Lithium in tektites and impact glasses: Implications for sources, histories and large impacts

Lithium (Li) abundances and isotope compositions were determined in a representative suite of tektites (moldavites, Muong Nong-type tektites and an australite, Ivory Coast tektites and bediasites), impact-related glasses (Libyan Desert Glass, zhamanshinites and irghizites), a glass fragment embedded in the suevite from the Ries impact crater and sedimentary materials in order to test a possible susceptibility of Li to fractionation during hypervelocity impact events and to de-convolve links to their potential parental sources. The overall data show a large spread in Li abundance (4.7-58 ppm Li) and δ⁷Li values (−3.2‰ to 26.0‰) but individual groups of tektites and impact glasses have distinctive Li compositions.Most importantly, any significant high-temperature Li isotope fractionation can be excluded by comparing sedimentary lithologies from central Europe with moldavites. Instead, we suggest that Li isotope compositions in tektites and impact-related glasses are probably diagnostic of the precursor materials and their pre-impact geological histories. The Muong Nong-type tektites and australite specimen are identical in terms of Li concentrations and δ⁷Li and we tentatively endorse their common origin in a single impact event. Evidence for low-temperature Rayleigh fractionation, which must have operated prior to impact-induced melting and solidification, is provided for a subset of Muong Nong-type tektites. Although Li isotope variations in most tektites are broadly similar to those of the upper continental crust, Libyan Desert Glass carries high δ⁷Li ?24.7‰, which appears to mirror the previous fluvial history of parental material that was perhaps deposited in lacustrine environment or coastal seawater. Lithium isotopes in impact-related glasses from the Zhamanshin crater define a group distinct from all other samples and point to melting of chemically less evolved mafic lithologies, which is also consistent with their major and trace element patterns.Extreme shock pressures and the related extreme post-shock temperatures alone appear not to have any effect on the Li isotope systematics; therefore, useful information on parental lithologies and magmatic processes may be retrieved from analyses of Martian and lunar meteorites. Moreover, lack of significant Li depletion in tektites provides further constraints on the loss of moderately volatile elements during the Moon-forming impact.     

Advances in lithium analysis in solids by means of laser-induced breakdown spectroscopy: an exploratory study

Lithium is an important geochemical tracer for fluids or solids. However, because the electron microprobe cannot detect Li, variations of Li abundance at the micrometric scale are most often estimated from bulk analyses. In this study, the Li intense emission line at 670.706 nm in optical emission spectroscopy was used to perfect the analysis of Li at the micrometric scale by means of laser-induced breakdown spectroscopy (LIBS). To estimate lithium content for different geological materials, LIBS calibration of the emission line at 670.706 nm was achieved by use of synthetic glasses and natural minerals. The detection limit for this method is ∼5 ppm Li. Three applications to geological materials show the potential of LIBS for lithium determination, namely for Li-bearing minerals, melt inclusions, quartz, and associated fluid inclusions.For spodumene and petalite from granite pegmatite dikes (Portugal), the Li₂O concentrations are 7.6 ± 1.6 wt% and 6.3 ± 1.3 wt%, respectively, by use of LIBS. These values agree with ion microprobe analyses, bulk analyses, or both. For eucryptite crystals, the Li concentrations are scattered because grain size is smaller than the LIBS spatial resolution (6 to 8 μm). Lithium concentrations of melt inclusions from the Streltsovka U deposit (Siberia) are in the range of 2 to 6.2 wt% (Li₂O) for Li-rich daughter minerals. Lithium estimations on silicate glasses display values between 90 and 400 ppm.Lithium was also analyzed as a trace element in quartz. Transverse profiles were performed in hydrothermal barren quartz veins from the Spanish Central System (Sierra de Guadarrama). The highest Li concentrations (250 to 370 ppm) were found in specific growth bands in conjunction with the observed variation in optical cathodoluminescence intensity. Considering the fluid inclusion analysis, the source of fluid responsible to the Li enrichment in quartz is probably high-salinity fluids derived from sedimentary basins.     

Lithium enrichment and isotopic variation in minerals from peridotite xenoliths from northwestern Ethiopian plateau

We report Lithium (Li) concentrations and isotopic compositions for co-existing olivine, orthopyroxene (opx), and clinopyroxene (cpx) mineral separates from depleted and metasomatised peridotite xenoliths hosted by basaltic lavas from northwestern Ethiopian plateau (Gundeweyn area). The peridotites contain five lherzolites and one harzburgite and are variably depleted and enriched in LREE relative to HREE. In both depleted and enriched lherzolites, Li is preferentially incorporated into olivine (2.4-3.3 ppm) compared to opx (1.4-2.1 ppm) and cpx (1.4-2.0 ppm) whereas the Li contents of olivines (5.4 ppm) from an enriched harzburgiteare higher than those of lherzolites. Olivines from the samples show higher Li abundances than normal mantle olivines (1.6-1.9 ppm) indicating the occurrence of Li enrichments through melt-preroditite interaction. The average δ⁷ Li values range from +2.2 to +6.0‰ in olivine, from -0.1 to +2.0‰ in opx and from -4.4 to -0.9‰ in cpx from the lherzolites. The Li isotopic composition (3.5‰) of olivines from harzburgite fall within the range of olivine from lherzolites but the opxs show low in δ⁷Li (-2.0‰). Overall Li isotopic compositions of olivines from the peridotites fall within the range of normal mantle olivine, δ⁷Li values of ~+4±2‰ within uncertainty, reflecting metasomatism (enrichment) of the peridotites by isotopically heavy Li-rich asthenospheric melt. Li isotope zonation is also observed in most peridotite minerals. Majority of olivine grains display isotopically heavy cores and light rims and the reverse case is observed for some olivine grains. Orthopyroxene and clinopyroxene grains show irregular distribution in δ⁷Li. These features of Li isotopic compositions within and between grains in the samples reflect the effect of diffusion-driven isotopic fractionation during meltperidotite interaction and cooling processes.     

Gallium concentration in natural melts and fluids

We generalize, for the first time, published and original data on the gallium concentrations in natural magmatic melts and fluids obtained by studying quenched glasses in volcanic rocks and inclusions in minerals. Based on 2688 determinations, gallium concentrations in magmatic melts vary between 0.47 and 495 ppm at average content of 18.0 ppm (+4.2/–3.4). Gallium concentrations in magmatic melts generated in different geodynamic settings show different distribution. Minimum concentrations (on average, 16.0 ppm, +3.6/–2.9) are typical of the island-arc melts, while maximum contents were determined in melts of oceanic islands (on average, 29.1 ppm, +13.4/–9.2) and intracontinental rifts and hot spots (26.5 ppm, +25.4/–13.0). Published and new 339 determinations of gallium concentrations in natural fluids indicate the wider range of their variations as compared to those of melts: from 0.02 to 11260 ppm, at average 1.6 ppm (+10.8–1.4). The possible gallium fractionation in fluid—magmatic systems is discussed.     

Beryllium-10 in Australasian tektites: Constraints on the location of the source crater

By using accelerator mass spectrometry we have measured the ¹⁰Be concentrations of 86 Australasian tektites. Corrected to the time of tektite production ∼0.8 My ago, the ¹⁰Be concentrations (10⁶ atom/g) range from 59 for a layered tektite from Huai Sai, Thailand, to 280 for an australite from New South Wales, Australia. The average value is 143 ± 50. When tektites are sorted by country, their average measured ¹⁰Be concentrations increase slowly with increasing distance from Southeast Asia, the probable location of the tektite producing event, from 59 ± 9 for 6 layered tektites from Laos to 136 ± 20 for 20 splash-form tektites from Australia. The lowest ¹⁰Be concentrations for tektites fall on or within a contour centered off the shore of Vietnam, south of the Gulf of Tonkin (107°E; 17°N), but also encompassing two other locations in the area of northeastern Thailand previously proposed for the site of a single tektite-producing impact. The ¹⁰Be concentrations of layered tektites show only a weak anticorrelation (R ∼ −0.3) with the numbers of relict crystalline inclusions.Loosely consolidated, fine-grained terrestrial sediments or recently consolidated sedimentary rocks are the most likely precursor materials. Dilution of sediments with other kinds of rock raises problems in mixing and is not supported by petrographic data. Sedimentary columns that have the right range of ¹⁰Be concentrations occur off the coasts of places where sedimentation rates are high relative to those in the deep sea. A single impact into such a region, 15 to 300 m thick, could have propelled near-surface, high-¹⁰Be material farthest—to Australia—while keeping the deeper-lying, low-¹⁰Be layers closer to home. We do not rule out, however, other proposed mechanisms for tektite formation.     

Li distribution in aegirine lujavrite, Ilímaussaq alkaline intrusion, South Greenland: role of cumulus and post-cumulus processes

Li was analysed by activation analysis in 363 whole-rock samples and 53 minerals from a 200 m drill core through aegirine lujavrite I, Ilímaussaq intrusion. The rocks are interpreted as cumulates and Li is dominantly located in the intercumulus material which is thought to represent the coexisting magma with 540 ppm: whole-rock contents generally range from 80–260 ppm Li and reflect variations in the amount of intercumulus material from 25–48 wt. %. The proportion of intercumulus material is lowest in the deeper parts of the drill core, in layers with a moderate density stratification resulting from showers of near-liquidus crystals and in compressed cumulates beneath a large naujaite xenolith from the roof. Intercumulus arfvedsonite with an average of 2200 ppm Li contains the bulk of Li in most samples, but nearly every sample contains Li (0–176 ppm) outside the rock-forming minerals (Li-ORFM) which was unlocated by conventional mineral separation. Li-ORFM formed during late-magmatic crystallization (a) from the final residues of intercumulus magma which crystallised as accessory Li-mica and alteration products and (b) during in situ zeolitization of arvedsonite which released Li. A later, more intense zeolitization released Li from the rocks of the drill core. Naujaite xenoliths contain 42–130 ppm Li, except where Li-metasomatised, and are associated with low Li values in adjacent lujavrites. Shearing of consolidated lujavrite allowed mobilization of the Li and its reprecipitation along narrow channels (< 10 cm). Li is not concentrated in late hydrothermal coatings.     

Tektites: A post-Apollo view

Prior to the receipt of the lunar samples, it was the scientific consensus that tektites were melted and splashed material formed during large cometary or meteorite impact events. Whether the impact took place on the Earth or the Moon was the topic of a long-standing scientific debate, which raged with particular intensity during the decade previous to the lunar landings.Four definite and separate tektite-strewn fields are known: bediasites (North America, 34 m.y.); moldavites (Czechoslovakia, 14 m.y.); Ivory Coast (1.3 m.y.); and Southeast Asian and Australian fields (0.7 m.y.). A fifth possible occurrence, of high-Na australites, possibly 3–4 m.y. old, remains to be substantiated. The age of infall of the australites is not agreed upon. Radiometric and fission track dates agree with the magnetic stratigraphy for deep-sea core microtektite occurrences at about 0.7 m.y. Terrestrial stratigraphic evidence favours a recent (30,000 years) date.The chemistry of tektites appears to reflect that of the parent material, and losses during fusion appear to be restricted to elements and compounds more volatile than cesium. Terrestrial impact glasses provide small-scale analogues of tektite-forming events, and indicate that only the most volatile components are lost during fusion.The Apollo lunar missions provide critical evidence which refutes the hypothesis of lunar origin of tektites. Tektite chemistry is totally distinct from that observed in lunar maria basalts. These possess Cr contents which are two orders of magnitude higher than tektites, distinctive REE patterns with large Eu depletions, high Fe and low SiO₂ contents, low K/U ratios and many other diagnostic features, none of which are observed in the chemistry of tektites. The lunar uplands compositions, as shown by Apollo 14, 15 and 16 samples and the μ-ray and XRF orbiter data, are high-Al, low-SiO₂ compositions totally dissimilar to those of tektites. The composition of lunar rock 12013 shows typical lunar features and is distinct from that of tektites. The small amounts of lunar K-rich granitic material found in the soils have K/Mg and K/Na ratios 10–50 times those of tektites.The ages of the lunar maria (3.2–3.8 aeons) and uplands (> 4.0 aeons) are an order of magnitude older than the parent material of the Southeast Asian and Australian tektites, which yield Rb-Sr isochrons indicating ages of the order of 100–300 m.y. The lunar lead isotopic compositions are highly radiogenic whereas tektites have terrestrial Pb isotopic ratios. Lunar δ¹⁸ O values are low (< 7 per mil) compared with values of +9.6 to +11.5 per mil for tektites. In summary, a lunar impact origin for tektites is not compatible with the chemistry, age or isotopic composition of the lunar samples. A lunar volcanic origin, recently revived by O'Keefe (1970) encounters most of the same problems. Recent lunar volcanism (< 50 m.y.), if the source of tektites, should contribute tektite glass to the upper layers of the regolith. None has been found. The presence of meteoritic components in tektites, and the high pressure phase coesite, are more readily interpreted as evidence of impact.The element abundances and inter-element variations in tektites do not resemble those in terrestrial igneous rocks, but show a close similarity to terrestrial sandstones. The composition of the Southeast Asian tektites, australites and moldavites resembles that of micaceous sandstones or subgreywackes, the Ivory Coast tektite composition is similar to that of greywacke, and the bediasite chemistry is analogous to that of arkose.No suitable terrestrial impact site has been identified for the bediasites, Southeast Asian tektites and australites. It is suggested that a search for the source of these latter strewnfields be made using satellite photographs to look for wide shallow craters produced by super-Tunguska type events on areas of Mesozoic sandstones. The moldavites were possibly formed during the Ries Crater event but, if so, the precise source of the material remains to be identified. The Ivory Coast tektites are linked by chemistry, isotope and age evidence to the Bosumtwi Crater, Ghana. The overall evidence now supports the origin of tektites by cometary (or meteorite) impact on terrestrial sedimentary rocks.     

Trace element geochemistry by laser ablation ICP-MS of micas associated with Ta mineralization in the Tanco pegmatite,Manitoba, Canada

In the Tanco pegmatite, one of the world’s major Ta deposits, tantalum mineralization shows a complexity that reflects the complex petrogenesis of its host pegmatite. Micas are common in most of the pegmatite units and are intimately associated with the successive stages of Ta mineralization, from the wall zone to the central zones where micaceous replacement is pervasive. Different generations of micas, both primary and secondary, associated with Ta oxides, were selected for electron microprobe and laser ablation ICP-MS investigation. Their chemical trends are used to constrain the magmatic versus hydrothermal processes that played a role in their crystallization and their associated Ta mineralization. Micas range from dioctahedral muscovite to trioctahedral lepidolite through Al↔Li substitution. Unexpectedly, the most evolved compositions (low K/Rb ratios and high Li contents) occur in the wall zone; they are interpreted to reflect nonequilibrium crystallization from an undercooled melt, with or without boundary layer effects. In the central zones, the fine-grained mica–quartz assemblage hosts some coarser-grained Li-muscovite, which has the highest Ta contents (up to 400 ppm). These Li–F–a-rich micas are interpreted to originate from a magmatic metasomatic event, which was also at the origin of the MQM-style Ta mineralization at Tanco. However, the Li–Ta-poor, muscovite end-member compositions of fine-grained alteration micas suggest crystallization from an aqueous fluid, during a metasomatic (hydrothermal) event involving late pegmatitic fluids. The low Ta concentrations (around 50 ppm) of this fine-grained muscovite suggest that this fluid transported at least small amounts of Ta.     

Geochemistry, Monazite U–Pb Dating, and Li–Nd Isotopes of the Madi Rare Metal Granite in the Northeastern Part of the North China Craton

The Madi rare metal granite is a complex massif, which contains a variety of rare metals, such as Nb, Ta, Li, and Be. In this paper, the geochemical characteristics of the granite were obtained by multi-collector inductively coupled mass spectrometry (MC-ICP-MS). The precise crystalline age of the granite was obtained from monazite U-Pb dating, and the source of the granite was determined using Li-Nd isotopes. The Madi rare metal granite is a high-K (calc-alkaline), peraluminous, S-type granite. The U-Pb monazite age indicates that the crystalline age of the granite is 175.6 Ma, which is Early Jurassic. The granite is characterized by a relatively wide range of δ7Li values (+2.99‰ to +5.83‰) and high lithium concentrations (181 ppm to 1022 ppm). The lithium isotopic composition of the granite does not significantly correlate with the degree of magmatic differentiation. An insignificant amount of lithium isotope fractionation occurred during the granitic differentiation. The lithium isotopic composition of the granite significantly differs from that of the wall rock, but it is very similar to that of a primitive mantle peridotite xenolith (mean δ7Li value +3.5‰). The plot of Li concentration versus δ7Li indicates that the Li isotopic composition of the granite is similar to that of island arc lavas. Based on the above-described evidence, the granite was mainly derived from the crust, but it was contaminated by a deep granitic magma.     

An experimental study of bromine behaviour in water-saturated silicic melts

To assess the effect of the melt composition on bromine concentrations in magmas, we have investigated bromide solubility for water-saturated, iron-free silicic melts with variable Na+K/Al and Si/Al molar ratios (albite, haplogranite, rhyolite, and pantellerite). The experiments were performed in rapid quench cold-seal autoclaves over a range of pressure (1, 1.5, and 2 kbar) and temperature (900, 1000, and 1080 °C) with run durations from 5 to 7 days. A series of natural volcanic glasses and melt inclusions hosted in magmatic minerals were analysed together with the synthetic glasses by PIXE (proton-induced X-ray emission). The Br concentrations range from 5360 to 7850 ppm for albite, from 2800 to 3900 ppm for haplogranite, from 4300 to 5900 ppm for rhyolite, and from 9745 to 11,250 ppm for pantellerite. Br concentrations are negatively correlated with pressure in H₂O-saturated silicic melts and vary with (Na+K)/Al molar ratio with a minimum value at the ratio close to unity. Br behaves similarly to chlorine for all of these melt compositions. The bromide solubility is similar in albitic and rhyolitic melts, which implies that D^f/m is nearly the same for both compositions and is applicable for natural rhyolites as suggested in our previous study (Bureau et al., 2000). This means that the volcanic Br contribution to the atmosphere may be significant. In natural obsidian samples and MI hosted in quartz, olivine, and leucite, the Br concentration varies from < 3 to 28 ppm, with the highest concentrations in pantelleritic melts. We attribute the low Br concentrations of natural melts to a low initial abundance of this halogen in the Earth mantle. However, because Br behaves as an incompatible element before water exsolution, our results imply that magmas could contain much more dissolved Br before eruption and water degassing than the few ppm usually measured in volcanic rocks. Br behaviour during magma crystallisation is controlled by its partitioning into the H₂O-rich fluid phase when this occurs. In addition, its potential high solubility in silicate melts makes it a very sensitive chemical tracer of magma contamination by seawater and Br-rich material. This infers that the investigation of Br behaviour in subduction-zone samples may help for a better understanding of volatiles cycling between the Earth reservoirs.     

The rare alkalies in hydrothermal alteration at Wairakei and Broadlands,geothermal fields,N.Z.

Drillcores and waters from Wairakei and Broadlands geothermal areas New Zealand have been analyzed for Li, Rb, Cs, Na, K, Mg, Ca, Al, Ti, Mn, and Be. The drillcores were altered to various degrees at temperatures below 300°C in slightly alkaline chloride water, probably derived from rock-water interaction in untapped horizons at higher temperature. It changes its composition as it leaches Ca and Na from the rock and adds K, Rb, Cs and Li. Evaluation of these changes in relation to the dimensions of the altered zone under observation suggests that a high mass ratio of water to rock (e.g., 100) and a period of up to 1 million years are responsible for the present stage of alteration.Increase of K and Rb in the altered rocks is a result of the formation of abundant adularia in addition to illite. The $\text{K}\text{Rb}$ ratio of the rock decreases during alteration but remains higher than that of the fluid. Only clay materials and zeolites that preferentially absorb Rb give slightly lower $\text{K}\text{Rb}$ ratios than the fluid.The mineral phases responsible for the uptake of lithium during alteration are chlorite (300 ppm Li) and quartz (up to 430 ppm Li). Li uptake in quartz is considered to be the mechanism by which Al-rich quartz crystallises from alumino-silicates. $\text{Li}\text{Al}$ atomic ratios of 0.3–0.57 and Al concentrations up to 3000 ppm have been observed.Relatively small concentrations of Cs are found in potassic minerals (e.g. 10 ppm Cs in adularia, 44 ppm Cs in illite). However, 240 ppm Cs are found in wairakite from Wairakei equilibrated at 235°C. Lower equilibration temperatures may lead to higher cesium concentrations. This effect, in conjunction with a more concentrated hydrothermal fluid, could explain a content of 4500 ppm Cs in wairakite extracted from a drillcore taken in the El-Tatio geothermal field in Chile.     

Geochemistry and oxygen isotopic composition of olivine in kimberlites from the Arkhangelsk province: Contribution of mantle metasomatism

The paper presents data on the composition of olivine macrocrysts from two Devonian kimberlite pipes in the Arkhangelsk diamond province: the Grib pipe (whose kimberlite belongs to type I) and Pionerskaya pipe (whose kimberlite is of type II, i.e., orangeite). The dominant olivine macrocrysts in kimberlites from the two pipes significantly differ in geochemical and isotopic parameters. Olivine macrocrysts in kimberlite from the Grib pipe are dominated by magnesian (Mg# = 0.92–0.93), Ti-poor (Ti < 70 ppm) olivine possessing low Ti/Na (0.05–0.23), Zr/Nb (0.28–0.80), and Zn/Cu (3–20) ratios and low Li concentrations (1.2–2.0 ppm), and the oxygen isotopic composition of this olivine δ¹⁸O = 5.64‰ is higher than that of olivine in mantle peridotites (δ¹⁸O = 5.18 ± 0.28‰). Olivine macrocrysts in kimberlite from the Pionerskaya pipe are dominated by varieties with broadly varying Mg# = 0.90–0.93, high Ti concentrations (100–300 ppm), high ratios Ti/Na (0.90–2.39), Zr/Nb (0.31–1.96), and Zn/Cu (12–56), elevated Li concentrations (1.9–3.4 ppm), and oxygen isotopic composition δ¹⁸O = 5.34‰ corresponding to that of olivine in mantle peridotites. The geochemical and isotopic traits of low-Ti olivine macrocrysts from the Grib pipe are interpreted as evidence that the olivine interacted with carbonate-rich melts/fluids. This conclusion is consistent with the geochemical parameters of model melt in equilibrium with the low-Ti olivine that are similar to those of deep carbonatite melts. Our calculations indicate that the variations in the δ¹⁸O of the olivine relative the “mantle range” (toward both higher and lower values) can be fairly significant: from 4 to 7‰ depending on the composition of the carbonate fluid. These variations were formed at interaction with carbonate fluid, whose δ¹⁸O values do not extend outside the range typical of mantle carbonates. The geochemical parameters of high-Ti olivine macrocrysts from the Grib pipe suggest that their origin was controlled by the silicate (water–silicate) component. This olivine is characterized by a zoned Ti distribution, with the configuration of this distribution between the cores of the crystals and their outer zones showing that the zoning of the cores and outer zones is independent and was produced during two episodes of reaction interaction between the olivine and melt/fluid. The younger episode (when the outer zone was formed) likely involved interaction with kimberlite melt. The transformation of the composition of the cores during the older episode may have been of metasomatic nature, as follows from the fact that the composition varies from grain to grain. The metasomatic episode most likely occurred shortly before the kimberlite melt was emplaced and was related to the partial melting of pyroxenite source material.     

Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from Shangzhi,NE China: products of recent melt/fluid-peridotite interaction

Lithium elemental and isotopic disequilibrium has frequently been observed in the continental and oceanic mantle xenoliths, but its origin remains controversial. Here, we present a combined elemental and Li isotopic study on variably metasomatised peridotite xenoliths entrained in the Cenozoic basalts from Shangzhi in Northeast (NE) China that provides insight into this issue. Li concentration (0.3–2.7 ppm) and δ⁷Li (mostly 2‰–6‰) in olivine from the Shangzhi peridotites are similar to the normal mantle values and show roughly negative correlations with the indices of melt extraction (such as modal olivine and whole rock MgO). These features are consistent with variable degrees of partial melting. In contrast, clinopyroxene from the Shangzhi xenoliths shows significant Li enrichment (0.9–6.1 ppm) and anomalously light δ⁷Li (??13.8‰ to 7.7‰) relative to normal mantle values. Such features can be explained by Li diffusion from silicate melts or Li-rich fluids occurring over a very short time (several minutes to several hours). Moreover, the light Li isotopic compositions preserved in some bulk samples also indicate that these percolated melts/fluids have not had enough time to isotopically equilibrate with the bulk peridotite. We thus emphasize that Li isotopic fractionation in the Shangzhi mantle xenoliths is mainly related to Li diffusion from silicate melts or Li-rich fluids that took place shortly before or coincident with their entrainment into the host magmas.     

Iron local structure in tektites and impact glasses by extended X-ray absorption fine structure and high-resolution X-ray absorption near-edge structure spectroscopy

The local structure of iron in three tektites has been studied by means of Fe K-edge extended X-ray absorption fine structure (EXAFS) and high-resolution X-ray absorption near-edge structure (XANES) spectroscopy in order to provide quantitative data on <Fe-O> distance and Fe coordination number. The samples studied are a moldavite and two australasian tektites. Fe model compounds with known Fe oxidation state and coordination number were used as standards in order to extract structural information from the XANES pre-edge peak. EXAFS-derived grand mean <Fe-O> distances and Fe coordination numbers for the three tektite samples are constant within the estimated error (<Fe-O > =2.00 Å ± 0.02 Å, CN = 4.0 ± 0.4). In contrast to other data from the literature on Fe-bearing silicate glasses, the tektites spectra could not be fitted with a single Fe-O distance, but rather were fit with two independent distances (2 × 1.92 Å and 2 × 2.08 Å). High-resolution XANES spectra of the three tektites display a pre-edge peak whose intensity is intermediate between those of staurolite and grandidierite, thus suggesting a mean coordination number intermediate between 4 and 5. Combining the EXAFS and XANES data for Fe, we infer the mean coordination number to be close to 4.5.Comparison of the tektites XANES spectra with those of a suite of different impact glasses clearly shows that tektites display a relatively narrow range of Fe oxidation state and coordination numbers, whereas impact glasses data span a much wider range of Fe oxidation states (from divalent to trivalent) and coordination numbers (from tetra-coordinated to esa-coordinated). These data suggest that the tektite production process is very similar for all the known strewn fields, whereas impact glasses can experience a wide variety of different temperature-pressure-oxygen fugacity conditions, leading to different Fe local structure in the resulting glasses. These data could be of aid in discriminating between tektite-like impact glasses and impact glasses sensu strictu.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

The chemical composition of specular hematite from Tilkerode, Harz, Germany: implications for the genesis of hydrothermal hematite and comparison with the Quadrilátero Ferrífero of Minas Gerais, Brazil

The black shale-hosted selenide vein-type deposit at Tilkerode, eastern Harz, Germany, has specular hematite enclosed in clausthalite (PbSe). The specular hematite has Ti and V in amounts of up to ～1 wt.% TiO₂ and ～3 wt.% V₂O₅, and subordinate, but important, contents of Mo (22–372 ppm) and B (up to 68 ppm). The Tilkerode hematite serves as a reference for hydrothermal hematite formed at relatively low temperatures (<150 °C). The composition of the Tilkerode hematite is compared with that of two generations of specular hematite from itabirite-hosted iron-ore deposits in the Quadrilátero Ferrífero of Minas Gerais, Brazil. The first generation of specular hematite represents an early tectonic hematitisation of dolomitic itabirite at Águas Claras and occurs as fine-grained crystals. Reconnaissance data indicate that the Águas Claras hematite is poorer in Ti and V, relative to the Tilkerode hematite, but has ～5–10 ppm B and ～7–11 ppm Li. The second generation of specular hematite defines the pervasive tectonic foliation of the Gongo Soco iron ore. This hematite has Ti contents of up to ～2 wt.% TiO₂ and subordinate amounts of V (62–367 ppm); its B and Li concentrations are mostly below <2 ppm B and <1 ppm Li. The presence of Ti and B in the Tilkerode hematite can be explained by highly saline, B-bearing fluids that were capable of mobilising otherwise immobile Ti. The Mo signature of the Tilkerode hematite suggests that Mo was derived from the host black shale. In Minas Gerais, B and Li were incorporated into the early tectonic hematite from saline fluids at relatively low temperatures (Águas Claras) and then released during metamorphic hematite growth at higher temperatures, as suggested by the foliation-defining hematite without B–Li signature (Gongo Soco).     

Behaviour of Li and its isotopes during metasomatism of French Massif Central lherzolites

Li behaviour and distribution in the mantle were investigated by ion microprobe in situ measurements on co-existing olivine (ol), orthopyroxene (opx), clinopyroxene (cpx) and amphibole (amp) in xenoliths from the French Massif Central. The fertile spinel lherzolites of this study record increasing degrees of mantle metasomatism, from unmetasomatised anhydrous samples through cryptically metasomatised samples to highly metasomatised amphibole-rich samples. In anhydrous lherzolites, Li is preferentially incorporated into olivine (1.1-1.4 ppm, average values) compared to pyroxenes (0.2-0.9 ppm). The hydrous samples clearly show enrichment of Li in ol (1.5-5.0 ppm), opx (1.1-2.4 ppm) and cpx (2.4-5.4 ppm), while amphibole incorporates less Li than the co-existing phases (0.8-1.3 ppm). Average δ⁷Li values range from +7.6 to +14.5‰ in ol, from 5.1 to +13.7‰ in opx and from 8.8 to +10.3‰ in cpx from the anhydrous lherzolites. A layered peridotite sample (Sdi) shows higher Li content in all phases, with lighter isotopic composition in opx and cpx (−0.6 and −2‰ average δ⁷Li values, respectively). In the hydrous lherzolites average δ⁷Li values both overlap and extend beyond these ranges in ol (up to 17.5 ‰) and in opx (up to 22.9‰), and vary widely in cpx (−2.7 to +9.7‰). Low δ⁷Li values are observed in some opx (−10.4‰) and cpx (−13‰) from sample Sdi, and in cpx from three hydrous samples (from −9.7 to −5.3‰). The different anhydrous phases from the hydrous samples show large intra-grain variations in Li isotopic ratios (e.g., up to 18‰) compared to the same phases from the anhydrous samples (mostly less than 6‰), excepting sample Sdi which has up to 20.4‰ variation in cpx. Similar to the anhydrous silicates, amphiboles show a wide variation of δ⁷Li values on the intra-grain scale (2-27‰). These variations are interpreted to result from fractionation processes during metasomatism by a silicate melt undergoing compositional changes as it percolates through and reacts with the peridotite phases. Thus Li abundances and isotopic in situ measurements are useful for tracing metasomatic processes but the heterogeneities observed in the samples preclude any identification of a specific mantle source by its Li signature.     

Lithium isotopic systematics of peridotite xenoliths from Hannuoba, North China Craton: Implications for melt-rock interaction in the considerably thinned lithospheric mantle

Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ⁷Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ⁷Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ⁷Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ⁷Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ⁷Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.     

Petrology and Li-Be-B geochemistry of muscovite-biotite granite and associated pegmatite near Yellowknife,Canada

Prosperous granite (Rb-Sr 2520±25 Ma) occurs as several plutons (1–380 km² outcrop area) in a thick succession of metamorphosed greywacke-mudstone of the Yellowknife Supergroup. The average mineral content of the Sparrow pluton (in vol.%) is quartz (32), plagioclase (31), K-feldspar (24), muscovite (9), biotite (3), and apatite (<1). Average trace-element concentrations (in ppm) are Li (140), Be (4), B (28), Zn (47), Rb (250), Sr (76), Zr (75) and Ba (360). The central portion of the pluton is slightly richer in K, Sr, and Ba than the margin. Li is concentrated in mica (Li in biotite/Li in muscovite=4.7), and Be and B in muscovite and plagioclase. Countless pegmatite dikes occur in the Sparrow pluton and in schist-hornfels to the east; the outer limit is marked by the cordierite isograd, 9 km from the granite contact. Dikes vary greatly in size (1 km to a few cm in length), in mineral content (quartz, albite, K-feldspar, muscovite, tourmaline, beryl, spodumene), in major element composition (especially the NaK ratio), and in trace-element content (Li 18–5000 ppm, Be 5–260 ppm, B 20–150 ppm). Compared with Prosperous granite, the pegmatite bodies are richer in P and Rb, and poorer in Ti, Fe, Mg, Zr, and Ba. Dikes rich in tourmaline, beryl, and spodumene occur in overlapping zones situated progressively farther from the centre of the Sparrow pluton. The composition of tourmaline is related to host rock; the highest concentrations of Fe and Zn occur in crystals from pegmetite and the highest concentrations of Mg and V occur in crystals from tourmalinized schist, while those from granite and quartz veins occupy on intermediate position. Complex compositional zoning is present in some tourmaline crystals in pegmatite. Estimates of temperature (500°–600° C) and pressure (2–4 kb) of granite emplacement, based on the distribution of andalusite and sillimanite in the contact rocks, suggest that the final stage of granite emplacement occurred at sub-solidus conditions. A vaportransport model is proposed to explain the widespread distribution of the pegmatite dikes and their extreme compositional variability. Some of the pegmatite constituents, including Li, Be, and B, were possibly derived from Yellowknife graywacke and mudstone.     

Li-Sr-Nd isotope signatures of the plume and cratonic lithospheric mantle beneath the margin of the rifted Tanzanian craton (Labait)

Lithium concentrations and isotopic compositions of olivine and ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd of coexisting clinopyroxene from peridotite xenoliths from the Quaternary Labait volcano, Tanzania, document the influence of rift-related metasomatism on the ancient cratonic mantle. Olivines show negative correlations between Fo content and both δ⁷Li and Li concentrations. Olivines in iron-rich peridotites (Fo_85–87) have high Li concentrations (3.2–4.8 ppm) and heavy δ⁷Li (+5.2 to +6.6). In contrast, olivines in ancient, refractory peridotites have lower Li concentrations (∼2 ppm) and relatively light δ⁷Li (+2.6 to +3.5). This reflects mixing between ancient, refractory cratonic lithosphere and asthenosphere-derived rift magmas. A uniquely fertile, deformed, high-temperature garnet lherzolite, interpreted to be from the base of the lithosphere, has a ⁸⁷Sr/⁸⁶Sr of 0.7029 and ¹⁴³Nd/¹⁴⁴Nd of 0.51286, similar to HIMU oceanic basalts. It provides the best estimate of the Sr–Nd isotope composition of the upwelling mantle (i.e., plume, sensu lato) underlying this portion of the East African Rift, and is slightly less radiogenic compared to previous estimates of the plume that were based on rift basalts. Although elevated δ⁷Li are not exclusive to HIMU source regions, the data collectively indicate that the plume beneath Labait has HIMU characteristics in Sr, Nd and Li isotope composition. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.