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Melt storage and supply beneath arc volcanoes may be distributed between a central stratovolcano and wider fields of monogenetic cones, indicating complex shallow plumbing systems. However, the impact of such spatially variable magma storage conditions on volatile degassing and trace element geochemistry is unclear. This study explores magma generation and storage processes beneath the Tolbachik volcanic field, Kamchatka, Russia, in order to investigate the evolution of the magmatic volatile phase and, specifically, the strong enrichment of chalcophile metals (in particular, Cu) in this system. We present new geochemical data for a large suite of olivine- and clinopyroxene-hosted melt inclusions (and host phenocrysts) from five separate monogenetic cones within the Tolbachik volcanic field. These high-Al composition magmas likely reflect the homogenised fractionation products of primitive intermediate-Mg melt compositions, stored at shallow depths after significant fractional crystallisation. Boron isotope compositions and incompatible trace element ratios of the melt inclusions suggest a deeper plumbing system that is dominated by extensive fractional crystallisation and fed by melts derived from an isotopically homogeneous parental magma composition. Volatile components (H2O, CO2, S, Cl, F) show that magmas feeding different monogenetic cones had variable initial volatile contents and subsequently experienced different fluid-saturated storage conditions and degassing histories. We also show that melts supplying the Tolbachik volcanic field are strongly enriched in Cu compared with almost all other Kamchatka rocks, including samples from the Tolbachik central stratocones, and other volcanoes situated in close proximity in the Central Kamchatka Depression. The melt inclusions record Cu concentrations ≥450 μg/g at ca. 4–5 wt.% MgO, which can only be explained by bulk incompatible partitioning behaviour of Cu, i.e. evolution under sulphide-undersaturated conditions. We suggest that initial mantle melting in this region exhausted mantle sulphides, leading to sulphide undersaturated primitive melts. This sulphide-free model for the high-Al cone melts is further supported by S/Se and Cu/Ag values that overlap those of the primitive mantle and MORB array, with bulk rock Cu/Ag ratios also overlapping other with other global arc datasets for magma evolution prior to fractionation of a monosulfide solid solution. We therefore demonstrate that the combination of novel chalcophile metal analyses with trace element, isotopic, and volatile data is a powerful tool for deciphering complex magmatic evolution conditions across the entire volcanic field.

Exposed plumbing systems provide important insight into crystallization and differentiation in shallow sills beneath volcanic fields. We use whole rock major element, trace element and radiogenic isotopic compositions, along with mineral geochemical data on 125 samples to examine the conditions of melt differentiation in shallow sills from the exposed 4-Ma-old San Rafael subvolcanic field (SRVF), Utah. The field consists of ∼2000 dikes, 12 sills and 63 well preserved volcanic conduits. Intrusive rocks consist of mainly fine-grained trachybasalts and coarse-grained syenites, which are alkaline, comagmatic and enriched in Ba, Sr and LREE. Within sills, syenite is found as veins, lenses, and sheets totally enveloped by the basalt. The SRVF intrusions have geochemical signatures of both enriched sub-continental lithospheric and asthenospheric mantle sources. We estimate partial melting occurred between 1·2 and 1·9 GPa (50–70 km), with mantle potential temperatures in the range 1260–1326 ± 25°C, consistent with those estimated for volcanic rocks erupted on the Colorado Plateau. Geobarometry results based on clinopyroxene chemistry indicate that (1) basalt crystallized during ascent from at least 40 km deep with limited lithospheric storage, and (2) syenites crystallized only in the sills, ∼1 km below the surface. San Rafael mafic magma was emplaced in sills and started to crystallize inward from the sill margins. Densities of basalt and syenite at solidus temperatures are 2·6 and 2·4 g/cc, respectively, with similar viscosities of ∼150 Pa s. Petrographic observations and physical properties suggest that syenite can be physically separated from basalt by crystal compaction and segregation of the tephrophonolitic residual liquid out of the basaltic crystal mush after reaching 30–45% of crystallization. Each individual sill is 10–50 m thick and would have solidified fairly rapidly (1–30 years), the same order of magnitude as the duration of common monogenetic eruptions. Our estimates imply that differentiation in individual shallow sills may occur during the course of an eruption whose style may vary from effusive to explosive by tapping different magma compositions. Our study shows that basaltic magmas have the potential to differentiate to volatile-rich magma in shallow intrusive systems, which may increase explosivity.

International Ocean Discovery Program (IODP) Expedition 351 ‘Izu–Bonin–Mariana (IBM) Arc Origins’ drilled Site U1438, situated in the northwestern region of the Philippine Sea. Here volcaniclastic sediments and the igneous basement of the proto-IBM volcanic arc were recovered. To gain a better understanding of the magmatic processes and evolution of the proto-IBM arc, we studied melt inclusions hosted in fresh igneous minerals and sampled from 30–40 Myr old deposits, reflecting the maturation of arc volcanism following subduction initiation at 52 Ma. We performed a novel statistical analysis on the major element composition of 237 representative melt inclusions selected from a previously published dataset, covering the full age range between 30 and 40 Ma. In addition, we analysed volatiles (H2O, S, F and Cl) and P2O5 by secondary ion mass spectrometry for a subset of 47 melt inclusions selected from the dataset. Based on statistical analysis of the major element composition of melt inclusions and by considering their trace and volatile element compositions, we distinguished five main clusters of melt inclusions, which can be further separated into a total of eight subclusters. Among the eight subclusters, we identified three major magma types: (1) enriched medium-K magmas, which form a tholeiitic trend (30–38 Ma); (2) enriched medium-K magmas, which form a calc-alkaline trend (30–39 Ma); (3) depleted low-K magmas, which form a calc-alkaline trend (35–40 Ma). We demonstrate the following: (1) the eruption of depleted low-K calc-alkaline magmas occurred prior to 40 Ma and ceased sharply at 35 Ma; (2) the eruption of depleted low-K calc-alkaline magmas, enriched medium-K calc-alkaline magmas and enriched medium-K tholeiitic magmas overlapped between 35 and 38–39 Ma; (3) the eruption of enriched medium-K tholeiitic and enriched medium-K calc-alkaline magmas became predominant thereafter at the proto-IBM arc. Identification of three major magma types is distinct from the previous work, in which enriched medium-K calc-alkaline magmas and depleted low-K calc-alkaline magmas were not identified. This indicates the usefulness of our statistical analysis as a powerful tool to partition a mixture of multivariable geochemical datasets, such as the composition of melt inclusions in this case. Our data suggest that a depleted mantle source had been replaced by an enriched mantle source owing to convection beneath the proto-IBM arc from >40 to 35 Ma. Finally, thermodynamic modelling indicates that the overall geochemical variation of melt inclusions assigned to each cluster can be broadly reproduced either by crystallization differentiation assuming P = 50 MPa (∼2 km deep) and ∼2 wt% H2O (almost saturated H2O content at 50 MPa) or P = 300 MPa (∼15 km deep) and ∼6 wt% H2O (almost saturated H2O content at 300 MPa). Assuming oxygen fugacity (fO2) of log fO2 equal to +1 relative to the nickel–nickel oxide (NNO) buffer best reproduces the overall geochemical variation of melt inclusions, but assuming more oxidizing conditions (log fO2 = +1 to +2 NNO) probably reproduces the geochemical variation of enriched medium-K and calc-alkaline melt inclusions (30–39 Ma).

The last Plinian-type eruption of Volcán de Colima, Mexico, occurred in 1913; this resulted in the removal of the top 100 m of the edifice and the deposition of a tephra layer that blanketed the slopes of the Colima Volcanic Complex (CVC). Road-cuts on the flanks of the nearby Nevado de Colima edifice expose pre-1913 air-fall tephra, pyroclastic flow and ash-rich surge deposits resulting from numerous highly explosive events throughout the Holocene. The majority of the pumice and scoria fallout deposits are medium-K subalkaline basaltic andesite and andesite in composition, defining a clear major element differentiation trend. In contrast, three newly discovered scoria fallout deposits are high-K subalkaline, transitional to alkaline, basaltic andesite in composition and are characterized by the presence of phlogopite; these deposits have high MgO (up to 7·9 wt %), K2O (up to 2·6 wt %) and P2O5 (up to 0·67 wt %) contents. They are also strongly enriched in fluid- and melt-mobile large ion lithophile elements (LILE; Rb, Ba, K, Sr and Th) and light REE (LREE; La, Ce, Pr and Nd) relative to the majority of the Colima tephra fallout deposits. Strontium and Nd isotope systematics reveal that the high-K mafic scoria have more radiogenic Sr (87Sr/86Sr = 0·70365–0·70408) and less radiogenic Nd (143Nd/144Nd = 0·51279–0·51294) compared with the majority of the subalkaline tephras (87Sr/86Sr = 0·70338–0·70371 and 143Nd/144Nd = 0·51290–0·51295). Two-component mixing models, using whole-rock geochemical data, indicate the importance of magma mixing in the petrogenesis of the Colima magmas, with addition of up to 50% by volume of an alkaline mafic magma component in the most potassic magmas. This is supported by mineral chemistry and textural data, which reveal multiple episodes of decompression and magma mingling within a shallow crustal magma storage region. The presence of these potassic tephra fall deposits among the otherwise prevailing medium-K subalkaline stratigraphy indicates that pulses of K-rich alkaline mafic magmas periodically enter the CVC plumbing system on timescales of a few thousand years and may trigger Plinian explosive eruptions.