability in the quartz. We thus suggest that both processes operated. Trace element enrichments may be more sensitive to growth rate while Li isotope ratios may be more sensitive to changes in the isotopic composition of the pegmatitic fluids during crystallization of the quartz.

Distinct Geochemical Behavior of Water in Olivine between Silicate and Carbonatite Metasomatism

Metasomatism by silicate or carbonatite melts can significantly modify the mineral physical and chemical properties, and the hydrogen geochemical behavior during the interaction of olivine and melt remains unclear. In this study, olivine wate content was measured by SIMS on two peridotite xenolith suites. The water content in the silicate-metasomatized olivine increases along with the metasomatism intensity, whereas the opposite trend is present in the carbonatite-metasomatized ones. These results reflect that H enters olivine via silicate metasomatism, whereas it is extracted by carbonatite melts due to its high-water solubility. In addition, as 7Li (more hydrotropic than 6Li) have more similar geochemical behavior to H, 7Li preferentially enter olivine during silicate metasomatism, but remain in the melt during carbonatite metasomatism, resulting in distinct Li isotope behavior during the two different metasomatism. Therefore, the water content of olivine can be used to distinguish metasomatic melts, as well as to explain the δ7Li differentiation.

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.

Extraction separation of lithium isotopes with Bromobenzene-15-crown-5/ionic liquids system: Experimental and theoretical study

Controlled fusion energy is considered to be one kind of sustainable energy source with clean and green properties. The fusion process requires a large number of lithium isotopes, but the naturally stable lithium isotopes 6Li and 7Li cannot be directly applied to the fusion process and must be further enriched. In this paper, a system for the separation of lithium isotopes by extraction was investigated, which mainly consists of bromobenzene-15-crown-5 and ionic liquids. The effects of ionic liquids, lithium salts, crown ether concentration, and temperature on the separation performance of lithium isotopes were explored. It was found that 6Li was enriched in the organic phase and the single-stage separation factor reached 1.032. It was proved by the temperature experiment that the exchange of lithium isotopes was a spontaneous and exothermic process. The complexation ratio of crown ether and lithium ions was 1:1. The optimized complexation model and the interaction of crown ether and lithium ions were calculated by DFT and Multiwfn. Lithium ions were weakly bonded to the crown ether and strongly bonded to the water molecule as demonstrated by the non-bonded interactions and Mayer bond order of Li-O. Meanwhile, the mechanism of lithium isotope separation with crown ether was clarified by mutual verification of experiment and theoretical calculations.

Characterization of Thermoluminescent Dosimeters for Neutron Dosimetry at High Altitudes.

Neutrons constitute a significant component of the secondary cosmic rays and are one of the most important contributors to natural cosmic ray radiation background dose. The study of the cosmic ray neutrons’ contribution to the dose equivalent received by humans is an interesting and challenging task for the scientific community. In addition, international regulations demand assessing the biological risk due to radiation exposure for both workers and the general population. Because the dose rate due to cosmic radiation increases significantly with altitude, the objective of this work was to characterize the thermoluminescent dosimeter (TLDs) from the perspective of exposing them at high altitudes for longtime neutron dose monitoring. The pair of TLD-700 and TLD-600 is amply used to obtain the information on gamma and neutron dose in mixed neutron-gamma fields due to the present difference in 6Li isotope concentration. A thermoluminescence dosimeter system based on pair of TLD-600/700 was characterized to enable it for neutron dosimetry in the thermal energy range. The system was calibrated in terms of neutron ambient dose equivalent in an experimental setup using a 241Am-B radionuclide neutron source coated by a moderator material, polyethylene, creating a thermalized neutron field. Afterward, the pair of TLD-600/700 was exposed at the CERN-EU High-Energy Reference Field (CERF) facility in Geneva, which delivers a neutron field with a spectrum similar to that of secondary cosmic rays. The dosimetric system provided a dose value comparable with the calculated one demonstrating a good performance for neutron dosimetry.

Differentiation between carbonate and silicate metasomatism based on lithium isotopic compositions of alkali basalts

Abstract Carbonate and silicate metasomatism occurring in subduction zones is an important mechanism underlying mantle heterogeneity and compositional diversity of mantle-derived rocks. However, distinguishing between the two kinds of metasomatism is often difficult. Lithium (Li) and its isotopes have great potential in this regard because of the different Li isotopic compositions of recycled marine carbonate and silicate components. We report Li isotopic data from Cenozoic and Mesozoic alkali basalts of the West Qinling orogen in central China. Relative to those for normal basalts, very high δ7Li values (up to +11.2‰) were observed for the Cenozoic alkali basalts, but significantly and systematically lower values (as low as −3.3‰) were estimated for the Mesozoic alkali basalts. Their abnormal Li isotopic compositions, combined with major- and trace-element contents and Sr-Mg isotope ratios, indicate that the Cenozoic and Mesozoic alkali basalts originated from carbonated and silicated mantle sources, respectively, reflecting metasomatism of the mantle by slab-derived carbonate and silicate melts during Paleotethyan oceanic subduction. Interactions of such melts with the mantle peridotite in subduction channels can account for the elemental and isotopic differences of the studied alkali basalts. The present study demonstrates an effective way to distinguish between carbonate and silicate metasomatism in subduction zones by studying Li isotopic compositions of alkali basalts and highlights the prospect of Li isotopes in tracing the deep carbon cycle.

Tracing the origin of lithium in Li-ion batteries using lithium isotopes

Rechargeable lithium-ion batteries (LIB) play a key role in the energy transition towards clean energy, powering electric vehicles, storing energy on renewable grids, and helping to cut emissions from transportation and energy sectors. Lithium (Li) demand is estimated to increase considerably in the near future, due to the growing need for clean-energy technologies. The corollary is that consumer expectations will also grow in terms of guarantees on the origin of Li and the efforts made to reduce the environmental and social impact potentially associated with its extraction. Today, the LIB-industry supply chain is very complex, making it difficult for end users to ensure that Li comes from environmentally and responsible sources. Using an innovative geochemical approach based on the analysis of Li isotopes of raw and processed materials, we show that Li isotope ‘fingerprints’ are a useful tool for determining the origin of lithium in LIB. This sets the stage for a new method ensuring the certification of Li in LIB.

Lithium Isotope Geochemistry in the Barton Peninsula, King George Island, Antarctica

Lithium (Li) has two stable isotopes, 6Li and 7Li, whose large relative mass difference is responsible for significant isotopic fractionation during physico-chemical processes, allowing Li isotopes to be a good tracer of continental chemical weathering. Although physical erosion is dominant in the Polar regions due to glaciers, increasing global surface temperature may enhance chemical weathering, with possible consequences on carbon biogeochemical cycle and nutriment flux to the ocean. Here, we examined elemental and Li isotope geochemistry of meltwaters, suspended sediments, soils, and bedrocks in the Barton Peninsula, King George Island, Antarctica. Li concentrations range from 8.7 nM to 23.3 μM in waters, from 0.01 to 1.43 ppm in suspended sediments, from 9.56 to 36.9 ppm in soils, and from 0.42 to 28.3 ppm in bedrocks. δ7Li values are also variable, ranging from +16.4 to +41.1‰ in waters, from −0.4 to +13.4‰ in suspended sediments, from −2.5 to +6.9‰ in soils, and from −1.8 to +11.7‰ in bedrocks. Elemental and Li isotope geochemistry reveals that secondary phase formation during chemical weathering mainly control dissolved δ7Li values, rather than a mixing with sea salt inputs from atmosphere or ice melting. Likewise, δ7Li values of suspended sediments and soils lower than those of bedrocks indicate modern chemical weathering with mineral neoformation. This study suggests that increasing global surface temperature enhances modern chemical weathering in Antarctica, continuing to lower δ7Li values in meltwater with intense water-rock interactions.

Experimental Investigation of Oxide Leaching Methods for Li Isotopes.

To examine the applicability of different leaching methods used to extract secondary oxides from silicate solids for lithium isotope (δ7Li) measurement, this study has conducted leaching experiments on five different types of silicate solids, including a fresh basalt, two weathered basalts, a Yellow River sediment (loess‐dominated) and a shale. Four factors were assessed in the experiments: the concentration of the leaching reagent hydroxylamine hydrochloride (HH), the leaching temperature (20 °C vs 95 °C), the leaching time and the reagent/solid ratio. Based on elemental concentrations and Li isotopes, 0.04 mol l−1 hydroxylamine hydrochloride (HH) in 25% v/v acetic acid at room temperature for 1 h with 40 ml g−1 reagent/solid ratio is recommended. At high temperatures, low δ7Li and high magnesium/iron ratios indicate that minerals other than secondary oxides are dissolved. With increased leaching time, there is no evidence for Li isotopic fractionation at room temperature. However, longer leaching time or increased reagent/solid ratios may increase the risk of leaching from non‐oxide phases. Meanwhile, results suggest that low concentrations of HH are not sufficient to target the secondary oxides evenly, while high concentrations of HH can leach out more non‐oxides. We also examined the optimal oxide leaching method within a full sequential leaching procedure (i.e., exchangeable, carbonate, oxide, clay and residual phases). Elemental concentrations show that no elements exist exclusively in oxides, so it is essential to analyse multi‐elemental concentrations to verify that the leaching has accessed this phase in a given sample. Comparing secondary oxides with their corresponding solutions, we estimate the isotopic fractionation (Δ7Lioxide‐solution) is −16.8‰ to −27.7‰.

Measurement of cosmogenic Li9 and He8 production rates at RENO

We report the measured production rates of unstable isotopes $^9$Li and $^8$He produced by cosmic muon spallation on $^{12}$C using two identical detectors of the RENO experiment. Their beta-decays accompanied by a neutron make a significant contribution to backgrounds of reactor antineutrino events in precise determination of the smallest neutrino mixing angle. The mean muon energy of its near (far) detector with an overburden of 120 (450) m.w.e. is estimated as 33.1 +- 2.3 (73.6 +- 4.4) GeV. Based on roughly 3100 days of data, the cosmogenic production rate of $^9$Li ($^8$He) isotope is measured to be 44.2 +- 3.1 (10.6 +- 7.4) per day at near detector and 10.0 +- 1.1 (2.1 +- 1.5) per day at far detector. This corresponds to yields of $^9$Li ($^8$He), 4.80 +- 0.36 (1.15 +- 0.81) and 9.9 +- 1.1 (2.1 +- 1.5) at near and far detectors, respectively, in a unit of 10$^{-8}$ $\mu^{-1}$ g${^-1}$ cm${^2}$. Combining the measured $^9$Li yields with other available underground measurements, an excellent power-law relationship of the yield with respect to the mean muon energy is found to have an exponent of $\alpha$ = 0.75 +- 0.05.

A rapid method of simultaneous chromatographic purification of Li and Mg for isotopic analyses using MC-ICP-MS

Lithium (Li) and Magnesium (Mg) isotopes have been widely used as valuable tracers to study geological processes. In general, several column separation procedures have been used to separate Li and Mg. In this study, we present an optimized protocol for the rapid and simultaneous purification of Li and Mg, which significantly reduces the separation time, required reagent volume, and procedural blanks compared to previous methods. Samples with small amounts of Li (generally 5 ng Li yielding Mg masses of 1–1200 μg) were separated, with the corresponding yields of Li and Mg being nearly 100%. Lithium and Mg isotope analyses were performed using an MC-ICP-MS (Thermo Scientific NEPTUNE Plus) and only <0.2 ng Li and <150 ng Mg were consumed for each analysis. Matrix-doping experiments reveal that the matrix effect is negligible for the determination of Li and Mg isotopes from a wide array of geological samples using our protocol. The robustness of the protocol has been validated by replicated analyses of standard solutions and geological standards, which yield long-term external 2σ precision better than ±0.6‰ for δ7Li and ±0.08‰ for δ26Mg. Lithium and Mg isotopic ratios of all reference materials measured in this study agreed well with previous data within uncertainties. The method developed in this study allows for the rapid and high-purity separation of Li and Mg and subsequent high-precision isotopic analyses of these elements.

Lithium isotope fractionation during magmatic differentiation and hydrothermal processes in post-collisional adakitic rocks

To investigate the behavior of Li isotopes during magmatic differentiation and the petrogenesis of Cu-bearing ore deposits, a suite of post-collisional adakitic rocks from Qulong region, southern Tibet, was studied. Their lithologies range from diorite through granodiorite to granite porphyry with the latter containing giant Cu deposits. Detailed evidence of field observation and geochemical signature suggest that these three sets of rocks were most likely formed by various degrees of partial melting and fractional crystallization from the same source. The dioritic enclave, granodiorite and granite porphyry have δ7Li values ranging from 0.2 to 8.2‰, 3.1 to 6.8‰, and 3.9 to 7.4‰, respectively. Most of these samples are overlapping in Li isotope composition, comparable to other granitoids worldwide, indicating insignificant Li isotope fractionation during partial melting and magma differentiation in adakite-like rocks. By contrast, their Li concentrations are mainly controlled by fractional crystallization as suggested from different modal mineralogy. This process does not lead to further enrichment of Cu although they have initial high concentrations (an average of ∼ 104 ppm). In comparison, granite porphyry has extremely high Cu contents (up to 2000 ppm) and their δ7Li values are positively correlated with Cu content, suggesting the involvement of magmatic fluids that most likely exsolved from deep magma chamber. Such fluids not only modified the Li isotopic compositions of granite porphyries, but also extracted metal elements from the highly evolved magma, eventually resulting in the Cu mineralization. Our work here provides new insight into the formation and evolution of the porphyry Cu-bearing deposit.

Element Partitioning and Li‐O Isotope Fractionation Between Silicate Minerals and Crustal‐Derived Carbonatites and Their Implications

AbstractIn order to investigate element partitioning and Li‐O isotope fractionation between silicate minerals and carbonatite melts at variable levels from mantle to crust, we document elemental and Li‐O isotopic data for major minerals from crust‐derived carbonatites at Eppawala, Sri Lanka. Partition coefficients (D) of elements between olivine or clinopyroxene and carbonatite melts are consequently estimated. The estimated D values indicate that Li, Zn, Co, Cr, Mn, and Ni behave compatibly in olivine, while P and Sc are slightly compatible, and V and Al are mildly incompatible. Partition coefficients of elements between clinopyroxene and carbonatite melts are defined here, including highly compatible Li, Sc, Ti, V, Al, and Na, moderately compatible Zn, Co, Cr, and Ga, and incompatible Mn, Ni, P, and Cu. They are systematically higher than literature values obtained from mantle conditions, but their relative compatibilities at different systems are consistent. This indicates that element partitioning between silicates and carbonatite melts is highly temperature‐ and pressure‐dependent and can be used to evaluate geochemical proxies of carbonatite metasomatism, and evolution and mineralization of carbonatite melts. Profile analyses on olivine grains reveal that Fe‐loving elements in olivine could well preserve features of crystal growth and modal metasomatic interaction, while Li and O isotope fractionations are strongly controlled by element diffusion and Li isotopes are robust indicators of cryptic metasomatic interaction.

Lithium isotope behaviour during basalt weathering experiments amended with organic acids

Lithium (Li) isotopes are a tracer of silicate weathering processes, but how they react to different components of organic and plant-assisted weathering is poorly known. To examine the effect of organic acids compared to a strong mineral acid (HCl) on Li isotope behaviour, basalt-water weathering experiments were amended with different organic acids (glycine, malic acid, cinnamic acid, and humic acid; 0.01 M). The presence of the different acids significantly affects the behaviour of dissolved elemental concentrations (such as Mg, Fe, and Al), both by increasing primary rock dissolution and hindering rates of secondary mineral formation. However, the behaviour of Li isotopes appears unaffected, with all experiments following an almost identical trend of δ7Li versus Li/Na. This observation was consistent with a single fractionation factor during the uptake of Li into secondary minerals, yet both calculated saturation states and leaching experiments on the reacted solids indicated that Li was removed into multiple phases, suggesting that the bulk combined fractionation factor barely varied. Of the Li lost from solution in the organic experiments, we estimated that on average 76% went into neoformed clays, 16% into oxides/oxyhydroxides, and 10% into the exchangeable fraction. The fractionations observed for each phase were Δ7Liexch-soln = −12.7 ± 1.7‰, Δ7Liox-soln = −26.7 ± 0.4‰, and Δ7Liclay-soln = −21.6 ± 3.3‰. These fractionations were identical, within error, to those from experiments with organic-free water, implying that the Li isotope behaviour was unaffected by the presence of organic acids in the weathering reaction. This result has interesting consequences for the interpretation of Li isotopes in terms of plant-assisted weathering and the geological record of terrestrialisation. In particular, it appears to imply that seawater Li isotope records can be expected to resolve the integrated effect of plants on weathering fluxes or weathering congruence, rather than being sensitive to specific organic-mediated weathering mechanisms.

Weathering intensity and lithium isotopes: A reactive transport perspective

Lithium isotopes have emerged as a powerful tool to probe the response of global weathering to changes in climate. Due to the preferential incorporation of ^6^Li into clay minerals during chemical weathering, the isotope ratio δ^7^Li may be used to interrogate the balance of primary mineral dissolution and clay precipitation. This balance has been linked to relative rates of chemical and physical denudation, such that dissolved δ^7^Li (δ^7^Li~diss~) is highest at moderate weathering intensities when chemical and physical denudation are comparable. However, we argue that current theory linking δ^7^Li to weathering regimes through fluid travel times are unable to explain observations of low δ^7^Li and high Li concentrations in rapidly eroding settings. In this study, we re-examine the relationships between δ^7^Li, Li concentration, and weathering regime by incorporating Li isotopes into simulations of weathering profiles using a reactive transport model (CrunchFlow) that includes advective fluxes of regolith to simulate variable erosion rates in response to uplift. In these simulations, fractionation is implemented through a kinetic fractionation factor during clay precipitation, which allows the δ^7^Li of dissolved and suspended loads in the model to vary as a function of Li/Al ratios in primary and secondary minerals. When the model is run over a range of infiltration and erosion rates, simulations reproduce observed global patterns of δ^7^Li~diss~ and suspended load δ^7^Li as a function of weathering intensity, controlled primarily by water travel times and mineral residence times in weathered bedrock. We find that reduced water travel times at low weathering intensity, however, are inconsistent with observations of high Li concentrations. As an alternative, we demonstrate how the rapid weathering of soluble, Li-rich minerals such as chlorite under low weathering intensities may resolve this apparent discrepancy between data and theory. We also suggest that observed patterns are consistent with geothermal Li sources under low weathering intensities. This work offers a foundation guiding future studies in testing potential mechanisms underlying global riverine δ*^7^*Li~diss~.

Seasonal River Chemistry and Lithium Isotopes in the Min Jiang at Eastern Tibetan Plateau: Roles of Silicate Weathering and Hydrology

Riverine lithium (Li) isotopes have been considered as a robust tracer for silicate weathering, but processes controlling riverine δ7Li ratios remain controversial. To address the impacts of weathering and hydrology on riverine δ7Li, the seasonal variation of water chemistry in the Min Jiang at the eastern Tibetan Plateau was investigated over December of 2009 to the end of 2010. The results showed distinct seasonal variations in ionic chemistry and δ7Li. Increased river discharge in the monsoon season diluted dissolved ions, and monsoonal hydrological changes caused frequent δ7Li fluctuations. High discharge caused by monsoonal rainfall reduced Li isotope fractionation by shortened rock–fluid interaction time, resulting in lower δ7Li, whereas the input of high δ7Li groundwater and landslide seepage elevated riverine δ7Li, together with lengthened rock–fluid interaction time in less rain intervals. Based on the high-resolution sampling strategy and dataset over one hydrological year, this study highlights that changes of hydrological conditions can have a significant impact on weathering processes and water sources, and therefore on riverine δ7Li variation.

Hydrogeochemical processes controlling the water composition in a hyperarid environment: New insights from Li, B, and Sr isotopes in the Salar de Atacama

Northern Chile, NW Argentina, and SW Bolivia, (“the lithium triangle”), represent a world class reservoir of lithium, but this extraordinary enrichment is still controversial, and different processes have been invoked over the years, including, geothermal waters associated with active volcanism, leaching of soluble salts from volcanic rocks and leaching of lithium-rich clays. The Salar de Atacama (SDA) represents one of the richest reservoirs of Li in northern Chile and has been extensively studied during the past years. Most of the studies have been focused in the southern and southeastern portions, where the highest lithium concentrations have been reported. However, a comprehensive model of water recharge at SDA is still imprecise. We used a combination of isotopic methods, including δ7Li, δ11B and 87Sr/86Sr ratios, with their chemical composition of a set of water samples from salt lakes, geothermal manifestations, groundwaters and surficial diluted waters (rivers and streams with low salinity). This study explores the hydrogeochemical processes controlling the water composition and solute distribution of the SDA. Our data confirm that weathering of the ignimbrites constitutes one of the most important processes in relation of solute origin in the region, where deep water-rock interactions would operate at high temperature, enhancing leaching of Li and other solutes. We determine that groundwater flow entering the SDA has undergone pre-enrichment processes (e.g., leak from Altiplano salt lakes; evaporite dissolution, among others) associated with salt inputs in the Western Cordillera. Our results provide a step forward to a comprehensive understanding of the processes that govern brine formation and lithium enrichment in a hyperarid environment, contributing to a sustainable exploration and exploitation of lithium in these environments.

Lithium isotope behavior under extreme tropical weathering: A case study of basalts from the Hainan Island, South China

Chemical weathering of silicate rocks (especially basalt) is an important sink of atmospheric carbon dioxide, and has an important impact on long-term carbon cycle and storage. Lithium (Li) isotopes have been regarded as a good tracer of chemical weathering, however, the behavior of Li isotopes in tropical settings is poorly understood. In this study, we studied the Li elemental and isotopic variation in the solid weathering products (soil and saprolite) from a highly-weathered (CIA ∼100%) basalt weathering profile (>15 m thick, including soil, saprolite, semi-weathered rock and fresh basalt) on the tropical Hainan Island in South China. The weathering products have 1.99–58.1 ppm Li, mostly below the average fresh basalt value (4.6 ppm, n = 5). The δ7Li values (−14.3 to 8.9‰) of the solid weathering products exhibit complex stratigraphic variation across the weathering profile. The Li and Mn enrichments coincide spatially, with the Mn-rich samples having the highest Li content and lowest δ7Li value. Lithium is enriched in the semi-weathered basalt sample, but its δ7Li value (−2.7‰) is close to that of fresh basalts (0.7–5.3‰, avg. 3.0‰, n = 5). Strontium isotope data show that the weathering profile is affected by marine aerosol input, and the marine strontium may have been leached to the profile bottom or out of it under extreme weathering. Sequential extraction results indicate that Li in the soil, saprolites (lower part), and semi-weathered basalt occurs mainly in the residual phase, while Li in the saprolites (middle part) occurs largely in Fe–Mn oxides. We suggest that Li isotope fractionation in the upper, middle and lower parts of the profile was controlled by, respectively, marine aerosol input and secondary mineral leaching, dissolution/re-precipitation of Fe–Mn oxides, and neoformation of secondary minerals from heavy pore water. Our results show that the preferential light Li isotope uptake by Fe–Mn oxides may have been the main cause for the major Li isotope fractionation in the Wenchang weathering profile.

Behaviors of lithium and its isotopes in groundwater with different concentrations of dissolved CO2

Lithium (Li) isotopes have shown large potential in tracing weathering in various water bodies, but there is limited study on Li isotopes in subsurface conditions where CO2 has been largely consumed. In this study, we use a thick sandstone aquifer in the Ordos Basin, NW China, as a natural setting to investigate the behaviors of Li isotopes in hydrogeochemical conditions with different concentrations of dissolved CO2. For young groundwater in the recharge area (group R) where CO2 is abundant (mean PCO2 = 10-2.5 atm), clay formation accompanying with weathering leads to the enrichment of 7Li in groundwater. The four deep samples in the recharge area have uniform Li/Na ratios (with a mean of 2.52 μmol/mmol) and δ7Li (with a mean of 25.0‰), corresponding to a mean Li removal rate of 81.2% compared with the sandstone leachate. For groundwater in the shallow part of the discharge area (group D1), Li was firstly removed by clay formation during weathering in the recharge area and was later removed by physisorption when CO2 becomes much lower (mean PCO2 = 10-3.1 atm). Different degrees of weathering lead to a wide range of δ7Li varying from 19.7‰ in the deepest well to 33.0‰ in the shallowest well. The proportion of Li removal caused by physisorption is found to increase with groundwater age. After the stage of Li removal by adsorption, Li was released in the deeper part of the discharge area (group D2), and the positive correlation of δ7Li versus Li/Na is explained by a ternary mixing model. The endmember of water brought by cation exchange is inferred to have a heavier δ7Li than sandstone leachate, demonstrating that cation exchange could cause an enrichment of 7Li in water. This study enhances our understanding of the controlling factors of Li isotopes in deep groundwater with low dissolved CO2, which have implications for the application of Li isotopes in subsurface water.

Episodic fluid flow in an eclogite-facies shear zone: Insights from Li isotope zoning in garnet

Abstract Episodic fluid overpressure and escape is invoked as a cause or consequence of many subduction-zone seismic phenomena but can be challenging to constrain in exhumed high-pressure metamorphic rocks. In situ measurements of lithium isotopes in garnet reveal evidence of episodic fluid transport in a subduction shear zone now exposed in the Monviso ophiolite (Western Alps). Garnet from an eclogite block and associated metasomatic reaction rind was analyzed by secondary ion mass spectrometry (SIMS). All analyzed garnet preserves core-rim zoning in δ7Li and large negative δ7Li excursions (NEs) in mantles. These excursions cannot be explained by instrumental mass fractionation during analysis, equilibrium fractionation, or intracrystalline diffusion of Li within garnet. Instead, NEs were produced by kinetic fractionation of Li isotopes during bulk diffusion through a pore fluid, and the fractionated isotopic compositions were incorporated into garnet by syn-diffusion growth. Disequilibrium garnet growth textures associated with negative δ7Li support this interpretation and suggest metasomatism drove rapid garnet growth. Four distinct NEs were identified requiring that at least four pulses of fluid were transported within the adjacent shear zone. This evidence of episodic fluid transport along a subduction shear zone at eclogite facies supports models of intermediate-depth seismicity that rely on cyclic fluid overpressure and escape.