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We have used multiple-regression methods to calibrate new, pressure-independent empirical chemometric equations to calculate the major element composition of basanitic to rhyolitic melts in equilibrium with calcic amphibole. The equations are based on amphibole stoichiometric formula components ± temperature from published experimental P- T- X data and avoid some problems of previous studies associated with uncertainties in pressure determination. Compared with the pressure-dependent equations of , tests run using an independent data set indicate that the new equations yield improved precision and accuracy, in particular for SiO2, TiO2, CaO, and K2O. The results are only marginally more precise when temperature is used as a dependent variable, demonstrating that temperature has a relatively minor role in controlling amphibole crystal chemistry compared with melt composition. This allows us to accept a small decrease in precision in excluding temperature from the analysis, which is very convenient for application of the equations to natural amphiboles where temperature is typically unknown. Using the new chemometric equations, reconstructed melt compositions in equilibrium with the rims of amphiboles in pumice clasts of the Ongatiti ignimbrite are in good agreement with coexisting matrix glass compositions, lending support for our analysis. The compositionally variable cores of the amphiboles give predicted melt compositions with large compositional variations from andesitic (63 wt% SiO2) to high-Si rhyolite. These compositional variations in the predicted melt compositions suggest that there may be a range of heterogeneous melts undergoing progressive differentiation within a major crustal magma storage region underneath the volcano. The results support the existence of genuine intermediate composition melts within the storage region. Interaction between these stored melts, disaggregating mush fragments and replenishing magmas gives rise to the chemical complexity observed in erupted magmas. We also used our multiple regression model to predict the compositions of melts that were in equilibrium with amphiboles in plutonic nodules from Grenada lavas. The predicted melts cover a wide range of compositions, perhaps as a result of in situ fractionation, but are consistent with melt inclusions hosted in those cumulates, as reported by . Overall, our new pressure- and temperature-independent equations resolve issues associated with previous pressure-dependent studies and represent a useful tool for further investigation of crustal processes at subduction zones. [ABSTRACT FROM AUTHOR]

Abstract: Highly siderophile element concentrations (HSEs: Os, Ir, Ru, Pt, Pd, and Re) have been determined for a suite of fresh, submarine mafic lavas from the northern Tonga Arc front and the nascent backarc Fonualei Spreading Centre (FSC). Prior melt depletion of the Tongan mantle wedge combined with a high degree of fluid fluxed melting is thought to have produced boninitic magmas at several arc and FSC locations. As such, this arc system provides an opportunity to assess the fluid mobility of HSEs and to investigate the effects of fluid-induced melting and prior melt depletion on HSE behaviour during both mantle melting and magma evolution. Tongan lavas display extreme enrichment of Pt (2.5–32ng/g) and Pd over Os (0.002–0.6ng/g), Ir, and Ru, significantly greater than basalts from mid-ocean ridges. Magma evolution increases the degree of fractionation, resulting in the highest recorded Pt/Ru ratios (>300) in arc front samples with MgO <8 wt.%. This increasing fractionation is due to the mild incompatibility of Pt and Pd, and concurrent compatibility of Ru, during sulphide undersaturated magma evolution. However, the fractionation of Pt and Pd from Os, Ir, and Ru is observed in the highest MgO samples, indicating source inheritance. Prior melt depletion of the mantle and elevated oxygen fugacity both increase the likelihood of complete consumption of sulphide in the source during melting, which typically leads to melts with high concentrations of all the HSE. Indeed, modelling indicates that 25% aggregate partial melting of a depleted MORB-mantle source, proposed for the Tonga Arc, will lead to complete base-metal sulphide consumption unless there is considerable addition of S by the slab flux (at least 200μg/g). Although source enrichment of Pt, Pd, and Re by slab fluids may take place, the fractionation of Pt and Pd from Os, Ir, and Ru can largely be explained by relatively low-temperature, yet high-degree, melting of fluid-fluxed melt-depleted mantle. The high Pt and Pd contents can be produced by the exhaustion of sulphide in the source, while the presence of Ru–Os–(Ir) alloys or sulphides (e.g. laurite) associated with Cr-spinel can explain Os, Ir, and Ru retention in the source residue. Such phases have been documented in fluid-fluxed sub-arc mantle from ophiolites. Osmium isotopes co-vary negatively with Os abundance and thus appear to be dominated by shallow level contamination. The most Os-rich samples, however, have 187Os/188Os ratios (0.126–0.132) which are typical of DMM and MORB, suggesting an indistinguishable flux of radiogenic Os from the slab. The significant fractionation of Pt and Re from Os in arc settings will lead, over time, to elevated 186Os and 187Os which may be relevant to the observed enrichments of these isotopes in some mantle regions. In addition, the differing behaviour of Ru and Ir, and the implication of a mantle source containing Ru-rich microphases, may have consequences for the estimation of the HSE composition of primitive upper mantle. [Copyright &y& Elsevier]

Abstract: New volatile data (CO2, H2O, He, Ne, and Ar) are presented for 24 submarine basaltic glasses from the Kolbeinsey Ridge, Tjörnes Fracture Zone and Mohns Ridge, North Atlantic. Low CO2 and He contents indicate that magmas were strongly outgassed with the extent of degassing increasing toward the south, as expected from shallower ridge depths. Ne and Ar are significantly more abundant in the southernmost glasses than predicted for degassed melt. The strong atmospheric isotopic signal associated with this excess Ne and Ar suggests syn- or posteruptive contamination by air. Degassing, by itself, cannot generate the large variations in δ13C values of dissolved CO2 or coupled CO2-Ar variations. This suggests that δ13C values were also affected by some other processes, most probably melt-crust interaction. Modelling indicates that degassing had a negligible influence on water owing to its higher solubility in basaltic melt than the other volatiles. Low H2O contents in the glasses reflect melting of a mantle source that is not water-rich relative to the source of N-MORB. Before eruption, Kolbeinsey Ridge melts contained ∼400 ppm CO2 with δ13C of −6‰, 0.1 to 0.35 wt.% H2O, 3He/4He ∼11 R A, and CO2/3He of ∼2 × 109. We model restored volatile characteristics and find homogeneous compositions in the source of Kolbeinsey Ridge magmas. Relative to the MORB-source, He and Ne are mildly fractionated while the 40Ar/36Ar may be low. The 3He/4He ratios in Tjörnes Fracture Zone glasses are slightly higher (13.6 R A) than on Kolbeinsey Ridge, suggesting a greater contribution of Icelandic mantle from the south, but the lack of 3He/4He variation along the Kolbeinsey Ridge is inconsistent with active dispersal of Icelandic mantle beyond the Tjörnes Fracture Zone. [Copyright &y& Elsevier]

Quantifying the storage conditions and evolution of different magmatic components within sub-volcanic plumbing systems is key to our understanding of igneous processes and products. Whereas erupted magmas represent a portion of the eruptible volcanic system, plutonic xenoliths provide a complementary record of the mushy roots of the plumbing system that cannot be mobilised easily to form lavas and consequently offer a unique record of magma diversity within the sub-volcanic plumbing system. Here, we present a detailed petrological and geochemical study of erupted plutonic xenoliths from the island of Sint Eustatius (Statia), in the northern Lesser Antilles volcanic arc. The plutonic xenoliths are predominantly gabbroic, but vary in texture, mineral assemblage and crystallisation sequence. We report major, trace and volatile (H2O and CO2) concentrations of xenolith-hosted melt inclusions (MIs) and interstitial glass. The MIs have a very large range in major element (49–78 wt% SiO2 and 0.1–6.1 wt% MgO) and trace element concentration (72–377 ppm Sr, 32–686 ppm Ba, 39–211 ppm Zr). Their chemistry varies systematically with host phase and sample type. Significantly, it shows that (1) plutonic xenoliths record a complete differentiation sequence from basalt to rhyolite (2) apatite, but not zircon, saturation was reached during crystallisation, (3) amphibole breakdown reactions play a role in the genesis of shallow gabbronorite assemblages, and (4) mixing between crystal cargos and multiple discrete bodies occurred. Residual melt volatile contents are high (≤ 9.1 wt% H2O and ≤ 1350 ppm CO2), returning volatile saturation pressures of 0–426 MPa. Multiple reaction geobarometry and experimental comparisons indicate that equilibration took place in the upper-middle crust (0–15 km). We infer that the Statia plutonic xenoliths represent portions of a large heterogeneous crystal mush within which a great diversity of melts was stored and mixed prior to eruption. Our data show that compositional variations in magmatic plumbing systems exceed those observed in volcanic products, a likely consequence of the blending that occurs prior to and during eruption. [ABSTRACT FROM AUTHOR]

Volcanoes at subduction zones reside above complex magma plumbing systems, where individual magmatic components may originate and interact at a range of pressures. Because whole-rock compositions of subduction zone magmas are the integrated result of processes operating throughout the entire plumbing system, processes such as mixing, homogenisation and magma assembly during shallow storage can overprint the chemical signatures of deeper crustal processes. Whereas melt inclusions provide an effective way to study the uppermost 10-15 km of the plumbing system, challenges remain in understanding magma intrusion, fractionation and hybridisation processes in the middle to lower crust (15-30 km depth), which commonly involves amphibole crystallisation. Here, we present new insights into the mid-crustal plumbing system at Mount St. Helens, USA, using multiple regression methods to calculate trace element partition coefficients for amphibole phenocrysts, and thus infer the trace element compositions of their equilibrium melts. The results indicate vertically distributed crystal fractionation, dominated by amphibole at higher pressures and in intermediate melts, and by plagioclase at lower pressures. Variations in Nb, Zr and REE concentrations at intermediate SiO2 contents suggest repeated scavenging of partially remelted intrusive material in the mid-crust, and mixing with material from geochemically diverse sources. Amphibole is an effective probe for deep crustal magmatism worldwide, and this approach offers a new tool to explore the structure and chemistry of arc magmas, including those forming plutonic or cumulate materials that offer no other constraints on melt composition. [ABSTRACT FROM AUTHOR]

Abstract: Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O–Sr–Nd–Os–Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50ppt) lavas from El Hierro (δ18Oolivine =5.17±0.08‰; 87Sr/86Sr=0.7029 to 0.7031; εNd =+5.7 to +7.1; 187Os/188Os=0.1481 to 0.1750; 206Pb/204Pb=19.1 to 19.7; Pd/Ir=6±3) versus those from La Palma (δ18Oolivine =4.87±0.18‰; 87Sr/86Sr=0.7031 to 0.7032; εNd =+5.0 to +6.4; 187Os/188Os=0.1421 to 0.1460; 206Pb/204Pb=19.5 to 20.2; Pd/Ir=11±4) are revealed from the dataset. Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal–liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2–6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (⩾110km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07±0.05 Os, 0.17±0.16 Ir, 0.34±0.32 Ru, 2.6±2.5 Pt, 1.4±1.2 Pd, 0.39±0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites. The HIMU affinities of the lavas, in conjunction with the low δ18Oolivine and high 206Pb/204Pb for La Palma, and elevated 187Os/188Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic 206Pb/204Pb, 187Os/188Os, elevated Re/Os and Pt/Os, and low-δ18O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50km). [Copyright &y& Elsevier]

Abstract: Arc magmas are commonly assumed to form by melting of sub-arc mantle that has been variably enriched by a component from the subducted slab. Although most magmas that reach the surface are not primitive, the impact of assimilation of the arc crust is often ignored with the consequence that trace element and isotopic compositions are commonly attributed only to varying contributions from different components present in the mantle. This jeopardises the integrity of mass balance recycling calculations. Here we use Sr and O isotope data in minerals from a suite of volcanic rocks from St Lucia, Lesser Antilles arc, to show that assimilation of oceanic arc basement can be significant. Analysis of 87Sr/86Sr in single plagioclase phenocrysts from four Soufrière Volcanic Complex (SVC; St Lucia) hand samples with similar composition (87Sr/86Sr=0.7089–0.7091) reveals crystal isotopic heterogeneity among hand samples ranging from 0.7083 to 0.7094 with up to 0.0008 difference within a single hand sample. measurements in the SVC crystals show extreme variation beyond the mantle range with +7.5 to for plagioclase ( ), +10.6 to for quartz ( ), +9.4 to for amphibole ( ) and +9 to for pyroxene ( ) while older lavas (Pre-Soufriere Volcanic Complex), with less radiogenic whole rock Sr composition (87Sr/86Sr=0.7041–0.7062) display values closer to mantle range: +6.4 to for plagioclase ( ) and +6 to for pyroxene ( ). We argue that the 87Sr/86Sr isotope disequilibrium and extreme values provide compelling evidence for assimilation of material located within the arc crust. Positive correlations between mineral and whole rock 87Sr/86Sr, 143Nd/144Nd and 206,207,208Pb/204Pb shows that assimilation seems to be responsible not only for the isotopic heterogeneity observed in St Lucia but also in the whole Lesser Antilles since St Lucia encompasses almost the whole-arc range of isotopic compositions. This highlights the need for detailed mineral-scale investigation of oceanic arc suites to quantify assimilation that could otherwise lead to misinterpretation of source composition and subduction processes. [Copyright &y& Elsevier]

• Ambient mantle metasomatism and melting degree traced through Nb/Zr, Ce/B, and δ 11 B. • δ 11 B consistent with isotopically heavy slab component(s) and DMM-OIB mantle source. • Greater δ 11 B complexity in melt inclusion suites reveals melt mixing processes. • Combined melt inclusions and whole-rocks record assembly of diverse melt batches. • Contributions from shallow crustal repositories of B remain poorly constrained. The chemistry of primitive arc rocks provides a window into compositional variability in the mantle wedge, as well as slab-derived inputs to subduction-related magmatism. However, in the long-term cycling of elements between Earth's internal and external reservoirs, a key unknown is the importance of retaining mobile elements within the subduction system, through subduction-related metasomatism of the mantle. To address these questions, we have analysed olivine-hosted melt inclusions and corresponding bulk rocks from the Kamchatka arc. Suites of melt inclusions record evidence for entrapment along melt mixing arrays during assembly of diverse parental magma compositions. Systematic variations in parental magma B/Zr, Nb/Zr, Ce/B, and δ 11 B are also apparent among the different eruptive centres studied. These element ratios constrain the nature of subduction-related metasomatism and provide evidence for ambient mantle heterogeneity and variable degrees of mantle melting. High Nb/Zr and low B/Zr in back-arc rocks indicate smaller degree melts, lower slab-derived inputs, but relatively enriched mantle compositions. Similarly, small monogenetic eruptive centres located away from the main stratocones also tend to erupt magmas with relatively lower slab contribution and overall smaller melting degrees. Conversely, arc-front compositions reflect greater slab contributions and larger degree melts of a more depleted ambient mantle. Across-arc variations in δ 11 B (ranging from ca. − 6 ‰ in the rear-arc and Sredinny Ridge to + 7 ‰ in the Central Kamchatka Depression) are generally consistent with variable addition of an isotopically heavy slab-derived component to a depleted MORB mantle composition. However, individual volcanic centres (e.g. Bakening volcano) show correlations between melt inclusion δ 11 B and other geochemical indicators (e.g. Cl/K 2 O, Ce/B) that require mixing between isotopically distinct melt batches that have undergone different extents of crustal evolution and degassing processes. Our results show that while melt inclusion volatile inventories are largely overprinted during shallower melt storage and aggregation, incompatible trace element ratios and B isotope compositions more faithfully trace initial mantle compositions and subduction inputs. Furthermore, we suggest that the signals of compositional heterogeneity generated in the sub-arc mantle by protracted metasomatism during earlier phases of subduction can be preserved during later magma assembly and storage in the crust. [ABSTRACT FROM AUTHOR]