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An interlaboratory comparison (ILC) was organised to characterise 87Sr/86Sr isotope ratios in geological and industrial reference materials by applying the so‐called conventional method for determining 87Sr/86Sr isotope ratios. Four cements (VDZ 100a, VDZ 200a, VDZ 300a, IAG OPC‐1), one limestone (IAG CGL ML‐3) and one slate (IAG OU‐6) reference materials were selected, covering a wide range of naturally occurring Sr isotopic signatures. Thirteen laboratories received aliquots of these six reference materials together with a detailed technical protocol. The consensus values for the six reference materials and their associated measurement uncertainties were obtained by applying a Gaussian, linear mixed effects model fitted to all the measurement results. By combining the consensus values and their uncertainties with an uncertainty contribution for potential heterogeneity, reference values ranging from 0.708134 mol mol‐1 to 0.729778 mol mol‐1 were obtained with relative expanded uncertainties of ≤ 0.007 %. This study represents an ILC on conventional 87Sr/86Sr isotope ratios, within which metrological principles were considered and the compatibility of measurement results obtained by MC‐ICP‐MS and by MC‐TIMS is demonstrated. The materials characterised in this study can be used as reference materials for validation and quality control purposes and to estimate measurement uncertainties in conventional 87Sr/86Sr isotope ratio measurement. [ABSTRACT FROM AUTHOR]

Salars with lithium-rich brines are a characteristic feature of the Central Andes, but knowledge about the main sources of lithium and the mobilization processes of lithium in the salar deposits is still incomplete. This work focuses especially on the Salar de Diablillos (southern Puna) as part of a larger area that includes the neighboring Salar Centenario and Salar de Ratones. Building on the ability of Li as a tracer of silicate weathering, we investigate the Li content and isotope composition of samples from the depocenter and catchment of the Diablillos basin (3-D) and conduct a surface reconnaissance in the Centenario and Ratones depocenters to identify the key metallogenic processes. Radiogenic Sr and Nd isotope compositions are also provided to discriminate the main local Li sources. The isotope data in all three depocenters show that most of the Li in the brines and evaporite deposits are derived from Cenozoic volcanic rocks, despite the dominance of the Paleozoic basement in the catchment. In the Centenario and Ratones depocenters, near-surface chemical weathering appears to be the dominant Li mobilization process. In contrast, hydrothermal mobilization of Li also plays a role in the Salar de Diablillos, possibly related to the presence of a fractured basement with pressure zones and artesian conditions in the aquifer at depth. These fluids also show a larger element contribution from the basement. [ABSTRACT FROM AUTHOR]

Dissimilatory iron reduction (DIR) is suggested to be one of the earliest forms of microbial respiration. It plays an important role in the biogeochemical cycling of iron in modern and ancient sediments. Since microbial iron cycling is typically accompanied by iron isotope fractionation, stable iron isotopes are used as tracer for biological activity. Here we present iron isotope data for dissolved and sequentially extracted sedimentary iron pools from deep and hot subseafloor sediments retrieved in the Nankai Trough off Japan. Dissolved iron (Fe(II)aq) is isotopically light throughout the ferruginous sediment interval but some samples have exceptionally light isotope values. Such light values have never been reported in natural marine environments and cannot be solely attributed to DIR. We show that the light isotope values are best explained by a Rayleigh distillation model where Fe(II)aq is continuously removed from the pore water by adsorption onto iron (oxyhydr)oxide surfaces. While the microbially mediated Fe(II)aq release has ceased due to an increase in temperature beyond the threshold of mesophilic microorganisms, the abiotic adsorptive Fe(II)aq removal continued, leading to uniquely light isotope values. These findings have important implications for the interpretation of dissolved iron isotope data especially in deep subseafloor sediments. [ABSTRACT FROM AUTHOR]

The Central Andes of South America host the largest known lithium resources in a confined area, but the primary lithium sources of the salar deposits and the mobilisation process of lithium are still a matter of speculation. Chemical weathering at or near the surface and leaching in hydrothermal systems of the active magmatic arc are considered the two main mechanisms of Li extraction from the source rock. The lithium and strontium isotope composition of typical salar deposits offer insights into the processes on how Li brine deposits in Andean evaporites are formed. Data from the Salar de Pozuelos indicate near-surface chemical weathering in a cold and dry climate as the dominant mobilisation process of Li, with evaporation being responsible for the enrichment. The Cenozoic ignimbrites are the favoured source rock for the Li, with subordinate additions from the Palaeozoic basement. The identification of the source rocks is supported by radiogenic Nd and Pb and stable B isotope data from salar deposits. A comparison with other Li brine and salt deposits in the Altiplano-Puna Plateau and its western foothills places the Salar de Pozuelos as an endmember of Li solubilisation by chemical weathering with only minor hydrothermal mobilisation of Li. [ABSTRACT FROM AUTHOR]

The chemical composition of metasediments is a valuable source of paleogeographic information about the protolith's sedimentary environment. Here, we compile major- and trace-element whole-rock data, including B contents, and 10/11B-isotope ratios from the Permo-Triassic metasedimentary cover of the Pfitsch-Mörchner basin, overlying the Variscan basement in the western Tauern Window, Eastern Alps (Austria and Italy). The basement consists of orthogneiss ("Zentralgneis", metamorphosed Variscan granitoids with intrusion ages between 305 and 280 Ma), and the roof pendant consists of granites (amphibolites, paragneiss, and minor serpentinites). The Zentralgneis is partly hydrothermally altered into pyrite quartzite with high Al-S contents, low Na-Sr-Ca-Mg contents, and very strong depletion of the light rare earth elements. Comparison with published detailed mapping of this and other time-equivalent basins in the western TauernWindow, with radiometric age data in the literature, and with unmetamorphosed basins in the South Alpine realm yields a late Permian to Early Triassic age of sedimentation. Although during Alpine metamorphism all rocks were strongly deformed, the whole-rock chemical compositions of the metasediments were not pervasively changed during deformation. We show that the sediments were deposited in a small, probably lacustrine-fluviatile, intramontane basin, under arid to semi-arid climatic conditions. The sequence starts with metaconglomerates, which can be interpreted as a mixture of the different basement rocks, based on a combination of major-element ratios Na2O= (Na2OCK2O) and MgO= (MgOCFe2O3) with concentrations of trace elements Cr, V, and Ni. The sequence is overlain by a fining-upwards sequence of clastic sediments, in which the behavior of K, Rb, and Sr allows the reconstruction of intense diagenetic K-B metasomatism, which raised the K2O contents up to ~ 10 wt %. The average B content of 218 µg g-1 is well above the B content of common sediments, and the B-isotope composition reaches extremely low values of down to -33 -11B. The top of the sequence is a lazulite quartzite, interpreted as a former conglomeratic phosphatic sandstone, which marks the transition from a closed Permian basin to an open Triassic basin. Within the clastic sequence, the presence of hydrothermal tourmalinite veins documents a hydrothermal event after deposition but before the onset of Alpine metamorphism. A metamorphosed mafic dike swarm in the orthogneiss indicates a post-Variscan event of basaltic magmatism, and this event is tentatively correlated with increased heat flow in the Triassic basin and hydrothermal activity. A consistent conceptual model of this basin and its diagenetic modifications, based on a combination of geochemical data with petrographical and field information, provides the geodynamic context of the European margin at the onset of the Alpine orogeny. [ABSTRACT FROM AUTHOR]

Chlorine, lithium, and boron are trace elements in rhyolite but are enriched in groundwater flowing through rhyolite because they tend to partition into the fluid phase during high‐temperature fluid‐rock reactions. We present a large data set of major element and δ37Cl, δ7Li, and δ11B compositions of thermal water and rhyolite from Yellowstone Plateau Volcanic Field (YPVF). The Cl/B, Cl/Li, δ37Cl (−0.2‰ to +0.7‰), and δ11B (−6.2‰ to −5.9‰) values of alkaline‐chloride thermal waters reflect high‐temperature leaching of chlorine, lithium, and boron from rhyolite that has δ37Cl and δ11B values of +0.1‰ to +0.9‰ and −6.3‰ to −6.2‰, respectively. Chlorine and boron are not reactive, but lithium incorporation into hydrothermal alteration minerals result​s in a large range of Cl/Li, B/Li, and δ7Li (−1.2‰ to +3.8‰) values in thermal waters. The relatively large range in δ7Li values of thermal waters reflects a large range of values in rhyolite. Large volumes of rhyolite must be leached to account for the chloride, lithium and boron fluxes, implying deep groundwater flow through rhyolite flows and tuffs representing Yellowstone's three eruptive cycles (∼2.1 Ma). Lower Cl/B values in acid‐sulfate waters result from preferential partitioning of boron into the vapor phase and enrichment in the near‐surface water condensate. The Cl/B, Cl/Li, δ7Li (−0.3‰ to +2.1‰), and δ11B (−8.0‰ to −8.1‰) values of travertine depositing calcium‐carbonate thermal waters which discharge in the northern and southern YPVF suggest that chlorine, lithium, and boron are derived from Mesozoic siliciclastic sediments which contain detrital material from the underlying metamorphic basement. Plain Language Summary: High concentrations of chlorine, lithium, and boron are typically measured in groundwater that chemically react at elevated temperatures with rocks such as rhyolite that have high silica (SiO2) concentrations. The elevated concentrations result from the partitioning of these elements into groundwater during chemical reactions. Understanding how the stable isotopes of chlorine, lithium, and boron partition between groundwater and rocks in continental hydrothermal systems can provide guidance for geothermal energy and mineral deposit exploration and for characterizing degassing in active magmatic systems. We present a large data set of major element and stable isotope compositions of thermal waters and rhyolite from the Yellowstone hydrothermal system. Results suggest that the ratios of chlorine to boron and chlorine to lithium and the stable isotope compositions of these three elements mostly reflect the compositions of the rocks with which the hot water reacts. Some lithium is subsequently incorporated into hydrothermal alteration minerals and boron is enriched in vapor when the groundwater boils. Key Points: Cl, Li, and B in alkaline‐chloride thermal water in the Yellowstone Caldera are derived from leaching large volumes of rhyoliteCl and B are not incorporated into hydrothermal alteration minerals, but small amounts of Li are transferred from thermal water to rockIn calcium‐carbonate thermal waters which deposit travertine, Cl, Li, and B are probably derived from Mesozoic siliciclastic sediments [ABSTRACT FROM AUTHOR]

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their 18O/16O and 7Li/6Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in 7Li/28Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ18O, Δ'17O and δ7Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ18O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future. [ABSTRACT FROM AUTHOR]

The continuous improvement of analytical procedures using multi‐collector technologies in ICP‐mass spectrometry has led to an increased demand for isotope standards with improved homogeneity and reduced measurement uncertainty. For magnesium, this has led to a variety of available standards with different quality levels ranging from artefact standards to isotope reference materials certified for absolute isotope ratios. This required an intercalibration of all standards and reference materials, which we present in this interlaboratory comparison study. The materials Cambridge1, DSM3, ERM‐AE143, ERM‐AE144, ERM‐AE145, IRMM‐009 and NIST SRM 980 were cross‐calibrated with expanded measurement uncertainties (95% confidence level) of less than 0.030‰ for the δ25/24Mg values and less than 0.037‰ for the δ26/24Mg values. Thus, comparability of all magnesium isotope delta (δ) measurements based on these standards and reference materials is established. Further, ERM‐AE143 anchors all magnesium δ‐scales to absolute isotope ratios and therefore establishes SI traceability, here traceability to the SI base unit mole. This applies especially to the DSM3 scale, which is proposed to be maintained. With ERM‐AE144 and ERM‐AE145, which are product and educt of a sublimation–condensation process, for the first time a set of isotope reference materials is available with a published value for the apparent triple isotope fractionation exponent θapp, the fractionation relationship ln α(25/24Mg)/ln α(26/24Mg). [ABSTRACT FROM AUTHOR]

We investigate the Li isotope composition and the Li concentrations of metamorphic and sedimentary rocks of the Palaeozoic (Pz) basement in the Central Andes and follow the trace of the Li in the Cenozoic volcanic rocks at the active continental margin. The average Li isotope composition of Pz-basement closely resembles global averages of upper crustal rocks with overlapping, but higher average Li content in the Pz-basement. Lithium isotope composition and content in the Cenozoic volcanic rocks of the Central Volcanic Zone (CVZ) range from mantle-like signatures to Pz-basement compositions with high δ7Li values and high Li contents. Evolutionary trends of the Li isotope composition in the CVZ volcanic rocks can be explained by assimilation of the Pz-basement. At a margin-wide scale, the abundance of Li in the CVZ volcanic rocks is higher than that of the Cenozoic volcanic rocks of the active Andean arc north and south of the CVZ. The CVZ volcanic and Pz-basement rocks are considered to be the primary source of Li in world-class Li-deposits in evaporates of the Altiplano-Puna high plateau and its western slope between ca 27° and 20° S. These deposits define the so-called "Lithium-Triangle", between southern Bolivia, NW Argentina and NE Chile. The pivotal processes of extraction of Li from its primary rock sources and of Li migration from the source rocks to the deposits still await detailed investigation. [ABSTRACT FROM AUTHOR]

This study investigates the effect of tetrahedral B ([4]B) in synthetic tourmaline on the B-isotope fractionation between tourmaline and fluid. This is important for the correct interpretation of B-isotope variations in natural tourmalines containing "excess" B (greater than three atoms per formula unit), which substitutes for Si at tetrahedral sites. Such tourmalines commonly occur in Li, Al-rich pegmatites and have been reported from glaucophane schists that formed at high pressures during subduction. Tourmaline synthesis experiments were performed in a piston-cylinder apparatus in the system SiO2-Al2O3-B2O3-NaCl-H2O at 4 GPa and 700 °C using different run durations, starting from quartz-γ-Al2O3-H3BO3 solid mixtures and NaCl-solutions. We were able to produce "olenitic" tourmaline with excess B between 1.2 and 2.5 [4]B per formula unit. The B-isotope compositions of the olenitic tourmaline and coexisting fluids were determined by secondary ion mass spectrometry and multi-collector plasma source mass spectrometry to derive isotope fractionation coefficients. The results indicate that for every 10 mol% of total B in tourmaline in tetrahedral coordination, the value of Δ11Btur-fluid is shifted to more negative values by about 1‰ at 700 °C. This is in good agreement with published ab initio calculations and corresponds to an intracrystalline fractionation of B-isotopes between the trigonal B and tetrahedral T sites of tourmaline on the order of 8 ± 5‰, whereby 10B partitions to the T site. [ABSTRACT FROM AUTHOR]

We determined the lithium isotope fractionation between synthetic Li-bearing serpentine phases lizardite, chrysotile, antigorite, and aqueous fluid in the P, T range 0.2–4.0 GPa, 200–500°C. For experiments in the systems lizardite-fluid and antigorite-fluid, 7Li preferentially partitioned into the fluid and Δ7Li values followed the T-dependent fractionation of Li-bearing mica-fluid (Wunder et al. ). By contrast, for chrysotile-fluid experiments, 7Li weakly partitioned into chrysotile. This contrasting behavior might be due to different Li environments in the three serpentine varieties: in lizardite and antigorite lithium is sixfold coordinated, whereas in chrysotile lithium is incorporated in two ways, octahedrally and as Li-bearing water cluster filling the nanotube cores. Low-temperature IR spectroscopic measurements of chrysotile showed significant amounts of water, whose freezing point was suppressed due to the Li contents and the confined geometry of the fluid within the tubes. The small inverse Li-isotopic fractionation for chrysotile-fluid results from intra-crystalline Li isotope fractionation of octahedral Li[6] with preference to 6Li and lithium within the channels (Li[Ch]) of chrysotile, favoring 7Li. The nanotubes of chrysotile possibly serve as important carrier of Li and perhaps also of other fluid-mobile elements in serpentinized oceanic crust. This might explain higher Li abundances for low- T chrysotile-bearing serpentinites relative to high- T serpentinites. Isotopically heavy Li-bearing fluids of chrysotile nanotubes could be released at relatively shallow depths during subduction, prior to complete chrysotile reactions to form antigorite. During further subduction, fluids produced during breakdown of serpentine phases will be depleted in 7Li. This behavior might explain some of the Li-isotopic heterogeneities observed for serpentinized peridotites. [ABSTRACT FROM AUTHOR]

The fractionation of boron isotopes between synthetic dravitic tourmaline and fluid was determined by hydrothermal experiments between 400 and 700°C at 200 MPa and at 500°C, 500 MPa. Tourmaline was crystallized from an oxide mix in presence of water that contained boron in excess. In one series of experiments, [B]fluid/[B]tour was 9 after the run; in another series it was 0.1. All experiments produced tourmaline as the sole boron-bearing solid, along with traces of quartz and talc. Powder XRD and Rietveld refinements revealed no significant amounts of tetrahedrally coordinated boron in tourmaline. 11B always preferentially fractionated into the fluid. For experiments where [B]fluid/[B]tour was 9, a consistent temperature-dependent boron isotope fractionation curve resulted, approximated by Δ11B(tour–fluid) = −4.20 · [1,000/ T (K)] + 3.52; R 2 = 0.77, and valid from 400 to 700°C. No pressure dependence was observed. The fractionation (−2.7 ± 0.5‰ at 400°C; and −0.8 ± 0.5‰ at 700°C) is much lower than that previously presented by Palmer et al. (). Experiments where [B]fluid/[B]tour was 0.1 showed a significant larger apparent fractionation of up to −4.7‰. In one of these runs, the isotopic composition of handpicked tourmaline crystals of different size varied by 1.3‰. This is interpreted as resulting from fractional crystallization of boron isotopes during tourmaline growth due to the small boron reservoir of the fluid relative to tourmaline, thus indicating larger fractionation than observed at equilibrium. The effect is eliminated or minimized in experiments with very high boron excess in the fluid. We therefore suggest that values given by the above relation represent the true equilibrium fractionations. [ABSTRACT FROM AUTHOR]

The fractionation of lithium isotopes between synthetic spodumene as representative of Li-bearing clinopyroxene and Cl- and OH-bearing aqueous fluids was experimentally determined between 500 and 900°C at 2.0 GPa. In all the experiments, 7Li was preferentially partitioned into the fluid. The fractionation is temperature dependent and approximated by the equation Δ7Li(clinopyroxene–fluid)=−4.61×(1,000/ T [K]) + 2.48; R 2=0.86. Significant Li isotopic fractionation of about 1.0‰ exists even at high temperatures of 900°C. Using neutral and weakly basic fluids revealed that the amount of fractionation is not different. The Li isotopic fractionation between altered basalt and hot spring water (350°C) in natural samples is in good agreement with our experimentally determined fractionation curve. The data confirm earlier speculations drawn from the Li isotopic record of dehydrated metamorphic rocks that fluids expelled from a dehydrating slab carry heavier Li into the mantle wedge, and that a light Li component is introduced into the deeper mantle. Li and Li isotopes are redistributed among wedge minerals as fluids travel across the wedge into hotter regions of arc magma production. This modifies the Li isotopic characteristics of slab-derived fluids erasing their source memory, and explains the absence of cross-arc variations of Li isotopes in arc basalts. [ABSTRACT FROM AUTHOR]

The 31.6±0.3 Ma old Bufa del Diente alkali-syenite (NE Mexico) intruded a sequence of Cretaceous limestones with intercalated sub-horizontal chert layers. The cherts acted as aquifers that facilitated transport of brines and pegmatitic melts within the shallow-level (<1 kbar) contact-metamorphic aureole. Fluid-driven reactions between chert and marble wallrock, and the influx of late melts and various fluids gave rise to distinct chemical and isotopic signatures within the aquifer and across the zones of infiltration and fluid-driven reaction. Aqueous brines of magmatic origin produced thick wollastonite mantles around the chert layers. Wollastonite formation occurred at the expense of limestone and chert and generated CO2. This CO2-induced fluid unmixing into an aqueous brine and a low-density CO2-rich fluid, which was lost to the overlying marble where it oxidized organic matter and caused δ13C and δ18O shifts in a zone some 5–10 cm wide. After wollastonite formation, the chert aquifers were locally intruded by pegmatite veins carrying alkali feldspar, quartz, aegirine-augite, eudialyte, zircon, and apatite. Aqueous fluids that exsolved during crystallization of the pegmatite veins escaped along late cross-fractures and migrated along the inner and outer borders of the wollastonite margins. Chemical dispersion patterns of U, Al, Na + K, P, S, Fe, and REE across the chert-to-marble boundary and its metasomatic rims are shown by autoradiography and neutron-induced radiography. Scavenging of cations at mineralogical contacts and cation transport into the marbles occurred only on the mm to cm scale. Isotopic data for Pb and Sr across a simple metachert-marble boundary and for Pb, Sr, Nd, B, and Li across a metachert-pegmatite-marble sequence demonstrate the following: (1) The Pb and Sr isotopic signature of early fluids was buffered by the carbonate wallrock. Only late fluids, shielded from wallrock interaction by a wollastonite mantle, variably preserved a memory of their initial magmatic signature. (2) Since the Nd isotope signature of marble and chert is bound to calcite and clay minerals, systematic shifts to unradiogenic Nd in marble reflect loss of carbonate-bound Nd as the wollastonite margin is approached. Nd in the wollastonite margin is dominated by Nd originally bound to clay minerals. The later emplacement of the pegmatite, which carried the Nd isotope signature of its alkali-syenite source, had little effect on the Nd isotopic composition of the wollastonite rim. (3) Although the Li and B isotopic compositions reflect the alkali-syenite source, they are also affected by isotopic fractionation and partitioning between melt, fluid, and solids. [ABSTRACT FROM AUTHOR]

The isotopic analysis of boron from material that carries only trace amounts of boron requires low boron blank levels. Large efforts are taken to keep blank levels low by purifying reagents. We performed exposure experiments and determined procedure blanks before and after the air-handling system was modified from silicate glass filters to polyethylene/polystyrole and active carbon filters. Our investigations demonstrate that the air-handling system may be the major source of boron blank in many laboratories, as the widely used silicate glass filters, which contain boron as a major component, in the form of borax and boric acid, release significant amounts of boron to the air. [ABSTRACT FROM AUTHOR]