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The occurrence of phlogopite and amphibole in mantle ultramafic rocks is widely accepted as the modal effect of metasomatism in the upper mantle. However, their simultaneous formation during metasomatic events and the related sub-solidus equilibrium with the peridotite has not been extensively studied. In this work, we discuss the geochemical conditions at which the pargasite-phlogopite assemblage becomes stable, through the investigation of two mantle xenoliths from Mount Leura (Victoria State, Australia) that bear phlogopite and the phlogopite + amphibole (pargasite) pair disseminated in a harzburgite matrix. Combining a mineralogical study and thermodynamic modelling, we predict that the P–T locus of the equilibrium reaction pargasite + forsterite = Na-phlogopite + 2 diopside + spinel, over the range 1.3–3.0 GPa/540–1500 K, yields a negative Clapeyron slope of -0.003 GPa K–1 (on average). The intersection of the P–T locus of supposed equilibrium with the new mantle geotherm calculated in this work allowed us to state that the Mount Leura xenoliths achieved equilibrium at 2.3 GPa /1190 K, that represents a plausible depth of ~ 70 km. Metasomatic K-Na-OH rich fluids stabilize hydrous phases. This has been modelled by the following equilibrium equation: 2 (K,Na)-phlogopite + forsterite = 7/2 enstatite + spinel + fluid (components: Na2O,K2O,H2O). Using quantum-mechanics, semi-empirical potentials, lattice dynamics and observed thermo-elastic data, we concluded that K-Na-OH rich fluids are not effective metasomatic agents to convey alkali species across the upper mantle, as the fluids are highly reactive with the ultramafic system and favour the rapid formation of phlogopite and amphibole. In addition, oxygen fugacity estimates of the Mount Leura mantle xenoliths [Δ(FMQ) = –1.97 ± 0.35; –1.83 ± 0.36] indicate a more reducing mantle environment than what is expected from the occurrence of phlogopite and amphibole in spinel-bearing peridotites. This is accounted for by our model of full molecular dissociation of the fluid and incorporation of the O-H-K-Na species into (OH)-K-Na-bearing mineral phases (phlogopite and amphibole), that leads to a peridotite metasomatized ambient characterized by reduced oxygen fugacity.

H2O, CO2, F, Cl and S concentrations in olivine-hosted melt inclusions (MI) from Cenozoic alkaline volcanics of Northern Victoria Land (NVL, Antarctica) were determined by Secondary Ion Mass Spectrometry (SIMS). The most undegassed H2O and CO2 values varies from 1.14 to 2.64 wt% H2O and from 2320 to 3900 ppm CO2 for the least differentiated alkaline basalts and basanites, respectively. The same MI have F and Cl contents varying from 471 to 888 and from 474 to 1135 respectively, although some other MI can get up to 1377 of F and 1336 of Cl. A H2O/(H2O + CO2) molar ratios from 0.88 to 0.92 were determined, and taking into account the MI with the highest water content, a CO2 content in the melts up to 4400 and 8800 ppm for basaltic and basanitic compositions were inferred. Assuming that these magmas were produced by about 3 to 7% of partial melting, the volatile content in the mantle sources were estimated and compared with the estimates obtained from amphibole-bearing mantle xenoliths abundantly entrained in the McMurdo basic lavas. The two approaches converge in obtaining the following values: H2O = 1160 ± 436 ppm; CO2 = 304 ± 64 ppm. Some discrepancies are observed for F and Cl, mainly due to the uncertainties in the F and Cl contents of amphibole and its modal content, both parameters spanning a rather large range. The resulting CO2/Nb and CO2/Ba ratios are lower and H2O/Ce higher than those estimated for Depleted MORB Mantle (DMM), suggesting that the NVL Cenozoic alkaline magmatism could be originated by an enriched mantle source composed by 60 to 70% Enriched Mantle (EM) and from 40 to 30% DMM. A global comparison of fluid-related, highly incompatible and immobile/low incompatible elements such as Li, K, Cl, Ba, Nb, Dy and Yb allow to put forward that the prolonged (~500 to 100 Ma) Ross subduction event played a fundamental role in providing the volatile budget to the lithospheric mantle before the onset of the Cenozoic continental rifting.

The complex European–Adria geodynamic framework, which led to the formation of the Alpine belt, is considered responsible for the orogenic magmatism that occurred in the Central Alps along the Periadriatic/Insubric Line (late Eocene–early Oligocene) and the anorogenic magmatism that occurred in the Southeastern Alps (late Paleocene–early Miocene). While the subduction-related magmatic activities are, as expected, near convergent margins, the occurrence of the intraplate-related magmatism is still puzzling. Therefore, in this work new geochemical and geochronological data of magmatic products from the Veneto Volcanic Province (VVP, north–east Italy) are provided to constrain the Cenozoic intraplate magmatism of the Southeastern Alps. The VVP is formed by dominant basic–ultrabasic (from nephelinites to tholeiites) magmatic products and by localized acid (latitic, trachytic, and rhyolitic) volcanic and subvolcanic bodies. Trace element patterns and ratios suggest that the mantle source of the alkaline magma types was a garnet lherzolite possibly metasomatised by carbonatitic melts and with residual phlogopite. According to the biostratigraphic records and our new 40Ar/39Ar ages, VVP eruptions occurred in several pulses, reflecting the extensional phases experienced by the Eastern Alpine domain. The volcanism started in the late Paleocene in the western sector of the VVP where activity was widespread also during the Eocene (45.21 ± 0.11 Ma – 38.73 ± 0.44 Ma). In the eastern sector eruptions took place in the early Oligocene (32.35 ± 0.09 Ma – 32.09 ± 0.29 Ma) and in the early Miocene (~23–22 Ma). From the studies so far undertaken, the anorogenic magmatic activity of the VVP was interpreted as resulting from mantle upwellings through slab window(s) following the European slab break-off, which occurred at ~ 35 Ma. However, considering (i) new tomographic images evidencing a continuous subvertical (~ 500 km in depth) slab beneath the Central Alps, and (ii) the onset of magmatic activity in the VVP in the late Paleocene (i.e., before the slab break-off) and its continuation until the Miocene, a better suited geodynamic scenario is required to explain the anorogenic magmatism. The westward rollback of the European slab caused the retreat and steepening of the subducting plate. As a consequence, sub-slab mantle material escaped and upwelled from the front of the slab and created a poloidal mantle flow. The latter induced the breakdown of carbonates in calcareous metasediments and carbonated metabasics within the subducting oceanic slab, providing carbonatitic melts, which could be responsible for the metasomatism of the VVP mantle sources. After that, the poloidal mantle flow also induced (i) the extensional deformation in the overriding Adria microplate, (ii) the decompressional melting of VVP mantle sources, and (iii) the intraplate affinity of the VVP magmatism. During these processes, the Adria microplate also rotated counterclockwise, forming sedimentary basins, and allowing the poloidal mantle flow to affect different portions of the overlying lithosphere, generating syn-estensional magmatism within the VVP.

The aluminium incorporation mechanism of perovskite was explored by means of quantum mechanics in combination with equilibrium/off-equilibrium thermodynamics under the pressure-temperature conditions of the Earth's lower mantle (from 24 to 80 GPa). Earth's lower mantle was modelled as a geochemically non-primitive object because of an enrichment by 3 wt% of recycled crustal material (MORB component). The compositional modelling takes into account both chondrite and pyrolite reference models. The capacity of perovskite to host Al was modelled through an Al2O3 exchange process in an unconstrained Mg-perovskite + Mg-Al-perovskite + free-Al2O3(corundum) system. Aluminium is globally incorporated principally via an increase in the amount of Al bearing perovskite [Mg-Al-pv(80 GPa)/Mg-Al-pv(24 GPa) ≈ 1.17], rather than by an increase in the Al2O3 content of the average chemical composition which changes little (0.11–0.13, mole fraction of Al2O3) and tends to decrease in Al. The Al2O3 distribution in the lower mantle was described through the probability of the occurrence of given compositions of Al bearing perovskite. The probability of finding Mg-Al-perovskite is comparable to Mg-perovskites. Perovskite with Al2O3 mole fraction up to 0.15 has an occurrence probability of ∼28% at 24 GPa, increasing up to ∼43% at 80 GPa; on the contrary, perovskite compositions in the range 0.19–0.30 Al2O3 mole fraction drop their occurrence probability from 9.8 to 2.0%, over the same P-range. In light of this, the distribution of Al in the lower mantle shows that, among the possible Al bearing perovskite phases, the (Mg0.89Al0.11)(Si0.89Al0.11)O3 composition is the likeliest, providing from 5 to 8% of the bulk perovskite in the pressure range from 24 to 80 GPa. The occurrence of the most Al rich composition, i.e. (Mg0.71Al0.29)(Si0.71Al0.29)O3, is a rare event (probability of occurrence < 1.7%). This study predicts that perovskite may globally host Al2O3 in terms of 4.3 and 4.8 wt% (with respect to the non-primitive lower mantle mass), thus accounting for ∼90% and 100% of the bulk Al2O3 estimated in the framework of pyrolite and chondrite reference models, respectively. A calcium-ferrite type phase (on the MgAl2O4-NaAlSiO4 join) seems to be the only candidate that can compensate for the 10% gap of the perovskite Al incorporation capacity, in the case of a pyrolite non-primitive lower mantle model.

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 (mid-ocean 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.

Calc-alkaline and alkaline magmatic activity is generally separated in space and/or in time. The Eastern Transylvanian Basin in Romania is one of the few places where, during Pleistocene, alkaline eruptions occurred contemporaneously with the calc-alkaline activity. Mantle xenoliths entrained in Persani Mts. alkaline volcanic products have been studied in order to investigate the interaction of metasomatic agents of different magmatic affinities with the mantle wedge. Based on mineral major and trace element and noble gases in fluid inclusions, two main events have been recognized. The first was a pervasive, complete re-fertilization of a previously depleted mantle by a calc-alkaline subduction-related melt, causing the formation of very fertile, amphibole-bearing lithotypes. This is shown by the a) increased amounts of modal clinopyroxene up to 21.9 % with Al2O3 contents up to 8.16 wt%, higher than what is expected for clinopyroxene in Primordial Mantle; b) 4He/40Ar* ratios up to 1.2, within the reported range for mantle production; c) 3He/4He in olivine, opx and cpx of 5.8 ± 0.2 Ra, among the most radiogenic values of European mantle, below the typical MORB mantle value (8 ± 1 Ra), reflecting recycling of crustal material in the local lithosphere. The second event is related to later interaction with an alkaline metasomatic agent similar to the host basalts that caused slight LREE enrichment in pyroxenes and disseminated amphiboles and precipitation of vein amphiboles with a composition similar to amphiboles megacrysts also found in the Persani Mts. volcanic deposits. This is highlighted by the 4He/40Ar* and 3He/4He values found in some opx and cpx, up to 2.5 and 6.6 Ra, respectively, more typical of magmatic fluids.

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 (Ohře) 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 δ13 C of mantle CO2 varies between −4.7‰and −3.1‰, which mostly spans the MORB range (−8‰ < δ13 C < −4‰). The3 He/4 He 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 in3 He/4 He 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.

Intrinsic and extrinsic stability of the (Mg, Fe) O solid mixture in the Fe-Mg-Si-O system at high P, T conditions relevant to the Earth's mantle is investigated by the combination of quantum mechanical calculations (Hartree-26 Fock/DFT hybrid scheme), cluster expansion techniques and statistical thermodynamics. Iron in the (Mg, Fe) O binary mixture is assumed to be either in the low spin (LS) or in the high spin (HS) state. Un-mixing at solid state is observed only for the LS condition in the 23-42 GPa pressure range, whereas HS does not give rise to un-mixing. LS (Mg, Fe) O un-mixings are shown to be able to incorporate iron by subsolidus reactions with a reservoir of a virtual bridgmanite composition, for a maximum total enrichment of similar to 0.22 FeO. At very high P (up to 130/3150 GPa/K), a predominant (similar to 0.7 phase proportion), iron-rich Fe-periclase mixture (Mg0.50Fe0.50) O is formed, and it coexists, at constrained phase composition conditions, with two iron-poor assemblages [(Mg0.90Fe0.10) O and (Mg0.825Fe0.175)O]. These theoretical results agree with the compositional variability and frequency of occurrence observed in lower mantle Fe-periclase from diamond inclusions and from HP-HT synthesis products. The density difference among the Fe-periclase phases increases up to similar to 10%, between 24 and 130 GPa. The calculated bulk Fe/Mg partitioning coefficient between the bridgmanite reservoir and Fe-periclase, Kd, is 0.64 at 24 GPa; it then drops to 0.19 at 80 GPa, and becomes quasi-invariant (0.18-0.16) in the lowermost portion of the Earth's mantle (similar to 80-130 GPa). These Kd-values represent an approximate estimate for the Fe/Mg-partitioning between actual bridgmanite and Fe-periclase. Consequently, our Kd-values agree with experimental measurements and theoretical determinations, hinting that iron preferentially dissolves in periclase with respect to all the other iron-bearing phases of the lower mantle. The continuous change up to 80 GPa (similar to 2000 km depth) of the products (compositions and phase proportions) over the MgO-FeO binary causes geochemical heterogeneities throughout the lower mantle, but it does not give rise to any sharp discontinuity. In this view, anomalies like the ULVZs, explained with a local and abrupt change of density, do not seem primarily ascribable to the mixing behavior and reactivity of (Mg, Fe) O at subsolidus. (C) 2017 Elsevier Ltd. All rights reserved.

Partitioning of hydrogen (often referred to as H2O) between periclase (pe) and perovskite (pvk) at lower mantle conditions (24–80 GPa) was investigated using quantum mechanics, equilibrium reaction thermodynamics and by monitoring two H-incorporation models. One of these (MSWV) was based on replacements provided by Mg2+ ↔ 2H+ and Si4+ ↔ 4H+; while the other (MSWA) relied upon substitutions in 2Mg2+ ↔ Al3+ + H+ and Si4+ ↔ Al3+ + H+. H2O partitioning in these phases was considered in the light of homogeneous (Bulk Silicate Earth; pvk: 75%–pe:16% model contents) and heterogeneous (Layered Mantle; pvk:78%–pe:14% modal contents) mantle geochemical models, which were configured for lower and upper bulk water contents (BWC) at 800 and 1500 ppm, respectively. The equilibrium constant, BWCK(P,T), for the reactions controlling the H-exchange between pe and pvk exhibited an almost negligible dependence on P, whereas it was remarkably sensitive to T, BWC and the hydrogen incorporation scheme. Both MSWV and MSWA lead to BWCK(P,T) ⩽ 1, which suggests a ubiquitous shift in the exchange reaction towards an H2O-hosting perovskite. This took place more markedly in the latter incorporation mechanism, indicating that H2O-partitioning is affected by the uptake mechanism. In general, the larger the BWC, the smaller the BWCK(P,T). Over the BWC reference range, MSWV led to BWCK(P,T)-grand average (〈BWCK〉) calculated along lower mantle P–T-paths of ≈0.875. With regard to the MSWA mechanism, 〈BWCK〉 was more sensitive to BWC (and LM over BSE), but its values remained within the rather narrow 0.61–0.78 range. The periclase–perovskite H2O concentration-based partition coefficient, Kd H 2 O pe / pvk , was inferred using 〈BWCK〉, assuming both hydrous and anhydrous-dominated systems. MSWV revealed a Kd H 2 O pe / pvk –BWC linear interpolation slope which was close to 0 and Kd H 2 O pe / pvk values of 0.36 and 0.56 (for anhydrous and hydrous system, respectively). MSWA, in turn, yielded a Kd H 2 O pe / pvk trend with a slightly steeper negative BWC-slope, while it may also be considered nearly invariant with Kd H 2 O pe / pvk values of 0.31–0.47 in the 800–1500 ppm interval. Combining the MSWV and MSWA results led to the supposition that Kd H 2 O pe / pvk lies in the narrow 0.31–0.56 interval, as far as the P–T–BWC values of interest are concerned. This implies that water always prefers pvk to pe. Furthermore, it also suggests that even in lower mantle with low or very low bulk water content, periclase rarely becomes a pure anhydrous phase.