Isotopic constraints on selenium degassing from basaltic magma and near-surface capture by fumarolic deposits: Implications for Se redistribution onto the Earth's surface

International audienceVolcanic emanations from cooling basaltic lava represent a diffuse and relatively poorly constrained source of metallic and non-metallic compounds to the Earth’s surface. These compounds become incorporated in fumarolic minerals and redeposit at the surface of lava flows before entering the environmental cycle. The semi-volatile and chalcophile element selenium (Se) can be either vital or toxic to animals and humans. Thus, understanding the pathways of Se capture and relative concentrations in fumaroles is imperative for estimating their contributions to soils and aquifers in volcanically active regions, with implications for animal and human health. In this study, we report Se concentrations and Se stable isotope composition in a sample suite comprising degassed and undegassed basaltic rocks and various fumarolic deposits (thenardite, Na-K sulfate, gypsum, fluoride, and native sulfur) fed from degassing lava flows at Piton de la Fournaise volcano, R´eunion Island. Erupted basaltic lavas (136–58 ng⋅g− 1 Se) lost up to more than half of their pre-eruptive Se due to subaerial degassing and retained a heavier isotope composition (δ82/76Se = 0.11 ± 0.17‰, 2 s.d.) compared to less undegassed volcanic glass (138 ng⋅g− 1 Se and δ82/76Se = − 0.19 ± 0.04‰, 2 s.e.). Fumarolic deposits that formed over a temperature range of ~800–100 ◦C and captured Se from the degassing lava show higher to very high Se concentrations ranging from 0.54 μg⋅g− 1 to 1578 μg⋅g− 1 and significant Se isotope fractionation (δ82/76Se = +0.6 to − 2.08‰). We propose two separate models that can explain the relative concentration and Se isotope composition of the deposits: 1) A compound oxidation state-dependent Se incorporation into the various fumarolic minerals, or 2) Temperaturedependent Rayleigh condensation from a cooling gas triggered by compound saturation. The Rayleigh condensation model can entirely explain the Se concentration and isotope composition of the fumaroles and predicts that up to 80% of the Se released from the lava is likely to be captured by precipitation to form solid phases within the lava pile, most dramatically in the coldest deposits below the sublimation temperature of SeO2 (< 315 ◦C). In contrast, mineral-dependent isotope pathways cannot fully explain our data, including the lighter Se isotope compositions in the more oxidized compounds compared to more reduced ones. Such a mineralogical effect cannot be excluded but further investigations and experimental studies are required in order to scrutinize and invoke its role. Finally, the environmental impact of these degassing-induced secondary products will be dependent on the relative compound water solubilities resulting in either Se mobilization towards aquifers or accumulation onto developing soils and plants. Such studies could prove useful for developing risk assessments in volcanically active regions on our planet, and for reaching a better understanding of the global continent-ocean Se isotope budget and signature

Genesis of ultra-high pressure garnet pyroxenites in orogenic peridotites and its bearing on the compositional heterogeneity of the Earth's mantle

International audienceWe present an integrated geochemical study of ultra-high pressure (UHP) garnet pyroxenites from the Ronda and Beni Bousera peridotite massifs (Betic-Rif Belt, westernmost Mediterranean). Based on their Sr-Nd-Pb-Hf isotopic systematics, we classify UHP garnet pyroxenites into three groups: Group A pyroxenites (Al2O3: 15–17.5 wt.%) have low initial 87Sr/86Sr, relatively high εNd, εHf and 206Pb/204Pb ratios, and variable 207Pb/204Pb and 208Pb/204Pb. Group B pyroxenites (Al2O3 < 14 wt.%) are characterized by high initial 87Sr/86Sr and relatively low εNd, εHf and 206Pb/204Pb ratios. Group C pyroxenites (Al2O3 ∼ 15 wt.%) have depleted radiogenic signatures with relatively low initial 87Sr/86Sr and 206Pb/204Pb, high εNd and εHf, and their 207Pb/204Pb and 208Pb/204Pb ratios are similar to those of Group B pyroxenites.The major and trace element and isotopic compositions of UHP garnet pyroxenites support their derivation from ancient (1.5–3.5 Ga) oceanic crust recycled into the mantle and intimately stirred with peridotites by convection. However, the genesis of these pyroxenites requires also the involvement of recycled continental lower crust with an isotopic composition akin to the lower crustal section of the lithosphere where these UHP garnet pyroxenites now reside in. These oceanic and continental crustal components were stirred in different proportions in the convective mantle, originating pyroxenites with a more marked geochemical imprint of either oceanic (Group A) or continental lower crust (Group B), or hybrid compositions (Group C). The pyroxenite protoliths likely underwent several melting events, one of them related to the formation of the subcontinental lithospheric mantle and continental crust, generating restitic UHP garnet pyroxenites now preserved in the Ronda and Beni Bousera orogenic peridotites. The extent of melting was mostly controlled by the bulk Mg-number (Mg#) of the pyroxenite protoliths, where protoliths with low Mg# experienced higher degrees of partial melting than sources with higher Mg#. Positive Eu and Sr anomalies in bulk rocks, indicative of their origin from cumulitic crustal gabbros, are preserved mostly in high Mg# pyroxenites due to their higher melting temperatures and consequent lower partial melting degrees.The results of this study show that the genesis of UHP garnet pyroxenites in orogenic peridotites requires a new recipe for the marble cake mantle hypothesis, combining significant recycling and stirring of both oceanic and continental lower crust in the Earth’s mantle. Furthermore, this study establishes a firm connection between the isotopic signatures of UHP pyroxenite heterogeneities in the mantle and the continental lower crust

Multi-stage evolution of the lithospheric mantle beneath the westernmost Mediterranean: Geochemical constraints from peridotite xenoliths in the eastern Betic Cordillera (SE Spain)

International audienceSpinel (± plagioclase) peridotite xenoliths from the Tallante and Los Perez volcanic centres in the eastern Betics (SE Spain) range from depleted (clinopyroxene-poor) harzburgites to fertile (clinopyroxene-rich) lherzolites and orthopyroxene-free wehrlites. Significantly, only one harzburgite, which is depleted in heavy rare earth elements (HREE), retains the imprint of ca. 20% ancient melting of an original garnet lherzolite source. In contrast, REE abundances of other harzburgites and lherzolites from the eastern Betics have been increased by melt-rock reaction. The whole-rock and mineral compositions of these mantle rocks are largely controlled by three types of modal metasomatism: 1) common clinopyroxene-orthopyroxene addition and olivine consumption which increased FeOt, SiO2 and Al2O3, and decreased MgO compared to the refractory melting products; 2) subordinate orthopyroxene dissolution and precipitation of clinopyroxene and olivine, which led to higher FeOt and MgO and lower SiO2 than in common (orthopyroxene-rich) lherzolites; and 3) rare orthopyroxene consumption and olivine addition that caused higher FeOt and lower SiO2 compared to the original melting residues. These mineral modal and major element variations have been produced mostly by interactions with relatively FeOt-rich/SiO2-poor melts, likely derived from a peridotite-pyroxenite lithospheric mantle with a highly heterogeneous isotopic composition. Melting of the lithospheric mantle in the western Mediterranean was triggered by upwelling of the asthenosphere induced by back-arc extension in the Late Oligocene-Early Miocene. Trapping of small fractions of exotic melts in whole-rocks — likely the parental magmas of Miocene back-arc dykes that intruded the Betic crust — caused local disequilibrium between the trace element signatures and Pb isotopic compositions of clinopyroxene and whole-rock. Subsequent interaction with SiO2-undersaturated magmas, similar to the parental melts of the Pliocene alkali basalts that host the xenoliths, promoted orthopyroxene consumption and clinopyroxene-olivine enrichment at locations close to magma conduits, and finally generated orthopyroxene-free wehrlites. This event constitutes the last episode of the Cenozoic magmatic evolution of the westernmost Mediterranean which is recorded in the mantle xenoliths from the eastern Betics

Sr-Nd-Pb isotopic systematics of crustal rocks from the western Betics (S. Spain): Implications for crustal recycling in the lithospheric mantle beneath the westernmost Mediterranean

International audienceWe present new Sr-Nd-Pb isotope data of the western Alpujárride metamorphic basement and the pre-Miocene Flysch sediments of the Betic Cordillera (southern Spain). Nd model ages are consistent with an increasing detrital input from the Alborán domain to the Flysch Trough in the western Mediterranean during the late Oligocene. The Alpujárride metamorphic crustal rocks derived from Archean-Paleoproterozoic terranes located along the northern margin of Gondwana in the Neoproterozoic. The heterogeneous isotopic signatures of the Alpujárride units indicate that they have different sedimentary protoliths and underwent contrasted Variscan and pre-Variscan tectono-magmatic evolutions. Melts/fluids derived from the western Alpujárride gneisses contaminated the mantle source of the Ronda high-Mg pyroxenite dykes, implying that the Alpujárride lower crust underthrusted the subcontinental lithospheric mantle of the Alborán domain generating subduction-like magmatism in the late Oligocene. The western Alpujárride upper crust is involved in the Neogene volcanism of the Alborán Sea basin, but only contaminated some LREE-enriched calc-alkaline lavas erupted along the continental margins. On the other hand, tholeiitic lavas in the center of the basin show no isotopic evidence of crustal assimilation. This indicates that most of the crust in the central Alborán Sea accreted by Miocene tholeiitic magmatism and that Alpujárride lower crust is absent and likely foundered close to the continental margins of the basin

Hyperextension of continental to oceanic-like lithosphere: The record of late gabbros in the shallow subcontinental lithospheric mantle of the westernmost Mediterranean

International audienceWe report gabbroic dikes in the plagioclase tectonite domains of the Ojén and Ronda massifs (Betic Cordillera, southern Spain), which record crystallization at low-pressure syn-, or slightly postkinematic to the late ductile history of the Betic Peridotite in the westernmost Mediterranean. We present mineral major and trace element compositional data of discordant gabbroic dikes in the Ojén massif and gabbroic patches in the Ronda massif, complemented by the whole rock and electron backscattered diffraction (EBSD) data of the Ojén occurrence. In the Ojén massif, gabbro occurs as 1–3 centimeter wide discordant dikes that crosscut the plagioclase tectonite foliation at high angle. These dikes are composed of cm-scale igneous plagioclase and clinopyroxene crystals that show shape preferred orientations subparallel to the lineation of the host peridotite and oblique to the trend of the dike. Intrusion of Ojén gabbro dikes is coherent with the stress field that formed the high temperature, ductile plagioclase tectonite foliation and then attests for a mantle igneous event prior to the intracrustal emplacement of the massif. In the Ronda massif, gabbroic rocks crystallized in subcentimeter wide anastomozing veins, or as interstitial patches in the host dunite. They are mostly composed of plagioclase and clinopyroxene. Plagioclase composition is bytownitic in the Ojén, and andesinic in the Ronda massif. Clinopyroxene in both places shows identical, light Rare-Earth Element (LREE) depleted trace element patterns. The calculated trace element composition of melts in exchange equilibrium with the studied igneous clinopyroxenes reflects LREE-enriched character coupled with negative Eu anomaly, and indicates that gabbro-forming melts in Ronda and Ojén share a common melt source with an island arc tholeiitic affinity. Geothermobarometric data and liquidus mineralogy indicate that gabbro crystallization occurred at shallow depths (0.2–0.5 GPa) in a 7–16 km thick lithospheric section. These data suggest that gabbro-forming melts in the Betic Peridotite record a mantle igneous event at very shallow depths and provide evidence for the hyperextension of the continental lithosphere compatible with extreme backarc basin extension induced by the slab rollback of the Cenozoic subduction system in the westernmost Mediterranean

Refertilization Processes in the Subcontinental Lithospheric Mantle: the Record of the Beni Bousera Orogenic Peridotite (Rif Belt, Northern Morocco)

International audienceCorrelations between major and minor transition elements in tectonically emplaced orogenic peridotites have been ascribed to variable degrees of melt extraction and melt–rock reaction processes, leading to depletion or refertilization. To elucidate how such processes are recorded in the subcontinental lithospheric mantle, we processed a large geochemical dataset for peridotites from the four tectono-metamorphic domains of the Beni Bousera orogenic massif (Rif Belt, northern Morocco). Our study reveals that variations in bulk-rock major and minor elements, Mg-number and modal mineralogy of lherzolites, as well as their clinopyroxene trace element compositions, are inconsistent with simple partial melting and mainly resulted from different reactions between melts and depleted peridotites. Up to 30% melting at < 3 GPa and cryptic metasomatism can account for the geochemical variations of most harzburgites. In Grt–Sp mylonites, melting and melt–rock reactions are masked by tectonic mixing with garnet pyroxenites and subsolidus re-equilibration. In the rest of the massif, lherzolites were mostly produced by refertilization of a refractory protolith (Mg-number ∼ 91, Ol ∼ 70%, Cpx/Opx = 0·4) via two distinct near-solidus, melt–rock reactions: (1) clinopyroxene and orthopyroxene precipitation and olivine consumption at melt/rock ratios <0·75 and variable mass ratio between crystallized minerals and infiltrated melt (R), which are recorded fairly homogeneously throughout the massif; (2) dissolution of orthopyroxene and precipitation of clinopyroxene and olivine at melt/rock ratios ≤1 and R = 0·2–0·3, which affected mainly the Ariègite–Seiland and Seiland domains. The distribution of secondary lherzolites in the massif suggests that the first refertilization reaction occurred prior to the differentiation of the Beni Bousera mantle section into petro-structural zones, whereas the second reaction was associated with the development of the tectono-metamorphic domains. Our data support a secondary, refertilization-related origin for most lherzolites in orogenic peridotite massifs