Coltorti, Massimo

Knowledge of the products originating from the subcontinental lithospheric mantle (SCLM) is crucial for constraining the geochemical features and evolution of the mantle. This study investigated the chemistry and isotope composition (noble gases and CO2) of fluid inclusions (FI) from selected mantle xenoliths originating from Wilcza Góra (Lower Silesia, southwest Poland), with the aim of integrating their petrography and mineral chemistry. Mantle xenoliths are mostly harzburgites and sometimes bear amphiboles, and are brought to the surface by intraplate alkaline basalts that erupted outside the north-easternmost part of the Eger (Ohˇre) Rift in Lower Silesia. Olivine (Ol) is classified into two groups based on its forsterite content: (1) Fo88.9−91.5, which accounts for a fertile-to-residual mantle, and (2) Fo85.5−88.1, which indicates large interactions with circulating (basic) melts. This dichotomy is also related to orthopyroxene (Opx) and clinopyroxene (Cpx), which show two ranges of Mg# values (87–90 and 91–93, respectively) and clear evidence of recrystallization. CO2 predominates within FI, followed by N2. The d13C of mantle CO2 varies between −4.7‰and −3.1‰, which mostly spans theMORB range (−8‰< d13C < −4‰). The 3He/4He ratio is 6.7–6.9 Ra in Cpx, 6.3–6.8 Ra in Opx, and 5.9–6.2 Ra in Ol. These values are within the range proposed for European SCLM (6.3±0.3 Ra). The decrease in 3He/4He from Cpx to Ol is decoupled from the He concentration, and excludes any diffusive fractionation from FI. The chemistry of FI entrapped in Ol indicates that the mantle is depleted by variable extents of partial melting, while that of Opx and Cpx suggests the overprinting of at least one metasomatic event. According to Matusiak-Małek et al. (2017), Cpx, Opx, and amphiboles were added to the original harzburgite by carbonated hydrous silicate melt related to Cenozoic volcanism. This process resulted in entrapment of CO2-rich inclusions whose chemical and isotope composition resembles that of metasomatizing fluids. We argue that FI data reflect a mixing between two endmembers: (1) the residual mantle, resulting from partial melting of European SCLM, and (2) the metasomatic agent, which is strongly He-depleted and characterized by MORB-like features.

The possibility of constraining the composition and evolution of specific portions of the Sub-Continental Lithospheric Mantle (SCLM) by means of an integrated study of petrography, mineral chemistry, and concentrations of volatiles in fluid inclusions (FI) is a novel approach that can provide clues on the recycling of volatiles within the lithosphere. This approach is even more important in active or dormant volcanic areas, where the signature of the gaseous emissions at the surface can be that of the underlying lithospheric mantle domains. In this respect, the ultramafic xenoliths brought to the surface in West Eifel (~0.5–0.01 Ma) and Siebengebirge (~30–6 Ma) volcanic fields (Germany) are ideal targets, as they provide direct information on one of the most intriguing portions of SCLM beneath the Central European Volcanic Province (CEVP). Five distinct populations from these localities were investigated using petrographic observations, mineral phase analyses and determination of He, Ne, Ar and CO2 contents in olivine-, orthopyroxene-, and clinopyroxene-hosted FI. The most refractory Siebengebirge rocks have highly forsteritic olivine, high-Mg#, low-Al pyroxene, and spinel with high Cr#, reflecting high extents (up to 30%) of melt extraction. In contrast, xenoliths from West Eifel are modally and compositionally heterogeneous, as indicated by the large forsterite range of olivine (Fo83–92), the Cr# range of spinel (0.1–0.6), and the variable Al and Ti contents of pyroxene. Equilibration temperatures vary from 870 ◦C to 1070 ◦C in Siebengebirge, and from ⁓900 ◦C to ⁓1190 ◦C in West Eifel xenoliths, at oxygen fugacity values generally between 􀀀 0.5 and + 1.3 ΔlogƒO2 [FMQ]. In both areas, the FI composition was dominated by CO2, with clinopyroxene, and most of the orthopyroxene had the highest concentrations of volatiles, while olivine was gas-poor. The noble gas and CO2 distributions suggest that olivine is representative of a residual mantle that experienced one or more melt extraction episodes. The 3He/4He ratio corrected for air contamination (Rc/Ra values) varied from 6.8 Ra in harzburgitic lithotypes to 5.5 Ra in lherzolites and cumulate rocks, indicating that the original MORB-like mantle signature was progressively modified by interaction with crustal-related components and melts having 3He/4He and 4He/40Ar* values consistent with those published for magmatic gaseous emissions. The Ne and Ar isotope systematics indicated that most of the data were consistent with mixing between a recycled atmospheric component and a MORB-like mantle, which does not necessarily require the involvement of a lower mantle plume beneath this portion of the CEVP. The major element distribution in mineral phases from West Eifel and Siebengebirge, together with the systematic variations in FI composition, the positive correlation between Al enrichment in pyroxene and equilibration temperatures, and the concomitant Rc/Ra decrease with increasing temperature, suggest that the SCLM beneath Siebengebirge represented the Variscan lithosphere in CEVP prior to the massive infiltration of melts/fluids belonging to the Quaternary Eifel volcanism. In contrast, West Eifel xenoliths reflect multiple heterogeneous metasomatism/refertilisation events that took place in the regional SCLM between ~6 and ~ 0.5 Ma.

Nominally anhydrous minerals (NAMs) may contain significant amounts of water and constitute an important reservoir for mantle hydrogen. The colloquial term ‘water’ in NAMs is related to the presence of hydroxyl-bearing (OH􀀀 ) point defects in their crystal structure, where hydrogen is bonded to lattice oxygen and is charge-balanced by cation vacancies. This hydrous component may therefore have substantial effects on the thermoelastic parameters of NAMs, comparable to other major crystal-chemical substitutions (e.g., Fe, Al). Assessment of water concentrations in natural minerals from mantle xenoliths indicates that olivine commonly stores ~0–200 ppm of water. However, the lack of samples originating from depths exceeding ~250 km coupled with the rapid diffusion of hydrogen in olivine at magmatic temperatures makes the determination of the olivine water content in the upper mantle challenging. On the other hand, numerous experimental data show that, at pressures and temperatures corresponding to deep upper mantle conditions, the water storage capacity of olivine increases to 0.2–0.5 wt%. Therefore, determining the elastic properties of olivine samples with more realistic water contents for deep upper mantle conditions may help in interpreting both seismic velocity anomalies in potentially hydrous regions of Earth’s mantle as well as the observed seismic velocity and density contrasts across the 410-km discontinuity. Here, we report simultaneous single-crystal X-ray diffraction and Brillouin scattering experiments at room temperature up to 11.96(2) GPa on hydrous [0.20(3) wt% H2O] Fo90 olivine to assess its full elastic tensor, and complement these results with a careful re-analysis of all the available single-crystal elasticity data from the literature for anhydrous Fo90 olivine. While the bulk (K) and shear (G) moduli of hydrous Fo90 olivine are virtually identical to those of the corresponding anhydrous phase, their pressure derivatives K′ and G′ are slightly larger, although consistent within mutual uncertainties. We then defined linear relations between the water concentration in Fo90 olivine, the elastic moduli and their pressure derivatives, which were then used to compute the sound velocities of Fo90 olivine with higher degrees of hydration. Even for water concentrations as high as 0.5 wt%, the sound wave velocities of hydrous and anhydrous olivines were found to be identical within uncertainties at pressures corresponding to the base of the upper mantle. Contrary to previous claims, our data suggest that water in olivine is not seismically detectable, at least for contents consistent with deep upper mantle conditions. In addition to that, our data reveal that the hydration of olivine is unlikely to be a key factor in reconciling seismic velocity and density contrasts across the 410-km discontinuity with a pyrolitic mantle.

Petrology and fluid inclusions (FI) geochemistry are increasingly used in tandem to constrain the compositional features and evolution of the lithospheric mantle. In this study, we combine petrography and mineral chemistry with analyses of noble gases (He, Ne and Ar) and CO2 in olivine, orthopyroxene- and clinopyroxene-hosted FI, as well as radiogenic isotope (Sr-Nd-Pb) systematics of ultramafic xenoliths collected at La Grille volcano in Grande Comore Island, aiming at better characterizing one of the most enigmatic and controversial portions of the western Indian Ocean lithospheric mantle. Xenoliths have been divided in three groups on the basis of their textural features: Group 1 (Opx-bearing), Group 2 (Opx-free) and Group 3 (Cumulate). Overall, petrographic observations and mineral phase compositions indicate that the sampled lithospheric portion experienced variable degrees of melting (from 5% to 35%), recorded by Group 1 most refractory harzburgites and lherzolites, as well as modal metasomatic processes as evidenced by the crystallization of cpx at the expense of opx in Group 1 fertile lherzolites and wehrlite and by Group 2 xenoliths. Crystallization of slightly oversaturated basic silicate melts seems also to have occurred, as shown by Group 3 xenoliths. A positive trend between temperature and ƒO2 is evident, with Group 2 and 3 xenoliths testifying for hotter and more oxidised conditions than Group 1. The variability of the 4He/40Ar* ratio (0.02–0.39) in Group 1, significantly below typical values of a fertile mantle (4He/40Ar* = 1–5), can be explained by the variable degrees of partial melting coupled to metasomatic enrichment that may account for modifying 4He/40Ar*, as also indicated by the mineral composition. He-Ar-CO2 relationships support the presence of a metasomatic CO2-rich process post-dating the melt extraction and the cumulate formation. The air-corrected 3He/4He isotopic ratios (6.30 to 7.36 Ra) are intermediate between the MORB mantle signature (8 ± 1Ra) and the SCLM (6.1 ± 0.9 Ra). The Ne and Ar isotopic signatures (20Ne/22Ne, 21/Ne/22Ne and 40Ar/36Ar) are consistent with mixing between an air-derived component and a MORB-like mantle, supporting the hypothesis for a lithospheric origin of the Comoros magmas, and arguing against any deep mantle plume-related contribution. This is also corroborated by combining Ne with He isotopes, showing that La Grille ultramafic xenoliths are far from the typical plume-type compositions. Sr-Nd-Pb isotope systematics in opx and cpx from La Grille additionally support a MORB-type signature for the lithospheric mantle beneath the area.

Soil surveys were performed in Medolla (Italy), a peculiar area characterized by spotty high soil temperature, gas vent, and lack of vegetation, to determine the migration mechanisms and spatial behavior of gas species. Hereby we present soil gas measurements and their isotopic ratios measured between 2008 and 2015, including the 2012 Emilia-Romagna seismic sequence. We found that soil gas concentrations markedly changed during the main shocks of May 20 and 29, 2012 (Mw 6.1 and 6.0, respectively), highlighting the presence of a buried fault intersecting the gas vents. We suggest that crustal dilation associated with seismic activity favored the uprising of geogas towards the surface. Changes in the isotopic signature highlight the contribution of two distinct sources, one deeper, thermogenic and another superficial related to organic-rich layer, whose relative contribution varied before, during and after the earthquake. We suppose an increase of microbial component likely due to the ground shaking of shallower layers linked to seismic sequence, which masks the thermogenic contribution. Although the changes we detect are specific for an alluvial plain, we deduce that analogous processes may be active elsewhere, and that soil gas geochemistry represents an useful tool to discriminate the gas migration related to seismic activity.

Crystal zoning plays a fundamental role in modern volcanology as a key to unravel the geometry and the dynamics of plumbing systems. In this study, a detailed textural and compositional study of clinopyroxene crystals entrained in intrusive, hypabyssal and effusive products from Cima Pape (Dolomites) is coupled with thermobarometric-hygrometricmodels to reconstruct the geometry and evolution of the feeding systembeneath Middle Triassic volcanic edifices. Whole-rock major, trace element distribution and Sr-Nd isotopic signature (87Sr/86Sri = 0.7045–0.7050; 143Nd/144Ndi = 0.51223–0.51228) show that the rocks from Cima Pape are SiO2- saturated and have shoshonitic affinity, and likely belong to the acme of the Mid-Triassic magmatismthat shaped the Southern Alps between 239 and 237.6Ma. Highly porphyritic trachybasaltic to basaltic trachyandesitic volcanic rocks contain a large number of concentric-zoned clinopyroxene crystals. Here, high-Mg# and -Cr2O3, REEdepleted bands (Mg# 80–91; Cr2O3 up to 1.2 wt%) with variable thickness grew between relatively low-Mg# and -Cr2O3 (Mg# 70–77; Cr2O3 < 0.1 wt%) augitic cores and rims. In contrast, the gabbroic to monzodioritic 50- to 300-m-thick sill cropping out belowthe volcanic sequences, though to represent a relic of the shallowest portion of the plumbing system, is mostly made up of unzoned clinopyroxene crystals. Thermobarometric and hygrometric models allowed us to define that a small “mush-type” batchwas located beneath the Cima Pape volcano at depths between 7 and 14 km. Here, augitic clinopyroxene formed in equilibrium with a slightly evolved (basaltic trachyandesitic), H2O-rich melt (Mg# = 43–45; T = 1035–1075 °C; H2O = 2.6–3.8 wt%). Periodic replenishments of the magma batch by primitive (Mg# = 65–70), hotter and relatively H2O-poor (T = 1130–1150 °C; H2O = 2.1–2.8 wt%) basaltic magmas led to the formation of diopsidic bands mantling the already formed augitic cores. Later on, re-equilibration of clinopyroxene with the mixed melt resulted in the formation of low-Mg#, LILE- and LREE-enriched rims. The most Mg-poor micro-phenocrystic clinopyroxene in the volcanic rocks and in the sill records the ultimate and shallowest conditions of crystallization, occurring at T of 975–1010 °C and P comprised between 50 and 150 MPa. Based on the presence of similar zoning in clinopyroxene phenocrysts, a comparison between the Mid-Triassic Cima Pape and active volcanoes was put forward to highlight the potential of studying ancient, entirely exposed volcanic systems for interpreting the feeding systemprocesses acting beneath active volcanoes. At a regional scale, this approach represents a new, powerful tool for investigating the evolution of the Mid-Triassic magmatism in the Southern Alps and shedding light on the interactions between mantle-derived melts and differentiated batches ponding in the crust.

Carbon in the upper mantle controls incipient melting of carbonated peridotite and so acts as a critical driver of plate tectonics. The carbon-rich melts that form control the rate of volatile outflux from the Earth’s interior, contributing to climate evolution over geological times. However, attempts to constrain the carbon concentrations of the mantle source beneath oceanic islands and continental rifts is complicated by pre-eruptive volatile loss from magmas. Here, we compile literature data on magmatic gases, as a surface expression of the pre-eruptive volatile loss, from 12 oceanic island and continental rift volcanoes. We find that the levels of carbon enrichment in magmatic gases correlate with the trace element signatures of the corresponding volcanic rocks, implying a mantle source control. We use this global association to estimate that the mean carbon concentration in the upper mantle, down to 200 km depth, is approximately 350 ppm (range 117–669 ppm). We interpret carbon mantle heterogeneities to reflect variable extents of mantle metasomatism from carbonated silicate melts. Finally, we find that the extent of carbon enrichment in the upper mantle positively correlates with the depth at which melting starts. Our results imply a major role of carbon in driving melt formation in the upper mantle.

The noble gases He, Ne and Ar in fluid inclusions from mantle xenoliths at three localities in Northern Victoria Land (Baker Rocks, Greene Point and Handler Ridge), spanning about 300 km, provide new constraints on the nature of the lithospheric mantle beneath the West Antarctic Rift System (WARS). Mantle xenoliths are anhydrous and hydrous spinel-bearing lherzolite and harzburgite samples. The 4He/40Ar* ratios (0.004–0.39) in olivines, two pyroxenes and amphiboles are much lower than those typical of fertile mantle (1–5), suggesting that this lithospheric domain are consistent with a variably depleted mantle, as also indicated by the major- and trace-element compositions of whole rock and minerals. The 3He/4He ratios vary from 2.30 to 19.79 Ra. However, the lowest and highest 3He/4He ratios are related to the post-eruptive accumulation of radiogenic 4He and cosmogenic 3He, respectively. After filtering the data for these secondary effects, we constrain the 3He/4He signature of the subcontinental lithospheric mantle below this area to 7.1 ± 0.4 Ra (mean ± standard deviation). This isotope signature results from mantle metasomatism by asthenospheric melts with a MORB (midocean ridge basalt)-type 3He/4He. The range of 7.1 ± 0.4 Ra is compatible with previous measurements in mantle xenoliths and lavas from other localities of the NVL, as far away as Mount Erebus, evidencing a homogeneous He-isotope signature beneath the entire rift. The He and Ne isotopes support the hypothesis that WARS origin is not related to a plume.

Unravelling the physical state and properties of mantle rocks is crucial for understanding both plate tectonics, seismic activity, and volcanism. In this context, the knowledge of accurate elastic parameters of constituent mineral phases, and their variations with pressure (P) and temperature (T), is an essential requirement, that coupled with the thermal state of the lithosphere can provide a better understanding of its petrophysics and thermochemical structure. In this paper, we present an assessment of the thermoelastic parameters [in the form of P–V–T–K Equations of State (EoS)] of orthopyroxene, clinopyroxene, spinel and garnet based on X-Ray diffraction data and direct elastic measurements available in literature. The newly developed EoS are appropriate to describe the elastic behaviour of these phases under the most relevant P–T conditions and bulk compositions of the Earth’s mantle. In combination with the published EoS for mantle olivine and magnesiochromite, these EoS are suitable to calculate the physical properties of mantle peridotites and their variation with P and T. Thanks to these EoS, we can evaluate how the variations in bulk composition and thermal regimes affect the density structure of the lithospheric mantle. Accordingly, the density structure of fertile and depleted peridotitic systems was calculated along the 35, 45 and 60 mWm􀀀 2 geothermal gradients at P comprised between 1 and 8 GPa. Under very cold geothermal gradients, the density of both fertile and depleted peridotitic systems progressively increases with depth, whereas under relatively hot conditions a first downwards decrease from 1 to ca 3 GPa is observed, followed by an increase downward. In mantle sections characterized by intermediate geotherms (45 mWm􀀀 2), the behaviour of the two systems differs up to ca 4 GPa, as the density of the depleted system remains nearly constant down to this depth whereas it moderately increases in the fertile system. The results of our simplified parameterisation, in agreement with classical thermodynamic modelling, indicate that the density structure of the lithospheric mantle is predominantly controlled by the P – T gradient variations, with some compositional control mostly arising at cold-intermediate thermal conditions. Integrated by geophysical and thermodynamic modelling, the newly developed and selected EoS could provide an alternative strategy to infer the elastic properties of mineral phases and peridotite rocks, under the most relevant P–T conditions and compositions of the Earth’s mantle, without requiring sets of end-member properties and solution models.

The petrological study of volcanic products emitted during the paroxysmal events of December 2015 from the summit craters of Mount Etna allow us to constrain T-P-XH2O phase stability, crystallization conditions, and mixing processes along the main open-conduit feeding system. In this study, we discuss new geochemical, thermo-barometric data and related Rhyolite- MELTS modelling of the eruptive activity that involved the concomitant activation of all summit craters. The results, in comparison with the previous paroxysmal events of the 2011–2012, reinforce the model of a vertically extended feeding system and highlight that the activity at the New South-East Crater was fed by magma residing at a significantly shallower depth with respect to the Central Craters (CC) and North-East Crater (NEC), even if all conduits were fed by a common deep (P = 530–440 MPa) basic magmatic input. Plagioclase dissolution, resorption textures, and the Rhyolite-MELTS stability model corroborate its dependence on H2O content; thus, suggesting that further studies on the effect that flushing from fluids with different H2O/ CO2 ratio are needed to understand the eruption-triggering mechanisms for high energetic strombolian paroxysmal episodes.