Geochemistry of sapphirine-apatite-calcite-bearing gabbroic dykes from the Finero Phlogopite Peridotite (Ivrea-Verbano Zone): evidence for multistage interaction with the ambient peridotite

The Finero Phlogopite-Peridotite (FPP) is a mantle unit outcropping in the northernmost tip of the Ivrea-Verbano Zone (IVZ, Southern Alps). It shows a virtually complete recrystallization due to pervasive to channelled melt migration. The pervasive metasomatism formed a main lithologic association constituted by phlogopite harzburgites associated to phlogopite pyroxenites (mainly olivine-websterites, websterites and orthopyroxenites). These lithologies are also rich in amphibole and do not show significant chemical gradients among them (Zanetti et al., 1999). The channelled migration stages formed dunite bodies, which sometimes contain stratiform chromitites and, more rarely, pyroxenite layers similar to those associated to phlogopite harzburgite. The FPP also shows a discrete number of other, subordinate rock-types, which are characterised by the presence of apatite usually associated to carbonates (i.e. calcite or dolomite) and exhibit marked modal and chemical gradients with respect to the host phlogopite harzburgite. Examples of these lithologies are apatite-dolomitebearing wehrlites and harzburgites (e.g. Zanetti et al. 1999; Morishita et al., 2008), apatite-calcite zircon-syenites and hornblendites. Ar-Ar amphibole analysis and U-Pb zircon and apatite data return Triassic ages for these rocks, which have been considered to document the time of melt/fluid injection. Notwithstanding the apparent mineralogical and chemical differences with the main lithologic sequences, apatite-carbonates-bearing rocks have been frequently interpreted as cogenetic to phlogopite harzburgites. To debate the petrogenesis of these rocks, a detailed field, petrological and geochemical investigation has been carried out on a swarm of apatite-calcite-bearing gabbroic veins that randomly cut the main lithologic association. Preliminary investigation evidenced as these veins show complex metasomatic haloes and a symmetric internal layering, characterised by crystallisation of magmatic sapphirine (Giovanardi et al., 2013). The mineral assemblage of the veins is dominated by titanian pargasite towards the host peridotite and by plagioclase at the vein centre. The veins also present phlogopite and spinel. Field and petrographic evidence, major and trace element data and the O isotopic composition of such gabbroic veins indicate that they formed at shallow mantle conditions by multistage fractional crystallisation of a migrating melt unrelated to those forming phlogopite harzburgites. Besides, local strong enrichments in LILE, LREE and 18O in vein minerals confirm that such melt was deeply modified by interaction with the host phlogopite peridotite. The genetic relationships with other intrusive events recorded by the FPP and the associated crustal sequence will be addressed with the aim of placing new constraints on the petrologic and geodynamic evolution of the IVZ

Melt-Rock Interaction at Mantle Conditions: Evidences from Finero Gabbroic Dykes

The Finero Phlogopite-Peridotite (FPP) is a worldwide famous mantle massif recrystallized through several events of melt migrations. These events have enriched the FPP in hydrous phases and crustal components and have been commonly interpreted as related to a subduction/post orogenic geodynamic setting. The last of these metasomatic events has produced composite sapphirine-bearing gabbroic dykes, interpreted as the result of the interaction of channelized migrating melts with the host rock in a two-steps intrusion process. In the first step, the melt reacted with the FPP rocks and evolved by fractional crystallization of amphibole cumulates. In the second step, the evolved melt reacted with the first cumulates producing magmatic sapphirine and segregating plagioclase-rich bands containing abundant apatites at the nucleus of the dike. New data suggest, however, a more complex evolution. New O and in situ Sr isotopes on minerals suggest that the gabbroic dykes have evolved from melt(s) that progressively were contaminated by the interaction with the FPP rocks during its fractionation. The δ18O increases from 5.81‰ in orthopyroxenes at the dykes border to ~6.90‰ in cumulitic amphiboles and 8.60‰ in plagioclases. The 87Sr/86Sr values for plagioclase and coexisting apatite show isotopic disequilibrium between the two phases (plagioclases at 0.70474 ± 0.00033, n=23, and apatites at 0.70369 ± 0.00025, n=6). These isotopic variations could be explained with an AFC-like process between mantle-derived melt(s) and a crustal-enriched host (the FPP). In situ Sr isotope analyses were performed at the CIGS laboratory of the Università di Modena e Reggio Emilia using a Thermo Fisher Scientific Neptune™ coupled to a 213 nm Nd:YAG laser ablation system (New Wave Research™). During the analytical sessions a new in house plagioclase reference material for Rb-Sr systematic, named BC84, has been successfully tested and used

Mantle-Derived Corundum-Bearing Felsic Dykes May Survive Only within the Lower (Refractory/Inert) Crust: Evidence from Zircon Geochemistry and Geochronology (Ivrea–Verbano Zone, Southern Alps, Italy)

Corundum-rich (up to 55 vol.%) felsic dykes formed with albite, +/- K-feldspar, +/- hercynite and +/- biotite-siderophyllite cut the lower crustal rocks exposed in the Ivrea–Verbano Zone (NW Italy). Zircon is an abundant accessory mineral and its investigation through laser ablation-inductively coupled plasma (multi-collector)-mass spectrometer (LA-ICP-(MC)MS) has allowed results to directly constrain the timing of emplacement, as well as petrology and geochemistry of parental melts. Zircons are characterized by very large concentration in rare earth elements (REE), Th, U, Nb and Ta, and negative Eu anomaly. U–Pb analysis points to Norian emplacement ages (223 +/- 7 Ma and 224 +/- 6 Ma), whereas large positive EHf(t) values (+13 on average) indicate a derivation from depleted to mildly enriched mantle source. The mantle signature and the corundum oversaturation were preserved thanks to limited crustal contamination of the host, high-temperature refractory granulites and mafic intrusives. According to the geochemical data and to the evidence of the development of violent explosions into the conduits, it is proposed that dykes segregated from peraluminous melts produced by exsolution processes affecting volatile-rich differentiates during alkaline magmatism. This work provides robust evidence about the transition of the geochemical affinity of Southern Alps magmatism from orogenic-like to anorogenic during Norian time, linked to a regional uprising of the asthenosphere and change of tectonic regime

Brittle-ductile deformation effects on zircon crystal-chemistry and U-Pb ages: an example from the Finero Mafic Complex (Ivrea-Verbano Zone, western Alps)

A detailed structural, geochemical and geochronological survey was performed on zircon grains from a leucocratic dioritic dyke discordantly intruded within meta-diorites/gabbros forming the External Gabbro unit of the Finero Mafic Complex. This latter is nowadays exposed as part of a near complete crustal section spanning from mantle rocks to upper crustal metasediments (Val Cannobina, Ivrea-Verbano Zone, Italy). The leucocratic dyke consists mainly of plagioclase (An18-24Ab79-82Or0.3-0.7) with subordinate amounts of biotite, spinel, zircon and corundum. Both the leucocratic dyke and the surrounding meta-diorites show evidence of ductile deformation occurred under amphibolite-facies conditions. Zircon grains (up to 2 mm in length) occur mainly as euhedral grains surrounded by fine grained plagioclasedominated matrix and pressure shadows, typically filled by oxides. Fractures and cracks within zircon are common and can be associated with grain displacement or they can be filled by secondary minerals (oxides and chlorite). Cathodoluminescence (CL) images show that zircon grains have internal features typical of magmatic growth, but with local disturbances. However EBSD maps on two selected zircon grains revealed a profuse mosaic texture resulting in an internal misorientation of ca. 10o. The majority of the domains of the mosaic texture are related to parting and fractures, but some domains show no clear relation with brittle features. Rotation angles related to the mosaic texture are not crystallographically controlled. In addition, one of the analysed zircons shows clear evidence of plastic deformation at one of its corners due to indentation. Plastic deformation results in gradual misorientations of up to 12o, which are crystallographically controlled. Trace elements and U-Pb analyses were carried out by LA-ICP-MS directly on petrographic thin sections and designed to cover the entire exposed surface of selected grains. Such investigations revealed a strong correlation between internal zircon structures, chemistry, U-Pb isotope ratios and mylonitic fabric. U-Pb data return highly discordant and variable ages: in particular, the 206Pb/238U ages range from Carboniferous to Triassic within the same zircon grain. The youngest 206Pb/238U data derive from narrow axial stripes oriented parallel or at low angle with respect to the foliation planes. These stripes are characterized by an overall HREE, Y, U and Th enrichment possibly reflecting deformation of the grain in presence of interstitial fluid phases, likely related to a concomitant magmatic activity. Deformation related structures (cracks and fractures) within zircon grains acted as fast-diffusion pathways allowing fluids to modify the geochemistry and isotopic systems of zircon. Our results suggest that fluid-assisted brittle-ductile deformation can severely modify the trace elements and isotopic composition of zircon with unexpected patterns constrained by stress regime. In similar cases, our observations suggest that, for a more appropriate interpretation of the petrologic evolution and age variability, a direct characterization of the internal structures of zircons still placed in their microtextural site is highly recommended

Transition from orogenic-like to anorogenic magmatism in the Southern Alps during the Early Mesozoic: Evidence from elemental and Nd-Sr-Hf-Pb isotope geochemistry of alkali-rich dykes from the Finero Phlogopite Peridotite, Ivrea–Verbano Zone

The Ivrea-Verbano Zone (IVZ) in the westernmost sector of the Southern Alps is an iconic upper mantle to lower continental crust sequence of the Adriatic Plate and provides a geological window into the tectono-magmatic events that occurred at the Gondwana–Laurussia boundary from Late Paleozoic to Early Mesozoic. In this work, we document new geochemical and Nd-Sr-Hf-Pb isotopic data for Early Mesozoic alkali-rich dyke swarms which intruded the Finero Phlogopite Peridotite (northern IVZ) to provide geological constraints on the nature, origin and evolution of Early Mesozoic magmatism in the Southern Alps. The studied dykes are amphibole-phlogopite-bearing and show geochemical features varying between two end-member groups. A dyke group is characterized by HFSE-poor, Al-rich amphibole (Al2O3 up to 16 wt.%) with high LILE and LREE contents, high radiogenic 87Sr/86Sr(i) (0.704732 to 0.704934) and low radiogenic Nd isotopes (εNd(i) from –0.1 to –0.7), which support the occurrence of significant amounts of recycled continental crust components in the parental mantle melts and impart an overall “orogenic-like” affinity. This dyke group was largely derived from metasomatized lithospheric mantle sources. The second group is HFSE-rich with Al-poorer amphibole enriched in LILE and LREE, low radiogenic 87Sr/86Sr(i) (0.703761–0.704103) and higher radiogenic Nd isotopes (εNd(i) from +3.4 to +5.4) pointing to an “anorogenic” alkaline affinity and asthenospheric to deep lithospheric mantle sources. Some dykes show both orogenic and anorogenic affinities, providing evidence that the orogenic-like magmatism in the IVZ predates the alkaline anorogenic magmatism. The Finero dyke swarms therefore record a geochemical change of the Early Mesozoic magmatism of the Southern Alps from orogenic-like magmatism, typical of post-collisional settings, to anorogenic alkaline magmatism, common in intraplate to extensional settings, and places a temporal correlation of Early Mesozoic magmatism in the IVZ to those in the eastern and central sectors of the Southern Alps

MELT-PERIDOTITE MULTISTAGE INTERACTION AT MANTLE CONDITIONS: PETROLOGICAL ANO GEOCHEMICAL EVIDENCES FROM SAPPHIRINE-APATITE-CALCITE-BEARING GABBROIC DYKES FROM THE FINERO PHLOGOPITE PERIDOTITE (IVREA-VERBANO ZONE)

The Finero Phlogopite-Peridotite (FPP) is a mantle uni! outcropping in the northernmost pari of the Ivrea-Verbano Zone (IVZ, Southern Alps). Multistage pervasive lo channelled meli migrations had completely recrystallized the entire FPP. The main metasomatic event pervasively formed an association of amphibole-rich phlogopite harzburgite with subordinated phlogopite-pyroxenites which do not show geochemical gradients (Zanelli et al., 1999). Channelled migrations lately formed dunite bodies, sometimes containing stratiform chromitites and, more rarely, pyroxenite layers similar lo those associated lo phlogopite harzburgite. Several other lithologies, showing geochemical gradients with rocks of the main FPP association and characterized by the presence of apatite sometimes associated lo carbonates (i.e. dolomite and calcite), are subordinated in volumes and abundances. Commonly these lithologies occur as dykes or veins along deformation zones. Geochronological data from apatite-calcite zircon syenites and apatite-dolomite wehrlites provide Triassic ages assumed lo document the lime of the meltlfluid migrations. Notwithstanding the apparent mineralogica! and chemical differences with the main lithologic sequences, apatite-carbonates-bearing rocks have been frequently interpreted as cogenetic lo phlogopite harzburgites and related lo the main metasomatic event. Recently, apatite-calcite-bearing gabbroic dykes randomly crosscutting the FPP lithologic associations were recognized as possibly the las! (or one of the las!) melt migration event within the mantle unii (Giovanardi et al., 2013). The dykes show symmetrical internal layering formed by melanocratic bands towards the host peridotite dominated by titanian pargasite and a centrai leucocratic zone dominated by plagioclase. Magmatic sapphirine occurs in plagues al the contaci of the leucocratic zone within the melanocartic bands. New field, petrographic and geochemical studies were conducted lo constrain the gabbroic veins intrusion and their genetic relationships with other FPP metasomatic events. Petrographic evidences, major and trace element data and the O isotopic composition of such gabbroic veins indicate that they formed al shallow mantle conditions by multistage fractional crystallisation of a migrating meli unrelated lo those forming the harzburgite-pyroxenite association and the dunite bodies. However, local strong enrichments in LILE, LREE and 1i180 in vein minerals confirm that such melt was deeply modified by interaction with the host phlogopite peridotite. However, the amphiboles in textural equilibrium with sapphirine show a marked M-H REE and Y depletion associated lo a marked positive Eu anomaly, which suppor! meli evolution through plagioclase assimilation. The genetic relationships with other intrusive events recorded by the FPP and the associated crustal sequence will be addressed with the aim of placing piace new constraints on the petrologic and geodynamic evolution of the IVZ

Niobium and Zirconium Phosphates as Green and Water-Tolerant Catalysts for the Acid-Catalyzed Valorization of Bio-Based Chemicals and Real Lignocellulosic Biomasses

Commercial niobium and synthesized zirconium phosphates were tested as water-tolerant heterogeneous acid catalysts in the hydrothermal conversion of different bio-based substrates. Different acid-catalyzed reactions were performed using biomass-derived model compounds and more complex real lignocellulosic biomasses as the substrate. The conversion of glucose and cellulose was preliminarily investigated. Then, a wide plethora of raw lignocellulosic biomasses, such as conifer wood sawdust, Jerusalem artichoke, sorghum, miscanthus, foxtail millet, hemp and Arundo donax, were valorized towards the production of water-soluble saccharides, 5-hydroxymethylfurfural (HMF), levulinic acid (LA) and furfural. The different catalytic performances of the two phosphates were explained on the basis of their acid features, total acidity, Brønsted/Lewis acid sites ratio and strength. Moreover, a better insight into their structure–acidity relationship was proposed. The different acid properties of niobium and zirconium phosphates enabled us to tune the reaction towards target products, achieving from glucose maximum HMF and LA yields of 24.4 and 24.0 mol%, respectively. Remarkably, when real Jerusalem artichoke biomass was adopted in the presence of niobium and zirconium phosphate, maximum yields of furanic compounds and cellulose-derived sugars of 12.7 and 50.0 mol%, respectively, were obtained, after only 1 h of reaction. The synthesized hydrolysates, which were found to be rich in C5 and C6 carbohydrates, can be better exploited for the cascade production of more added-value bio-products

Mantle Xenoliths from Huanul Volcano (Central-West Argentina): A Poorly Depleted Mantle Source under Southern Payenia

Huanul is a shield volcano with several lava flows hosting mantle xenoliths erupted during the Pleistocene (0.84 ± 0.05 Ma). It is located in the southern part of the Payenia Volcanic Province, which is among the largest Neogene-Quaternary volcanic provinces of South America. The vol-canism here has been ascribed as the northernmost expression of the back-arc volcanism of the Andean Southern Volcanic Zone. We present the first petrographic and mineral chemistry study of mantle xenoliths collected from Huanul lavas with the aim of reconstructing directly the mantle source of the Payenia Volcanic Province. Xenoliths are commonly small (<5 cm in radius) but scarcely crossed by basaltic veins. All xenoliths have a fertile lherzolitic modal composition and are equilibrated in the spinel-facies. Most of them exhibit an almost primitive-mantle geochemical affinity, characterized by slightly depleted clinopyroxene REE patterns reproducible by partial melting degrees between 0 and 4% of a PM source. Geothermobarometric P-T estimates of cli-nopyroxene-orthopyroxene couples form a linear trend between 10 and 24 kbar with constant increase of T from 814 to 1170 °C along a 50–60 mW/m2 geotherm. Evidences of interaction with the host basalts occur as spongy textures in clinopyroxene and reacted spinel, which tend to became more restitic in composition and show chromatographic or complete overprinting of the trace element compositions. The presence of plagioclase and calculated P-T values constrain this melt/rock reaction process between 6 and 14 kbar, during magma ascent, and fit the mantle ad-iabat model. Calculated melts in equilibrium with the primary clinopyroxenes do not fit the composition of the host basalt and, together with the geothermobarometric estimations, point to an asthenospheric mantle source for the magmatism in southern Payenia. The PM geochemical affinity of the xenoliths of Huanul is an extremely rare finding in the South America lithospheric mantle, which is commonly extensively refertilized by subduction-derived melts

Short-scale variability of the SCLM beneath the extra-Andean back-arc (Paso de Indios, Argentina): Evidence from spinel-facies mantle xenoliths

Cenozoic basalts carrying ultramafic mantle xenoliths occur in the Matilde, León and Chenque hills in the Paso de Indios region, Argentina. The mantle xenoliths from the Chenque and León hills mainly present porphyroclastic textures, whereas the Matilde hill xenoliths have coarse-grained to porphyroclastic textures. The equilibrium temperatures are in the range of 780 to 940°C, indicating a provenance from shallow sectors of the lithospheric mantle column that were subjected to a relatively low heat flux at Cenozoic Era. According to the modal compositions of xenoliths, the mantle beneath Matilde and León hills was affected by greater than 22% partial melting, while less depleted peridotites occur in the Chenque suite (starting from 10% partial melting). Such an observation is con rmed by the partial melting estimates based on Cr#Sp, which vary from 8 to 14% for the selected Chenque samples and from 14 to 18% for the Matilde ones. The common melting trend is overlapped by small-scale cross cutting local trends that may have been generated by open-system processes, such as open-system partial melting and/or post partial-melting metasomatic migration of exotic Na-Cr-rich melts. The two main mineralogical reaction schemes are: i) the dissolution of pyroxenes and the segregation of new olivine in olivine-rich peridotites, and ii) the replacement of primary olivine by orthopyroxene±clinopyroxene in orthopyroxene-rich peridotites. These were produced by channelled and/or pervasive melt extraction/ migration. Enhanced pyroxene dissolution is attributed to channelling of silica- undersaturated melts, whereas the replacement of primary olivine by orthopyroxene±clinopyroxene points to reaction with silica-saturated melts. Late disequilibrium reactions identified in the xenoliths comprise: the breakdown of orthopyroxene in contact with the host basalt, and (rarely) reaction coronae on orthopyroxene, clinopyroxene and spinel linked to glassy veins. Such features are apparently related to the injection of melt, likely during entrainment into the host basalts and ascent to the surface.Centro de Investigaciones Geológica