Constraints on the evolution of magmas from diffusion-driven chemical and Fe-Mg isotopic zoning in natural olivines analyzed by femtosecond-LA-ICP-MS

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Depth profile analyses by femtosecond laser ablation (multicollector) inductively coupled plasma mass spectrometry for resolving chemical and isotopic gradients in minerals

Femtosecond laser ablation (fs-LA) coupled to a multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) instrument has been proven to be a powerful means to analyze isotope ratios of “non-traditional” stable isotope systems with high spatial resolution, precision, and accuracy. The technique has been successfully applied, e.g., to investigate diffusion-generated isotopic zoning of the elements Li, Mg, and Fe in magmatic crystals. Here, we present a novel sampling technique employing a fs-LA system that is equipped with a computer numerical control (CNC) laser stage, using the open-source software LinuxCNC. Combining this laser set up with ICP-MS or MC-ICP-MS allows us to perform depth profile analyses of major and trace elements, respectively, as well as metal stable isotope variations of Fe and Mg in olivine crystals and in experimental diffusion couples. Samples are ablated in circular patterns with profile diameters of 100–200 µm using a laser spot size of 25–30 µm. Depending on the scan speed and the repetition rate of the laser, each ablated sample layer is between 300 nm and 3.0 µm thick. The integrated signal of one ablated layer represents one data point of the depth profile. We have tested this technique by analyzing 5–50 µm deep depth profiles (consisting of 15–25 individual layers) of homogeneous and chemically zoned olivine crystal cuboids. The minor and trace element analyses of the zoned cuboids, conducted by fs-LA-ICP-MS, were compared with “horizontal” profiles analyzed in polished sections of the cuboids with electron probe microanalysis (EPMA). Furthermore, we analyzed Fe–Mg isotopic depth profiles of the same cuboids with fs-LA-MC-ICP-MS, of which the chemically zoned ones also showed isotopic zoning at identical scales. Isotopic depth profiles were also conducted on an unzoned olivine cuboid that was coated with a 26Mg- and 56Fe-enriched olivine thin film (of ∼ 800 nm) in order to investigate top-to-bottom contamination during depth profiling. Our results indicate that (i) concentration data acquired by fs-LA depth profiling match well with EPMA data, (ii) precise and accurate Fe and Mg isotopic data can be obtained (i.e., precision and accuracy are ≤ 0.12 ‰ and ≤ 0.15 ‰ for both δ26Mg and δ56Fe, respectively), and (iii) potential top-to-bottom contamination during depth profiling of isotope ratios can be avoided. The technique presented herein is particularly suitable for the investigation of minerals or glasses with chemical and/or isotopic gradients (e.g., diffusion zoning) vertical to planar surfaces. It can also be applied in materials sciences in order to analyze thin films, coatings, or surface contaminations on solids

Multi-Stage Magma Evolution in Intra-Plate Volcanoes: Insights From Combined in situ Li and Mg–Fe Chemical and Isotopic Diffusion Profiles in Olivine

Understanding the timescales of magma evolution and ascent is essential for interpreting geophysical monitoring signals from active volcanoes. In this study, we explore the potential of diffusion-driven Li concentration and isotope zoning profiles recorded by magmatic olivine crystals to unravel time scales of magma evolution processes. Lithium is a fast-diffusing element and may provide the opportunity to investigate changes in magma composition during magma ascent, shortly before eruption. Lithium chemical and isotopic profiles were determined in olivines from two localities in the Massif Central volcanic region (France) that have previously been investigated for their Fe–Mg isotope systematics. The combined investigation of isotopic and chemical profiles makes it possible to distinguish between crystal growth and diffusion events. Extremely low δ7Li-values down to −30.7‰ (relative to the commonly used Li isotope standard IRMM-16) in the crystal core regions and elevated values at crystal rims (δ7Li ∼8 to 10‰), along with increasing concentrations from cores (∼3 to 1 μg/g) toward rims (12 to 6 μg/g) were found. The shape and orientation of both the chemical and isotopic profiles indicate that they were dominantly generated by Li diffusion into and within the olivine grains during magmatic differentiation. While Mg–Fe isotope and major element profiles have been modeled by a single diffusion event (Oeser et al., 2015), concentration and isotope profiles of Li indicate that a second diffusion event took place, that was not recorded by the Mg–Fe exchange diffusion couple. The first diffusion event was interpreted as reflecting the residence of the olivine crystals in a magma chamber. As diffusion coefficients for Fe–Mg exchange diffusion are very well determined, the time scales of this event are likely best quantified by Mg–Fe isotopic exchange diffusion modeling (Oeser et al., 2015). This event probably also generated the low δ7Li observed in olivine cores. Comparing the length of the Mg–Fe and Li profiles could thus be used to determine the less well-known diffusion coefficients of Li in the studied olivine crystals. The findings of this study indicate that Li diffusion at low Li concentration levels, as typically observed in natural olivine, may be not as fast as previously thought. The second diffusion event might represent a short-lived event, such as degassing, related to the ascent of the magma and/or magma cooling after emplacement of the lava. Such a process would only affect Li, which, in contrast to the refractory elements Fe and Mg, is volatile during degassing. The findings of this study show that, according to their different diffusion rates and physiochemical properties, the combined use of spatially resolved Li and Mg–Fe chemical and isotopic diffusion profiles, is a powerful tool to model even multi-stage evolution processes in magmatic systems. © Copyright © 2020 Steinmann, Oeser, Horn and Weyer

Mantle-derived trace element variability in olivines and their melt inclusions

Trace element variability in oceanic basalts is commonly used to constrain the physics of mantle melting and the chemistry of Earth's deep interior. However, the geochemical properties of mantle melts are often overprinted by mixing and crystallisation processes during ascent and storage. Studying primitive melt inclusions offers one solution to this problem, but the fidelity of the melt-inclusion archive to bulk magma chemistry has been repeatedly questioned. To provide a novel check of the melt inclusion record, we present new major and trace element analyses from olivine macrocrysts in the products of two geographically proximal, yet compositionally distinct, primitive eruptions from the Reykjanes Peninsula of Iceland. By combining these macrocryst analyses with new and published melt inclusion analyses we demonstrate that olivines have similar patterns of incompatible trace element (ITE) variability to the inclusions they host, capturing chemical systematics on intra- and inter-eruption scales. ITE variability (element concentrations, ratios, variances and variance ratios) in olivines from the ITE-enriched Stapafell eruption is best accounted for by olivine-dominated fractional crystallisation. In contrast, ITE variability in olivines and inclusions from the ITE-depleted Háleyjabunga eruption cannot be explained by crystallisation alone, and must have originated in the mantle. Compatible trace element (CTE) variability is best described by crystallisation processes in both eruptions. Modest correlations between host and inclusion ITE contents in samples from Háleyjabunga suggest that melt inclusions can be faithful archives of melting and magmatic processes. It also indicates that degrees of ITE enrichment can be estimated from olivines directly when melt inclusion and matrix glass records of geochemical variability are poor or absent. Inter-eruption differences in olivine ITE systematics between Stapafell and Háleyjabunga mirror differences in melt inclusion suites, and confirm that the Stapafell eruption was fed by lower degree melts from greater depths within the melting region than the Háleyjabunga eruption. Although olivine macrocrysts from Stapafell are slightly richer in Ni than those from Háleyjabunga, their overall CTE systematics (e.g., Ni/(Mg/Fe), Fe/Mn and Zn/Fe) are inconsistent with being derived from olivine-free pyroxenites. However, the major element systematics of Icelandic basalts require lithological heterogeneity in their mantle source in the form of Fe-rich and hence fusible domains. We thus conclude that enriched heterogeneities in the Icelandic mantle are composed of modally enriched, yet nonetheless olivine-bearing, lithologies and that olivine CTE contents provide an incomplete record of lithological heterogeneity in the mantle. Modally enriched peridotites may therefore play a more important role in oceanic magma genesis than previously inferred.</p

Li–Na interdiffusion and diffusion-driven lithium isotope fractionation in pegmatitic melts

In this study, we investigate the diffusion of Li and its stable isotopes (6Li and 7Li) in flux-rich (1.8 % Li2O, 2.6 % B2O3, 2.3 % P2O5 and 3 % F) pegmatitic melts in order to contribute to the understanding of Li enrichment in such systems. Two glasses were synthesized with a model pegmatitic composition, one of which is highly enriched in Li (> 1 wt %, PEG2-blue) and the other one essentially Li-free (PEG2-Li-free). Diffusion couple experiments were performed to determine the chemical diffusivity of Li in dry pegmatitic melts. Experiments were conducted using rapid-heat and rapid-quench cold-seal pressure vessels in a temperature range of 650–940 ∘C at 100 MPa with Ar as the pressure medium. We observed rapidly formed diffusion profiles, driven by an interdiffusive exchange of the monovalent alkalis Li and Na, while the other elements are immobile on the timescale of experiments (1–30 min). From these experiments, activation energies for Li–Na interdiffusion were determined as 99 ± 7 kJ mol−1 with a pre-exponential factor of log D0 = −5.05 ± 0.33 (D0 in m2 s−1). Li and Na partitioning between the stronger depolymerized PEG2-blue and the less depolymerized PEG2-Li-free leads to a concentration jump at the interface; i.e. Na is enriched in the more depolymerized PEG2-blue. Li–Na interdiffusion coefficients in the studied melt composition are in a similar range as Li and Na tracer diffusivities in other dry aluminosilicate melts, confirming little to no effect of aluminosilicate melt composition on Li diffusivity. Thus, added fluxes do not enhance the Li diffusivity in the same way as observed for H2O (Holycross et al., 2018; Spallanzani et al., 2022). Using melt viscosity as a proxy for the polymerization of the melt shows that water has a stronger potential to depolymerize a melt compared to other fluxing elements. Faster diffusion of 6Li compared to 7Li leads to a strong Li isotope fractionation along the diffusion profile, resulting in δ7Li as low as −80 ‰ relative to the diffusion-unaffected regions. This diffusive isotope fractionation can be quantified with an empirical isotope fractionation factor (β) of 0.20 ± 0.04, similar to previously observed β values for Li diffusion in melts. This suggests in accordance with previously published data that a β value of ca. 0.2 seems to be universally applicable to diffusive Li isotope fractionation in aluminosilicate melts

Hydrogenetic, Diagenetic and Hydrothermal Processes Forming Ferromanganese Crusts in the Canary Island Seamounts and Their Influence in the Metal Recovery Rate with Hydrometallurgical Methods

Four pure hydrogenetic, mixed hydrogenetic-diagenetic and hydrogenetic-hydrothermal Fe-Mn Crusts from the Canary Islands Seamount Province have been studied by Micro X-Ray Diffraction, Raman and Fourier-transform infrared spectroscopy together with high resolution Electron Probe Micro Analyzer and Laser Ablation Inductively Coupled Plasma Mass Spectrometry in order to find the correlation of mineralogy and geochemistry with the three genetic processes and their influence in the metal recovery rate using an hydrometallurgical method. The main mineralogy and geochemistry affect the contents of the different critical metals, diagenetic influenced crusts show high Ni and Cu (up to 6 and 2 wt. %, respectively) (and less Co and REY) enriched in very bright laminae. Hydrogenetic crusts on the contrary show High Co and REY (up to 1 and 0.5 wt. %) with also high contents of Ni, Mo and V (average 2500, 600 and 1300 μg/g). Finally, the hydrothermal microlayers from crust 107-11H show their enrichment in Fe (up to 50 wt. %) and depletion in almost all the critical elements. One hydrometallurgical method has been used in Canary Islands Seamount Province crusts in order to quantify the recovery rate of valuable elements in all the studied crusts except the 107-11H, whose hydrothermal critical metals’ poor lamina were too thin to separate from the whole crust. Digestion treatment with hydrochloric acid and ethanol show a high recovery rate for Mn (between 75% and 81%) with respect to Fe (49% to 58%). The total recovery rate on valuable elements (Co, Ni, Cu, V, Mo and rare earth elements plus yttrium (REY)) for the studied crusts range between 67 and 92% with the best results for Co, Ni and V (up to 80%). The genetic process and the associated mineralogy seem to influence the recovery rate. Mixed diagenetic/hydrogenetic crust show the lower recovery rate for Mn (75%) and Ni (52.5%) both enriched in diagenetic minerals (respectively up to 40 wt. % and up to 6 wt. %). On the other hand, the presence of high contents of undigested Fe minerals (i.e., Mn-feroxyhyte) in hydrogenetic crusts give back low recovery rate for Co (63%) and Mo (42%). Finally, REY as by-product elements, are enriched in the hydrometallurgical solution with a recovery rate of 70–90% for all the studied crusts

Prerequisites for coexistence: human pressure and refuge habitat availability shape continental‑scale habitat use patterns of a large carnivore

Context Adjustments in habitat use by large carnivores can be a key factor facilitating their coexistence with people in shared landscapes. Landscape composition might be a key factor determining how large carnivores can adapt to occurring alongside humans, yet broad-scale analyses investigating adjustments of habitat use across large gradients of human pressure and landscape composition are lacking. Objectives Here, we investigate adjustments in habitat use by Eurasian lynx (Lynx lynx) in response to varying availability of refuge habitats (i.e., forests and rugged terrain) and human landscape modifcation. Methods Using a large tracking dataset including 434 individuals from seven populations, we assess functional responses in lynx habitat use across two spatial scales, testing for variation by sex, daytime, and season. Results We found that lynx use refuge habitats more intensively with increasing landscape modifcation across spatial scales, selecting forests most strongly in otherwise open landscapes and rugged terrain in mountainous regions. Moreover, higher forest availability enabled lynx to place their home ranges in more human-modifed landscapes. Human pressure and refuge habitat availability also shaped temporal patterns of lynx habitat use, with lynx increasing refuge habitat use and reducing their use of human-modifed areas during periods of high exposure (daytime) or high vulnerability (postnatal period) to human pressure. Conclusions Our fndings suggest a remarkable adaptive capacity of lynx towards human pressure and underline the importance of refuge habitats across scales for enabling coexistence between large carnivores and people. More broadly, we highlight that the composition of landscapes determines how large carnivores can adapt to human pressure and thus play an important role shaping large carnivore habitat use and distributions.publishedVersio

Integrating animal tracking datasets at a continental scale for mapping Eurasian lynx habitat

Aim: The increasing availability of animal tracking datasets collected across many sites provides new opportunities to move beyond local assessments to enable de-tailed and consistent habitat mapping at biogeographical scales. However, integrating wildlife datasets across large areas and study sites is challenging, as species' varying responses to different environmental contexts must be reconciled. Here, we compare approaches for large-area habitat mapping and assess available habitat for a recolo-nizing large carnivore, the Eurasian lynx (Lynx lynx).Location: Europe.Methods: We use a continental-scale animal tracking database (450 individuals from 14 study sites) to systematically assess modelling approaches, comparing (1) global strategies that pool all data for training versus building local, site-specific models and combining them, (2) different approaches for incorporating regional variation in habi-tat selection and (3) different modelling algorithms, testing nonlinear mixed effects models as well as machine-learning algorithms.Results: Testing models on training sites and simulating model transfers, global and local modelling strategies achieved overall similar predictive performance. Model performance was the highest using flexible machine-learning algorithms and when incorporating variation in habitat selection as a function of environmental variation. Our best-performing model used a weighted combination of local, site-specific habi-tat models. Our habitat maps identified large areas of suitable, but currently unoccu-pied lynx habitat, with many of the most suitable unoccupied areas located in regions that could foster connectivity between currently isolated populations.Main Conclusions: We demonstrate that global and local modelling strategies can achieve robust habitat models at the continental scale and that considering regional variation in habitat selection improves broad-scale habitat mapping. More generally, we highlight the promise of large wildlife tracking databases for large-area habitat mapping. Our maps provide the first high-resolution, yet continental assessment of lynx habitat across Europe, providing a consistent basis for conservation planning for restoring the species within its former range.publishedVersio

Study of charmonium and charmonium-like contributions in B+ → J/ψηK+ decays

A study of B+→ J/ψηK+ decays, followed by J/ψ → μ+μ− and η → γγ, is performed using a dataset collected with the LHCb detector in proton-proton collisions at centre-of-mass energies of 7, 8 and 13 TeV, corresponding to an integrated luminosity of 9 fb−1. The J/ψη mass spectrum is investigated for contributions from charmonia and charmonium-like states. Evidence is found for the B+→ (ψ2(3823) → J/ψη)K+ and B+→ (ψ(4040) → J/ψη)K+ decays with significance of 3.4 and 4.7 standard deviations, respectively. This constitutes the first evidence for the ψ2(3823) → J/ψη decay