Li Isotope Research Articles

B–Li differential enrichment of geothermal systems in the Da Qaidam and Gonghe–Guide Basin, northeastern Tibetan Plateau: Evidence from water chemistry and H–O–B–Li isotopes

Typical geothermal systems in the Da Qaidam (DQ) and Gonghe–Guide Basin (GGB) on the northeastern Tibetan Plateau (NETP) discharged different BLi contents. A widely accepted metallogenic model is that the salt–lake type BLi deposits in the TP are recharged by geothermal fluids with B–Li–rich, carried by rivers and enriched in the terminal salt lakes. The B–Li–rich geothermal water is the key source of mineralization in salt lakes, however, enrichment mechanism governing differential BLi contents in DQ and GGB geothermal systems remains ambiguous. This study systematically deciphers water chemistry and isotope characteristics (δD, δ18O, δ11B, δ7Li) of river waters, geothermal waters, sinters and surrounding rocks to discuss the enrichment process of BLi elements in the DQ and GGB geothermal systems. The δD and δ18O values of geothermal systems in the DQ (δD = −79.60 ∼ −82.40 ‰, δ18O = −10.97 ∼ −11.38 ‰) and GGB (δD = −64.00 ∼ −97.10 ‰, δ18O = −8.70 ∼ −13.00 ‰) are close to the GMWL and LMWL, indicating meteoric origin. The δD and high Cl− values (300–900 mg/L) of geothermal waters in the DQ and Qiabuqia, Qunaihai, Zhacangsi along Riyueshan of the GGB imply that these geothermal waters mixed by magmatic fluid and meteoric water. The hot springs in the DQ (B = 38.35–46.29 mg/L, Li = 3.11–3.72 mg/L) and GGB (B = 0.17–8.16 mg/L, Li = 0.08–10.49 mg/L) exhibit differential BLi geochemical characteristics. B and Li contents are higher in DQ hot springs and in hot springs along Riyueshan of the GGB, respectively. Comparison of the BLi contents and δ11B–δ7Li values of geothermal waters, sinters and host rocks reveals that BLi contents of geothermal waters are controlled by B–rich HP-UHP metamorphic rocks formed by metamorphism and Li–rich granites or pegmatites formed by magmatism in the Qilian Shan, respectively. Moreover, metamorphic and magmatic processes, combining with deep circulation reactivated by the thrust or strike–slip faults, create differential enrichment of BLi elements in the geothermal systems, such as DQ and GGB on the NETP. This study highlights into understanding the differential enrichment of BLi in the geothermal system on the TP. Furthermore, the resource elemental abundance of geothermal waters can be applied as an important prospecting indicator of endogenous BLi deposits.

Lithium isotope systematics in an endorheic saline lacustrine system: Insights from Qinghai Lake, China

The study of lithium isotopic (δ7Li) signatures in sedimentary deposits has become a powerful tool to infer past silicate weathering regimes, thus informing our knowledge of the geological carbon cycle and paleoclimate evolution. Sediments from Qinghai Lake, the largest saltwater lake in China (4625 km2), offer an unparalleled archive for investigating the climatic history of the Qinghai-Tibet Plateau. However, prior to leveraging the δ7Li proxy in this context, it is imperative to unravel the mechanisms of lithium (Li) isotope fractionation and elemental cycling within the lake's aqueous and sedimentary systems. In this study, we collected and analyzed samples of Qinghai Lake's water, sediments, and recharge waters (rivers, groundwater, and rainfall) to investigate the processes controlling the δ7Li value recorded in Qinghai Lake sediments.Our data reveal subtle variances in Qinghai Lake water Li concentration ([Li]), ranging from 652 to 873 ng/g, suggesting interactions with iron oxides or suspended matter. The δ7Li signature, however, exhibits remarkable uniformity across the lake at 32.1‰ (±0.4‰). Near the estuary of the Buha River, there is a swift homogenization of [Li] and δ7Li, stabilizing within just 3 km of the inflow. Lake sediments exhibit δ7Li values ranging from 1.5‰ to 6.6‰, exceeding those of the upper continental crust (∼0‰ ± 4‰), yet approximately 30‰ lower than those in lake waters. This significant discrepancy between the δ7Li of lake water and sediments is likely due to the preferential incorporation of 6Li over 7Li during the neoformation of clay minerals.Lithium mass balance modeling for Qinghai Lake, incorporating inputs from river and groundwater (∼46.5 t/a with δ7Li ∼18.3‰) and outputs via clay mineral uptake (∼44 t/a with δ7Li ∼5.1‰), indicates that the lake's Li system is currently out of steady state. The model predicts a gradual rise in the lake's Li inventory, estimated to achieve steady state within 1.2 ka and the δ7Li value of lake water will increase until reaching ∼45‰ assuming constant climate conditions.

Моделирование чувствительности литийсодержащих кристаллических сцинтилляторов к нейтронному излучению

This paper presents the results of Monte Carlo modelling of the sensitivity of the lithium containing detectors CLYC, NaIL, CLLB to thermal neutrons. The difference between the sensitivity and the neutron freepath depth of the CLYC scintillator enriched and unenriched with the 6Li isotope is shown. The analysis of the distribution of alpha particles and neutrons in the scintillator volume is performed, showing the inefficiency of the unenriched scintillator due to the fact that not all neutrons react with the crystal material. Mathematical modelling by the Monte Carlo method of the scintillator sensitivity and its comparison with respect to the irradiation direction has been carried out. It is shown that for the scintillator in the face and side geometry with the size more than 38 mm the difference in sensitivity at change of the neutron flux direction is connected only with the scintillator cross section and 6Li concentration with the same value of the specific sensitivity. The obtained model results were compared with available experimental data for NaIL and CLLB scintillators, which showed the reliability of the developed models and calculation methods.

Heavy metal migration and lithium isotope fractionation under extreme weathering of basalt on tropical Hainan Island, China

Basalt weathering can cause heavy metal enrichment in soils, and lithium isotopes serve as an effective tracer for this weathering process. However, the relations among weathering intensity, heavy metal migration, and Li isotope fractionation remain unclear. We conducted systematic examinations of a basalt weathering profile on tropical Hainan Island in China. The characteristics of mineralogy, elemental and Li isotopic geochemistry indicate that the profile has undergone changes from initial to advanced and ultimately extreme weathering stages. The corresponding dominant minerals are primary minerals, clay minerals such as kaolin-group, and the Al–Fe–Ti (hydro)oxides. The variations of Fe-group heavy metals within the profile are very similarly to that of Fe, exhibiting a pattern of loss-gain-loss. Newly formed secondary minerals preferentially incorporate lighter 6Li, leading to a gradual increase in Li content and a decrease in δ7Li. Due to the high δ7Li value of rainwater input, the ongoing impact of secondary mineral adsorption is partially counteracted. This results in the δ7Li of laterite and topsoil being maintained within a narrow range (−3.2‰ ∼ −1.9‰), despite the broader variation observed across the entire profile (−3.2‰ ∼ +2.8‰). Comparing basalt weathering profiles in different climatic zones reveals a very complex Li isotope behavior and its controlling factors. Therefore, it is essential to carefully evaluate the influence of atmospheric input, secondary mineral adsorption, dissolution, and redeposition processes on Li isotopes. Throughout the entire profile, Cr, Ni, and Cu exhibit enrichment relative to soil background values, indicating that the weathering of tropical basalt may pose potential environmental risks for these elements.

The Differences in the Li Enrichment Mechanism between the No. 6 Li-Rich Coals and Parting in Haerwusu Mine, Ordos Basin: Evidenced Using In Situ Li Microscale Characteristics and Li Isotopes

As a potential strategic mineral resource, lithium (Li) in coal measures (including coal and parting) has attracted increasing attention from scholars globally. For a long time, Li in coal measures has been studied mainly on the macro-scale (whole rock); however, the microscopic characteristics of Li and Li isotope variations in coal measures are less well known. In this study, the No. 6 coal measures in the Haerwusu Mine were studied using ICP-MS, XRD, SEM-EDS, MC-ICP-MS, and LA-ICP-MS. The geochemical and mineralogical characteristics, the microscale distribution of Li in minerals, and the Li isotopes of Li-rich coal and parting in the No. 6 coal measure were investigated. The results show that the Li content in the No. 6 coal seam ranges from 3.8 to 190 μg/g (average 83 μg/g), which is lower than the parting (290 μg/g) and higher than the comprehensive evaluation index of Li in Chinese coal (80 μg/g). LA-ICP-MS imaging showed that Li in the coal is mainly contained within cryptocrystalline or amorphous lamellae aluminosilicate materials, and the Li content in lenticular aggregate kaolinite is low. The Li in parting is mainly found in illite/chlorite. The δ7Li of the coals was 3.86‰, which may be influenced by the input of the source rock. The δ7Li of the parting (7.86‰), which was higher than that of the coal, in addition to being inherited from the source rock, was also attributed to the preferential adsorption of 7Li by the secondary clay minerals entrapped in the parting from water during diagenetic compaction. Finally, by integrating the peat bog sediment source composition, sedimentary environment evolution, and Li isotope fractionation mechanism of No. 6 coal, a Li metallogenic model in the Li-rich coal measure was initially established. In theory, the research results should enrich the overall understanding of the Li mineralization mechanism in coal measures from the micro-scale in situ and provide a scientific basis for the comprehensive utilization of coal measure resources.

Evaluating evaporites as potential archives of lake and seawater lithium isotopic ratios: An experimental study using various natural saline fluids

Reconstructing the lithium isotope composition (δ7Li) of ancient seawater and lacustrine environment is crucial for tracing silicate weathering processes that regulate Earth's carbon cycle and climate. This study examines the reliability of evaporite minerals in preserving the Li isotope signature of the original brines from which they precipitate. We conducted evaporation experiments on modern natural waters from Qinghai Lake, the Yellow Sea, and Chaka Salt Lake, each with unique salinity and chemical composition, to examine the behavior of lithium isotope ratios in the evolving brine and precipitated evaporite minerals.Our results show that initial hydrochemical conditions of the lake and ocean are the primary control on the evolution of major and trace elements and the mineral precipitation sequences during evaporative concentration. Aragonite, calcite, gypsum, and/or nesquehonite precipitated prior to halite. Li isotope fractionation of these non-halite precipitates varied significantly between 4‰ and 17‰. However, the δ7Li values of halite closely mirror those of the initial lake and seawater, indicating negligible Li isotope fractionation (<1‰) during halite precipitation. The δ7Li values of the evolving brines remain unchanged throughout the evaporation experiment. Solid phases precipitating before halite constitute <1–2% of the total moles of salt precipitated from the complete evaporation of the initial waters, thus, having little to no influence on the δ7Li values of evolving brines. Although halite comprises >77% of the total moles of salt, it does not fractionate Li isotopes. Therefore, halite more accurately reflects the δ7Li values of the co-evolving brine as well as those of the initial, unevaporated lake and seawater. These results underscore the potential of late stage evaporites, particularly halite, to serve as high-fidelity archives of ancient lacustrine and seawater δ7Li values. Such records are instrumental in reconstructing past silicate weathering and climatic conditions.

Investigation of Lithium Deposition in Tri-Layer Llzo Garnet Structure As a Function of Cell Cycling Using Nuclear Reaction Analysis Method

A key challenge of lithium metal batteries is the volumetric expansion of battery after several charging cycles due to the non-uniform deposition of lithium on anode. This leads to lithium dendrite formation compromising battery safety, and poor lifetime. We adapted tri-layer (porous-dense-porous) Al-doped Lithium Lanthanum Zirconium Oxide (LLZO) host (separator) via tape casting. During cycling lithium is deposited in the porous structure preventing dendrite formation. XRD analysis of annealed host structure confirmed presence of cubic phase LLZO which provides higher ionic conductivity. We measured Li distribution on LLZO host structure before and after different cell cycling conditions and investigated the failure mechanism. We performed concentration depth profiles of 7Li and 6Li isotopes by Nuclear Reaction Analysis (NRA) using two different methods: Proton Induced Gamma-ray Emission (PIGE) and Proton Induced Alpha-particle Reaction (Particle-Particle reaction) and compared the results for accuracy. Depth profile of 7Li confirmed 33 at % Li at 0.44µm thickness before cycling which was increased after cycling. The Gaussian distribution of NRA data indicated a uniform Li depth profile in the dense layer. Through electrochemical testing, we measured that Li capacity loss after 5 and 25 charging cycles with 0.1C rate, 1.51mAh and 2.89mAh, respectively, in tri layered LLZO separator.

Lithium isotope ratio analysis of geological samples using atomic absorption spectrometry with improved spectral resolution

This study introduces an improved spectrometric method with enhanced precision to determine isotope ratios in geological samples without chromatographic separation. Firstly, the improvement is achieved by increasing the spectral resolution of the spectrometer applied in well-known high-resolution continuum source atomic absorption spectrometry (HR-CS-AAS). The resulting resolving power and linear dispersion of the upgraded setup, which is denoted in the following as HR+CS-AAS, is well adapted to the line widths of the Li isotope components we investigated. Secondly, our proposed method combines optical absorption spectrometry with machine learning data analysis using an extreme gradient boosting algorithm (XGBoost). This method was applied to analyze certified geological reference materials with δLSVEC(7Li/6Li) (hereafter δ7Li) values ranging from −0.5 ‰ to 4.5 ‰. With a pixel related optical resolving power of λ/∆λ ≈ 780 000, we obtain precisions in δ7Li measurements from 1.0 ‰ to 2.5 ‰. The method is validated by comparing the results with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), confirming its metrological compatibility. This work presents a fast, robust, and reliable method for δ7Li measurement in geological samples.

Lithium isotopic records of anthropogenic activity in the Xiaoqing River basin, eastern China

The environmental impact of the discharge of lithium (Li) by anthropogenic activity has been overlooked. By analyzing Li concentrations and isotope compositions (δ7Li) of water and sediment samples, this study evaluates the influence of anthropogenic Li discharge on the Xiaoqing River and Laizhou Bay, which are heavily polluted areas in China. High Li concentrations of the river water (up to 7.8 μmol/L) should be linked to anthropogenic Li discharge. However, no profound δ7Li anomalies were observed, preventing identification of the exact discharge sources. In the river sediments, Li concentrations (19.0–45.0 μg/g) were weakly correlated with Zn, Cu, and Cr concentrations, whereas δ7Li values ranged from 0.6 ‰ to 13.9 ‰ with high values being accompanied by high contents of total organic carbon and heavy Cr isotope compositions (δ53Cr). All these point to significant influence of anthropogenic activity on the Li budget of river sediments. A simple mass balance calculation indicates that smelters, Li-bearing therapeutic drugs, and secondary Li-ion batteries are the main anthropogenic Li sources. In contrast to river sediments, marine sediments in the Laizhou Bay were broadly homogeneous at both spatial and temporal scales, indicating no significant influence of anthropogenic Li discharge. Overall, our data indicate that Li isotope systematics in river sediments, especially sediments near intense anthropogenic activity, are effective at tracing potential Li pollution and can help obtain accurate results for environmental inspection.

Lithium Neutron Cross Sections During the Manhattan Project and the Quest for the H-Bomb

Neutron cross sections of the stable lithium isotopes 6Li and 7Li were of interest in the 1940s and 1950s in part because of their reactions, which form tritium using moderated neutrons on 6Li and higher-energy neutrons on either isotope. Lithium remains of interest today for use as a blanket and shielding material in fusion reactors, where it can be used to breed tritium for a self-sustaining fuel cycle. During the Manhattan Project, the resonance in the 6Li(n,t) reaction was discovered and later became important for enhancing tritium production for nuclear technologies. The dominant natural isotope 7Li was and remains of interest because of the expense of enriching 6Li. It has been oft reported that the 1954 Castle Bravo nuclear test had a yield twice as large as expected because the nuclear explosive device designers had not properly accounted for the benefits from the 7Li isotope in the fuel; we note that this explanation is false.

Energy and charge radii of Li isotopes in a two-body configuration

Energy and charge radii of Li isotopes in a two-body configuration

Genesis of the Ke’eryin Two-Mica Monzogranite in the Ke’eryin Pegmatite-Type Lithium Ore Field, Songpan–Garze Orogenic Belt: Evidence from Lithium Isotopes

Previous studies on the Ke’eryin pegmatite-type lithium ore field in the Songpan–Ganzi Orogenic Belt have explored the characteristics of the parent rock but have not precisely determined its magma source area. This uncertainty limits our understanding of the regularity of lithium ore formation in this region. In this study, to address the issue of the precise source area of the parent rock of lithium mineralization, a detailed analysis of the Li isotope composition of the ore-forming parent rock (Ke’eryin two-mica monzogranite) and its potential source rocks (Triassic Xikang Group metamorphic rocks) was conducted. The δ7Li values of the Ke’eryin two-mica monzogranite, Xikang Group metasandstone, and Xikang Group mica schist are −3.3–−0.7‰ (average: −1.43‰), +0.1–+6.9‰ (average: +3.83‰), and −9.1–0‰ (average: −5.00‰), respectively. The Li isotopic composition of the Ke’eryin two-mica monzogranite is notably different from the metasandstone and aligns more closely with the mica schist, suggesting that the mica schist is its primary source rock. The heavy Li isotopic composition of the two-mica monzogranite compared to the mica schist may have resulted from the separation of the peritectic garnet into the residual phase during the biotite dehydration melting process. Moreover, the low-temperature weathering of the source rocks may have been the main factor leading to the lighter lithium isotope composition of the Xikang Group mica schist compared to the metasandstone. Further analysis suggests that continental crust weathering and crustal folding and thickening play crucial roles in the enrichment of lithium during multi-cycle orogenies.

Hyperfine interactions of paramagnetic radiation-induced defect centres in advanced ceramic breeder pebbles

Advanced ceramic breeder (ACB) pebbles consisting of 65 mol% lithium orthosilicate (Li4SiO4) and 35 mol% lithium metatitanate (Li2TiO3) are developed for tritium breeding in the European Union’s (EU) helium cooled pebble bed (HCPB) breeder blanket concept of the demonstration fusion power plant (DEMO). Electron-nuclear double resonance (ENDOR) spectroscopy is a powerful and widely used magnetic resonance technique that combines aspects of electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR). In the present work, ENDOR spectroscopy was applied to investigate hyperfine (HF) interactions of paramagnetic radiation-induced defect centres (containing unpaired electrons) in the biphasic ACB pebbles after irradiation with 10 MeV accelerated electrons. To separate individual EPR signals of the formed and accumulated paramagnetic centres, isochronal annealing of the irradiated ACB pebbles followed by EPR spectra measurements at X- and Q-microwave frequency bands at room and low temperature were performed. Afterwards, X-band ENDOR spectra at low temperature were recorded for selected EPR signals to reveal HF interactions between the unpaired electron spins with the spins of magnetic 7Li and 1H isotope nuclei. The g-factor and HF coupling values determined from EPR and ENDOR spectra simulations provide novel insights into the local structure of paramagnetic hole- and electron-type centres in the irradiated ACB pebbles.

Genesis of the Jiada pegmatite lithium deposit in the Ke’eryin ore field, western Sichuan, China: Evidence from whole-rock trace element and Li isotope

The origin and petrogenesis of pegmatite-type lithium deposits within the Songpan-Garze Fold Belt (SGFB) of western China remain subjects of debate. To provide further insight on this subject, this study investigated the whole-rock trace elements and whole-rock Li isotopic compositions of the two-mica monzogranite (TMG) from the Ke’eryin composite pluton, the Jiada albite pegmatite (AP) and albite-spodumene pegmatite (ASP) and their metasedimentary wall rocks within the Ke’eryin ore field in the eastern SGFB. Modeling of muscovite-dehydration melting based on the whole-rock trace elements (e.g., Li, Rb, and Sr) and Rayleigh dehydration modeling related to the whole-rock Li isotopes suggest that the Jiada pegmatites are unlikely to have originated from the low-degree partial melting of metasandstone (MS) of the Zhuwo Formation. Variations in the whole-rock trace elements and Li isotope between the TMG and the Jiada pegmatites are consistent with the evolution trend of magmatic fractionation. However, the whole-rock Li isotopic compositions of the AP and ASP display inverse variation characteristics with the muscovite Li isotopic compositions, with the AP exhibiting lower Li concentrations and higher whole-rock δ7Li values than ASP. Furthermore, the variation patterns of whole-rock trace elements do not align perfectly with the Rayleigh-type fractional crystallization processes, implying other geological processes would be also involved in the formation of the Jiada pegmatites. Collectively considering the Li isotope behavior during various geological processes, the observed variations in whole-rock Li isotopic compositions between AP and ASP can be explained by aqueous fluid enrichment during the pegmatitic melt evolution. This suggests that fractional crystallization and fluid exsolution jointly contributed to pegmatite formation and Li mineralization in the Jiada deposit. Moreover, the whole-rock δ7Li values of the wall rock of ASP (MS2) are lower than those of MS and the wall rock of ASP (MS1), primarily due to metasomatism by 6Li-enriched fluids expelled from ASP and the kinetic diffusion of Li isotopes. The high concentrations of highly mobile elements, especially Li and Cs, combined with the low whole-rock δ7Li value of the metasandstone, could serve as effective tracers for locating concealed orebodies and evaluating the metallogenic potential of Li mineralization.

Continental crust recycling in collisional zones: insights from Li isotope compositions of the syn-exhumation and post-collisional mafic magmatic rocks

Syn-exhumation and post-collisional mafic magmatism in continental collision orogenic belts may provide insights into the nature of orogenic lithospheric mantle and recycled continental components in continental subduction zones. Lithium and its isotopes have emerged as potentially valuable tools for shedding light on the origin of these magmas, given the contrast Li contents and isotopic compositions between the subducting continental crust and the mantle. Here, we present high-precision Li isotopes data for representative orthogneiss, continental eclogite, syn-exhumation and post-collisional mafic magmatic rocks from the North Qaidam orogen. The syn-exhumation mafic magmatic rocks have relatively higher Li contents (26.5–50.0 ppm) and lower δ7Li values (−1.01‰–1.48‰) than those of the post-collisional mafic magmatic rocks (Li = 11.1–22.7 ppm, δ7Li = 1.20‰–3.38‰), which are comparable to those of orthogneiss and continental eclogite, respectively. Dehydration and melting modelling results show that these mafic magmatic rocks have similar Li contents and δ7Li values to the continental eclogite- and orthogneiss-derived melts but are different from their derived fluids. Monte Carlo simulation for Li-Nd isotopes suggests the syn-exhumation and post-collisional mafic rocks could be derived from an enriched mantle source that contains ∼3–8% continental crustal components dominated by the orthogneiss and continental eclogite. The calculated results are consistent with the results from the previous study simulated by trace elements. Therefore, our results highlight Li isotopes as a potential tool to trace the nature of the continental crustal components recycling in continental subduction zones.

Unveiling the Structure and Diffusion Kinetics at the Composite Electrolyte Interface in Solid‐State Batteries

AbstractThe “interface” between polymer and oxide within the polymer‐oxide composite electrolytes is widely acknowledged as a crucial factor influencing ionic conduction. However, a fundamental understanding of the precise composition and/or micro‐structure, and the ionic conduction mechanism at the complex interface has remained elusive, primarily due to a dearth of compelling experimental evidence. In this study, the intricate correlation between morphology and composition in composite electrolytes is discerned by leveraging advanced 1D and 2D exchange nuclear magnetic resonance spectroscopy (1D and 2D EXSY NMR) techniques. Notably, this research represents the inaugural elucidation of the microstructure of the interface. The findings underscore the pivotal role of the preparation conditions for polymer‐oxide composite electrolytes, particularly the solvent selection, in determining the formation of the interface structure. Direct insights into the lithium‐deficient surface of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) are provided and elucidate the timescales of Li‐ion exchange processes among various components. Furthermore, a comprehensive investigation into the roles of individual components within the composite electrolyte on the Li‐ion conduction mechanism is conducted through the 6Li→7Li isotope tracer technique as a function of current density.

The effect of diffusion on lithium isotope ratios in Icelandic basalts

In recent years, diffusion has gained increasing recognition as an important process for explaining the lithium (Li) isotope ratios (δ7Li) of magmatic systems. However, the role of diffusion in explaining the variability of mantle-derived basalts has not yet been investigated in detail. We have measured δ7Li values in a comprehensive suite of fresh, subglacial Icelandic basalt glasses and observe a wide range of values from 2.4‰ to 7.3‰, the largest range in Li isotope compositions identified at any ocean island. We find that δ7Li values do not correlate with lithophile element tracers, but do correlate with 3He/4He. One possibility is that the high diffusivities of both Li and He permit fractionation of Li isotope compositions that couple it to 3He/4He, and decouple it from other, slower-diffusing lithophile tracers. In this study, we explore this idea and model diffusive processes in crystal mushes and mantle melt channels, both with and without melt transport. Our modelling indicates that large (>3‰) fractionation of Li isotope compositions from MORB-like values can be generated by diffusion and that the coupling of Li isotope ratios and 3He/4He signatures can occur as a consequence of diffusive interactions within mantle melt channels. This suggests that the Li isotope compositions of melts cannot be used as a straightforward passive tracer of mantle heterogeneity, because they can be fractionated during magmatic processes. In contrast, we find that diffusive fractionation of 3He/4He is small (∼1 Ra) next to the variability in Icelandic basalts (∼8 to ∼35 Ra). Diffusive fractionation of Li isotope ratios should be most pronounced at OIB localities whose mantle melts have a wide range of [Li], such as Hawaii and Iceland. Although a mantle source can contain Li isotope heterogeneities as a result of crustal recycling, we show that a mantle that is homogenous in Li isotope composition can still generate melts that have variable δ7Li values via diffusion processes.The same diffusion models can also be applied to other stable isotope systems such as H, Mg, Ca, and Fe. Indeed our models show that diffusion during magmatic transport within the mantle may be a significant source of “noise” in the δ7Li, δD, and possibly δ26Mg isotopic systems.

Research progress on lithium isotopes separation by chemical exchange with crown ethers decorated materials

The separation of lithium isotopes (6Li and 7Li) is of great importance for the nuclear industry. The lithium amalgam method is the only lithium isotopes separation process in industry, and the extensive use of mercury has raised concerns about its potential environmental hazards, which have prompted the search for more efficient and environmentally friendly alternatives. Crown ethers can bind lithium ions highly selectively and separate lithium isotopes effectively. A chemical exchange-based lithium isotopes separation method using crown ether decorated materials could be a viable and cost-effective alternative to the lithium amalgam method. In this review, we provide a systematic summary of the recent advances in lithium isotopes separation using crown ether decorated materials.

Cycling of fluid-mobile elements through the forearc: Insights from the Cl, B, and Li isotope composition of Costa Rican spring fluids

Loss of slab-derived volatile and fluid-mobile elements (FME) through the forearc may represent a large, unaccounted for flux out of convergent margins. To address volatile recycling through the forearc and potential changes in fluid source from the progressively dehydrating subducting slab, we collected water samples from 44 different cold and thermal (>40 °C) springs on a transect across the outer forearc (∼20–40 km to the subducting slab), forearc (∼40–80 km to the slab), and arc (∼80–120 km to the slab) in Costa Rica. We focused on the heavy halogens (Cl, Br, I), as well as B and Li, given their high fluid mobility and thus limited potential for modification by subsequent fluid-rock interaction. Chlorine, boron, and lithium stable isotope ratios show dramatic ranges from −1.7 to +1.0 ‰ (n = 43), −12.0 to +30.9 ‰ (n = 35), and −2.4 to + 27.5 ‰ (n = 38), respectively, with distinct changes across the transect consistent with a sedimentary pore fluid component in the outer forearc, fluids sourced from dehydration of the slab (sediment and altered oceanic crust) in the forearc, and minimal slab input near the arc. Variations in elemental ratios (Br/Cl, I/Cl, B/Cl, Li/B) across the transect are also largely consistent with evolving FME sources during subduction. Boron isotope ratios in some higher-temperature fluids are modified due to phase separation, whereas, lithium and chlorine isotope ratios are minimally modified. Springs located in the outer forearc along a major fault (Falla Morote) deviate from the consistent across-arc trend and record almost the full range of observed isotopic values. This extreme range in values along the fault likely represents a combination of adsorption/desorption effects, weathering, and mixing with crustal fluids. Mass balance calculations show that up to ∼ 70 % of Cl, ∼50 % of Br, ∼30 % of B, ∼15 % of I, and minimal Li may be recycled through the outer forearc and forearc springs of the Costa Rican margin, therefore fluid emission via springs in global forearc regions are a potentially significant output for FME at convergent margins.

Wettability, imbibition and interdiffusion of lithium-based water-in-salt electrolytes in nanoporous carbon in relation to energy storage: A neutron radiography study

Superconcentrated lithium salt electrolytes, or lithium-based Water-in-Salt (WiS) electrolytes emerge as alternative electrolytes in supercapacitors and advanced batteries, such as the Li–O2 ones, especially when combined with a mesoporous carbon with very high surface area. In this work, we analyze the wettability, imbibition, and diffusivity of very concentrated lithium salts in a bimodal mesoporous carbon with pores of 5 nm and 25 nm in diameter. For the first time a neutron radiography technique is used to determine the imbibition and interdiffusion of lithium salts in mesoporous carbon. We found that a 20 m LiTFSI aqueous solution wets the surface of graphite and mesoporous carbon better than water. As a consequence, this WiS electrolyte is embedded rather fast in the mesoporous carbon by the action of capillary forces, exhibiting an intrinsic permeability K = (1.16 ± 0.03).10−18 m2. Finally, by resorting to the different cross-section of the 6Li and 7Li isotopes for the neutron capture, we could analyze the diffusion of LiCl in D2O confined in the mesoporous carbon. The interdiffusion coefficient of the confined LiCl is 5.0 10−7 cm2 s−1, corresponding to a tortuosity coefficient τ = 1.32. This moderate confinement effect results from the strong ion association of the LiCl that precludes the electrostatic interactions of Li+ ions with the negative charge on the pore walls. In summary, the combined properties of the lithium-based WiS electrolytes and the mesoporous carbon allow us to glimpse their use in supercapacitors and Li–O2 batteries.