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South-Eastern Spain is a key locality of the Western Mediterranean to unravel the origin of post-collisional magmatism and its relationships with the multi-stage evolution of the upper mantle in complex geodynamic settings. This study is focused on the Plio-Pleistocene post-collisional intraplate-like alkali basalts cropping out in the Tallante area (South-Eastern Spain) that are erupted in a region previously characterised by subduction related calc-alkaline to ultrapotassic (i.e., lamproitic) volcanism. Tallante alkali basalts represent a volcanic episode similar to other contemporary small volume intraplate volcanic occurrences of Western-Central Europe and North Africa, which are believed to derive from a Common Mantle Reservoir characterising the entire Circum Mediterranean asthenosphere. We report new major, trace element, and Sr-Nd-Pb isotope data on Tallante alkali basalts, showing compositions broadly similar to the other mafic volcanic rocks derived from the Common Mantle Reservoir and thus suggesting an asthenospheric component similar to other European within plate volcanic rocks. On the other hand, specific trace element ratios, such as Ce/Pb, Nb/U, Th/Yb, along with delta207Pb/204Pb and 87Sr/86Sr, clearly indicate the involvement of an enriched, subduction-related component, with a lamproitic geochemical and isotopic flavour. The trace element ratios suggest that low melting degree magmas from the Common Mantle Reservoir infiltrated and triggered melting of the strongly metasomatised sub-continental lithospheric mantle, which produced the lamproitic magmas previously erupted in the same area. The proposed origin of Tallante alkali basalts, located along a large scale left-lateral strike-slip fault, is consistent with analytical, numerical and laboratory models indicating that narrow subduction zones such as the Gibraltar Arc are characterised by mantle inflow around the slab edges determining upwelling and adiabatic melting of the asthenospheric mantle through slab tears.

High-MgO lamproite and lamproite-like (i.e. lamprophyric) ultrapotassic rocks are recurrent in the Mediterranean and surrounding regions. They are associated in space and time with ultrapotassic shoshonites and high-K calc-alkaline rocks. This magmatism is linked with the geodynamic evolution of the westernmost sector of the Alpine-Himalayan collisional margin, which followed the closure of the Tethys Ocean. Subduction-related lamproites, lamprophyres, shoshonites and high-K calc-alkaline suites were emplaced in the Mediterranean region in the form of shallow level intrusions (e.g. plugs, dykes and laccoliths) and small volume lava flows, with very subordinate pyroclastic rocks, starting from the Oligocene, in the Western Alps (northern Italy), through the Late Miocene in Corsica (southern France) and in Murcia-Almeria (southeastern Spain), to the Plio-Pleistocene in Southern Tuscany and Northern Latium (central Italy), in the Balkan peninsula (Serbia and Macedonia) and in the Western Anatolia (Turkey). The ultrapotassic rocks are mostly lamprophyric, but olivine latitic lavas with a clear lamproitic affinity are also found, as well as dacitic to trachytic differentiated products. Lamproite-like rocks range from slightly silica under-saturated to silica over-saturated composition, have relatively low Al2O3, CaO and Na2O contents, resulting in plagioclase-free parageneses, and consist of abundant K-feldspar, phlogopite, diopsidic clinopyroxene and highly forsteritic olivine. Leucite is generally absent, and it is rarely found only in the groundmasses of Spanish lamproites. Mediterranean lamproites and associated rocks share an extreme enrichment in many incompatible trace elements and depletion in High Field Strength Elements and high, and positively correlated Th/La and Sm/La ratios. They have radiogenic Sr and unradiogenic Nd isotope compositions, high 207Pb over 206Pb and high time-integrated 232Th/238U. Their composition requires an originally depleted lithospheric mantle source metasomatized by at least two different agents: (1) a high Th/La and Sm/La (i.e. SALATHO) component deriving from lawsonite-bearing, ancient crustal domains likely hosted in mélanges formed during the diachronous collision of the northward drifting continental slivers from Gondwana; (2) a K-rich component derived from a recent subduction and recycling of siliciclastic sediments. These metasomatic melts produced a lithospheric mantle source characterized by network of felsic and phlogopite-rich veins, respectively. Geothermal readjustment during post-collisional events induced progressive melting of the different types of veins and the surrounding peridotite generating the entire compositional spectrum of the observed magmas. In this complex scenario, orogenic Mediterranean lamproites represent rocks that characterize areas that were affected by multiple Wilson cycles, as observed in the Alpine-Himalayan Realm.

An analytical protocol for high-precision, in situ microscale isotopic investigations is presented here, which combines the use of a high-performing mechanical microsampling device and high-precision TIMS measurements on micro-Sr samples, allowing for excellent results both in accuracy and precision. The present paper is a detailed methodological description of the whole analytical procedure from sampling to elemental purification and Sr-isotope measurements. The method offers the potential to attain isotope data at the microscale on a wide range of solid materials with the use of minimally invasive sampling. In addition, we present three significant case studies for geological and life sciences, as examples of the various applications of microscale 87Sr/86Sr isotope ratios, concerning (i) the pre-eruptive mechanisms triggering recent eruptions at Nisyros volcano (Greece), (ii) the dynamics involved with the initial magma ascent during Eyjafjallajökull volcano’s (Iceland) 2010 eruption, which are usually related to the precursory signals of the eruption, and (iii) the environmental context of a MIS 3 cave bear, Ursus spelaeus. The studied cases show the robustness of the methods, which can be also be applied in other areas, such as cultural heritage, archaeology, petrology, and forensic sciences.

Ultramafic xenoliths are rarely found at convergent plate margins. A notable exception is in the Betic Cordillera of southern Spain, where the eruption of xenolith-bearing alkaline basalts during the Pliocene post-dated the Cenozoic phase of plate convergence and subduction-related magmatism. Mantle xenoliths of the monogenetic volcano of Tallante display extreme compositional heterogeneities, plausibly related to multiple tectono-magmatic episodes that affected the area. This study focuses on two peculiar composite mantle xenolith samples from Tallante, where mantle peridotite is crosscut by felsic veins of different size and mineralogy, including quartz, orthopyroxene, and plagioclase. The veins are separated from the peridotite matrix by an orthopyroxene-rich reaction zone, indicating that the causative agents were alkali-rich hydrous silica-oversaturated melts, which were likely related to recycling of subducted continental crust components. The present study reports new and detailed major and trace elements and Sr-Nd-Pb analyses of the minerals in the composite Tallante xenoliths that confirm the continental crust derivation of the metasomatic melts, and clarifies the mode in which subduction-related components are transferred to the mantle wedge in orogenic areas. The particular REE patterns of the studied minerals, as well as the variation of the isotopic ratios between the different zones of the composite xenoliths, reveal a complex metasomatic process. The distribution of the different elements, and their isotope ratios, in the studied xenoliths are controlled by the mineral phases stabilised by the interaction between the percolating melts and the peridotitic country rock. The persistence of marked isotopic heterogeneities and the lack of re-equilibration suggest that metasomatism of the sub-continental lithospheric mantle occurred shortly before the xenolith exhumation. In this scenario, the studied xenoliths and the metasomatic processes that affected them may be representative of the mantle sources of mafic potassic to ultrapotassic magmas occurring in post-collisional tectonic settings.

The Mediterranean area is one of the most intriguing places on Earth where geodynamics and volcanoes are strictly related, and evolved through time. The complexity of the tectonic setting is further enriched by the observed shift of the petrochemical affinity of magmas, in the same volcanic area, from subduction-related to intraplate. The successive opening of back-arc basins (e.g., Ligurian-Provençal basin, Tyrrhenian Sea), following the roll-back of the subducting Adria Plate, produced a migration of magmatism to form a transitional eastward pattern of volcanoes both onshore and offshore. The Mio-Pliocene volcanic rocks occurring in the Central Mediterranean area are characterised by exceptional variability of the petro-chemical and isotopic features, which allow the distinction of several sectors, when also the areal distribution is considered. Thus, the Mediterranean area has always been site of studies focused on magma genesis and on the geodynamic significance of the complex scenario achieved through time. In the scientific literature, a large number of papers were published on the magmatism of each single volcanic association/area, but very few dealt with the general picture of the offshore magmatic and geodynamic evolution. The aim of this chapter is to provide an outline of the most prominent geological, petrological, geochemical and isotopic characteristics of the submarine volcanic centres found in the Central Mediterranean basin, with the aim of providing a fairly complete picture of the existing relationships between the geodynamics and the igneous petrology in this area.

The active volcano of Ischia, the well-known island off-shore the city of Naples, has had a discontinuous volcanic activity characterised by caldera-forming paroxysmal eruptions, lava flows, and lava domes for >150 kyr. The overall geochemical composition of erupted magmas includes shoshonite, latite, and trachyte/trachyphonolite. In a complementary study, we demonstrated that the evolution of Ischia trachytes with Sr 10 wt.% outcrop a few kilometers apart at Procida island, and suggest that the evolved latites and trachytes at Ischia might have originated by crustal assimilation processes affecting Procida basalts. However, Energy Constrained Assimilation and Fractional Crystallisation modelling sets robust constraints against this hypothesis and provide geochemical arguments for a pristine mantle-derived radiogenic isotope signature for trachytes and latites, implying that they also evolved from parental basaltic magmas in a closed-system environment akin to trachytes with Sr

The fate of carbonate-rich sediments recycled at destructive plate margins is a key issue for constraining the budget of deep CO2 supplied to the atmosphere by volcanism. Experimental studies have demonstrated that metasomatic melts can be generated by partial melting of subducted carbonate-pelitic sediments, but signatures of the involvement of such components in erupted magmas are more elusive. We have made new U-Th disequilibria, Sr-Nd-Pb isotope, and high-precision delta238U analyses on lavas from Mount Vesuvius (Italy) and show that their measured 238U excesses require a mantle source affected by the addition of U-rich carbonated melts, generated by partial melting of subducted calcareous sediments in the presence of residual epidote. Accordingly, we argue that the occurrence of 238U excesses in "sediment-dominated" arc magmas represents diagnostic evidence of addition of carbonate sediments via subduction, hence providing constraints on deep carbon cycling within Earth. Our quantitative enrichment model, combined with published experimental results, allows us to estimate a resulting flux of 0.15-0.8 Mt/yr CO2 from the subducted carbonates to the mantle source of Mount Vesuvius.

The presence of crystal mushes in the feeding system of active volcanoes is generally revealed by antecrysts, representing the crystalline portion of old magmas recycled in the juvenile material, but very little is known about the fate of interstitial liquid hosted within the crystal-rich mush (i.e. antemelt). U-series disequilibria measured in magmas erupted in the past 18 years at Stromboli volcano provide the first geochemical evidence of the involvement of antemelt and help constraining the timescales of the processes occurring in the plumbing system of the volcano. Despite almost constant major and trace element composition, significant variations in isotope ratios are observed. (230Th/232Th) decreases with time, whilst (238U/232Th), (226Ra/230Th) and 87Sr/86Sr are different in the two types of magma erupted. Magma with low phenocryst content (lp) is erupted as pumices during paroxysm and is thought to belong to a deep reservoir. Highly porphyritic magma (hp) is erupted during the normal “Strombolian” activity as scoria and during the effusive events as lavas, and it is considered to derive from the former one within a shallow reservoir through degassing-driven crystallisation, mixing and incorporation of antecrysts. The distinct (238U/232Th) of lp and hp magma requires the involvement of a component with high 87Sr/86Sr and (238U/232Th) deriving from older magmas erupted earlier in the volcano history (up to 2.5 ka). The incompatibility of U and Th in major mineral phases limits the possible effect of antecrysts, hence requiring the involvement of a U- and Th-rich antemelt. The decrease of 226Ra-excess from lp to hp magmas provides further and independent evidence for the involvement of a few thousands years old antemelt. The variation with time of (230Th/232Th) within lp and hp magmas is exploited to constrain the residence time of magmas in the deep and shallow reservoir of the volcano to 55 yrs (inferred reservoir volume 0.5 km 3 ) and 2–10 yrs (inferred reservoir volume 0.02 – 0.09 km 3 ), respectively. Our results show the occurrence of magmatic processes operating at different timescale within the feeding system of a so-called steady state volcano, such as Stromboli. We show that, while most of the magma is erupted within few years, a portion of it, made of both crystals (antecrysts) and residual liquid (antemelt), can be stored in the plumbing system for thousands of years to be eventually rejuvenated and mixed back into the shallow reservoir. The presence of antemelts may also affect the eruptive mechanism by promoting heat transfer in locked crystal mushes, hence favouring their remobilisation.

In the Italian peninsula leucite-free and -bearing ultrapotassic rocks occur intimately associated but well separated in time. Silica-saturated ultrapotassic and associated shoshonitic magmas erupted during the Pliocene to Lower Pleistocene. Silica under-saturated leucite-bearing ultrapotassic rocks, mainly leucitites, were emplaced sometime later, during the Middle–Upper Pleistocene. The transition from leucite-free to -bearing rocks is diachronous and in some cases is complicated by the occurrence of crustal-derived magmas coeval with early leucite-free magma. The Monte Cimino–Vico area is a key locality for studying the transition from leucite-free to -bearing ultrapotassic rocks. There a volcanic complex is overlain by some 500 ka younger leucite-bearing rocks of Vico stratovolcano. Most of the potassic and ultrapotassic rocks of the Monte Cimino volcanic complex are characterised by high Mg-# (66.4–77.8), and compatible element abundances in spite of their high silica contents (52.9–58.0 wt.%). Ultrapotassic leucite-free rocks transitional to lamproites are olivine-bearing orthopyroxene- and plagioclase-free latites and K-rich basaltic trachyandesite and they are confined in the final mafic activity of the Monte Cimino volcanic complex. Two-pyroxene parageneses are observed in the early Monte Cimino volcanic complex giving equilibration temperature as high as 1050 °C and suggesting a sub-crustal derivation of their parental magmas. A two-pyroxene high-K calc-alkaline magma is then inferred for the genesis of the early Monte Cimino activity (e.g. dome complex and silicic lava flows and ignimbrites), which was modelled through crystal-fractionation from a high-K basaltic andesitic magma plus mixing with crustal anatectic rhyolitic magma. Final mafic lavas fill the isotopic and chemical gap between shoshonite-like and lamproite-like rocks, and each lava flow could be considered as a mantle-derived term from a heterogeneous sub-continental lithospheric mantle. Final mafic lavas are high-silica and -MgO ultrapotassic rocks due to crystallisation of primitive magmas generated by partial melting of a vein metasomatised network within a lithospheric upper mantle source, at low pressure and high P H2O . The shift to the younger Vico volcano, in which leucite-bearing magmas prevail, is thought to be due to the arrival in the mantle source of newly formed metasomatic agent from the undergoing slab characterised by the increasing of a sedimentary carbonate recycled component. This new component appears in the Middle Pleistocene and it is responsible for the composition of the magmatism of the Roman region. The recycling of carbonate-bearing pelitic sediments within the mantle wedge produces a carbonate-rich metasomatic agent. The latter is responsible for stabilisation of phlogopite-bearing wehrlitic veins within the mantle wedge. Partial melting of this newly formed vein network under high X CO2 generated silica under-saturated, and then leucite-bearing, ultrapotassic primary melts. A further shift is observed among the Vico post-caldera magmas, in which the appearance of a deep asthenospheric component is argued to be channelled late through slab-tears.

In situ Sr-isotope data by microdrilling, coupled with major and trace element analyses, have been performed on plagioclase and clinopyroxene from seven samples collected during the 2002-2003 eruptive crisis at Stromboli volcano (Aeolian Islands, Italy). On 28 December 2002, the persistent moderate explosive activity was broken by an effusive event lasting about 7 months. A more violent explosion (paroxysm) occurred on 5 April 2003. Two magma types were erupted, namely a volatile-poor and highly porphyritic magma (HP-magma) poured out as scoria or lava and a volatile-rich, phenocryst-poor magma (LP-magma) found as pumice. LP-magma differs from the HP-magma also for its slightly less-evolved chemistry, the groundmass composition and the lower Sr-isotope ratios. Micro-Sr-isotope data show the presence of zoned minerals in strong isotope disequilibrium, as previously found in products erupted in 1984, 1985 and 1996 AD, with (87)Sr/(86)Sr values generally decreasing from cores to rims of minerals. Only some outer rims testify for equilibrium with the host groundmass. The internal mineral zones with high Sr-isotope ratios (0.70665-0.70618) are interpreted as 'antecrysts', crystallised during the previous activity and recycled in the present-day system since the opening shoshonitic activity of the Recent Period, which occurred at about 2.5 ka ago. This result has implications for the dynamics of the present-day plumbing system of Stromboli at intermediate pressure (about 2-3 km depth) and allows us to propose a model whereby an HP-magma reservoir is directly interconnected at the bottom with a cumulate crystal much reservoir. Efficient mixing between residing HP-and input LP-magmas can occur in this reservoir, due to more similar rheological characteristics of the two magmas than in the conduit, where crystallisation is enhanced by degassing. Antecrysts (and possibly melts) re-enter in the HP-magma reservoir both from the bottom, recycled by ascending LP-magmas crossing the crystal mush, and from the top, recycled by descending degassed and dense HP-magma, residual of the periodic Strombolian explosions at the surface. The isotope variation measured in the groundmasses allows calculating the proportion of the LP-magma entering the shallow HP-magma reservoir at similar to 20%. From this proportion, we estimate that the total volume of LP-magma input during 2002-2003 closely matches the magma volume erupted in the effusive event, suggesting a steady-state system at broadly constant volume. The comparison with estimates of the LP-magma volume ejected by the paroxysm indicates that the LP-magma amount directly reaching the surface during the 5 April paroxysm is minimal with respect to that entering the system.

The Pachino-Capo Passero centre, located at the south-easternmost portion of Sicily, represents an Upper Cretaceous volcano within the Pelagian Block, a fragment in lithospheric continuity with the African Plate. The volcanic rocks of the Pachino-Capo Passero centre show fairly homogeneous mafic characteristics with a typical within-plate signature. Two groups with different levels of alkali and incompatible trace element enrichment have been recognised. Trace element modelling indicates that the two groups might be originated at different degrees of partial melting. The geochemical data suggest that Cretaceous rocks of Pachino-Capo Passero originated at greater depth than the neighbouring Neogene volcanic products of the Hyblean Plateau, likely from an asthenospheric mantle source. Sr-Nd-Pb isotope compositions of Pachino-Capo Passero rocks are presented along with those of Paleocene and Eocene lamprophyric dikes and small intrusive bodies from the adjacent Adria block, now representing the Apulian foreland (i.e., Pietre Nere and La Queglia dykes) in the context of investigating the presence and origin of a Common Mantle Reservoir beneath the Central Mediterranean area. The Sr-Nd-Pb isotopes of the Pachino-Capo Passero rocks are extremely similar to the recently redefined FOZO component whilst other suites (i.e., Pietre Nere) might require additional enriched components. Highly radiogenic Pb isotopes, along with high TiO2 contents and fractionated MREE/HREE argue for the presence of significant amount of recycled mafic oceanic crust in the mantle sources of these magmas as eclogitic lithologies dispersed within a depleted peridotitic mantle. The Sr-Nd-Pb isotope compositions of the studied rocks are also compared with literature data from the Canary Islands, as representative of a putative plume component contaminating the mantle region. The data show a clear distinction, especially in ?7/4 vs. ?8/4, indicating that the age and composition of the mafic crust recycled within the source of Pachino-Capo Passero rocks must be older and bear higher time-integrated U/Th ratios. The geochemical and isotope composition of Pachino-Capo Passero magmas, Pietre Nere and La Queglia is interpreted as a feature of the ambient asthenospheric mantle, due to the extremely widespread process of prolonged subduction and recycling of mafic oceanic crust of variable age and composition. Therefore no need for a unique reservoir related to a mantle plume is envisaged.