Melt Compositions In Equilibrium Research Articles

Mesoproterozoic depleted spinel peridotites metasomatized by high-K hydrous melt in the Patagonian back-arc

Here we report the first investigation of spinel-bearing mantle xenoliths from Los Gemelos volcano, Canquel Plateau, Patagonia. They are highly-depleted Mesoproterozoic (ReOs model ages of 1.3–0.9 Ga) harzburgites and clinopyroxene-poor lherzolites characterized by typical indicators of partial melt extraction, such as low whole-rock Al2O3 and CaO contents (<1.5 wt%), high Mg# of silicate phases (90–95), and Cr-rich spinel (Cr# 0.20–0.42). Depletion of incompatible highly siderophile elements (Re, Ru, Pd) relative to the primitive upper mantle supports high degrees of melt extraction. The occurrence of phlogopite and K-rich alkaline glass veins with high- and low-SiO2 compositions is clear evidence of modal metasomatism. The light rare earth element (LREE) enrichment in clinopyroxene, as well as the whole-rock U-shaped REE pattern, confirms cryptic metasomatism. This melt-rock interaction is corroborated by major (i.e., Mg# vs. basaltic elements) and trace (i.e., La/YbN vs. Sr/Y and Ti/Eu; and Sr vs. Ti/Eu) element contents of pyroxenes. The calculated compositions of melts in equilibrium with clinopyroxene coexisting with phlogopite suggest interaction with slab-derived materials. This metasomatism has been generated by a chromatographic fractionation-reaction process, from deep to shallow mantle domains. The percolation of a high-K hydrous magma probably is associated with the upwelling of asthenospheric material through a slab-window, which caused partial melting of oceanic crust and overlying sediments during the Paleocene. The varying intensities of metasomatic imprints recorded by mantle xenoliths from Los Gemelos provide valuable insights into the interaction of slab-derived materials near the lithosphere-asthenosphere boundary, at a distance of ∼600 km from the Andean volcanic arc.

Pre-eruptive magmatic processes at Taranaki volcano from an amphibole perspective

Amphibole phenocrysts in post-1 ka lava domes deposits of Taranaki volcano, an andesite arc volcano in New Zealand, provide an opportunity to explore late-stage changes in melt composition and volatiles in the run up to eruption. Amphibole is a subordinate phase (0–7% of modal phenocrysts) and the phenocrysts display three types of growth history. Type 1 are large compositionally and texturally uniform phenocrysts that have low MgO (<13 wt%) and high K2O (∼1–1.4 wt%) contents. In contrast, Type 2 have similar cores but have been partially resorbed and overgrown by a mafic rim distinguished by high MgO (up to 15 wt%) and low K2O (<1.0 wt%) contents. Type 3 are the least common, and have either normal zoned or concentrically zoned interiors with respect to MgO and FeO. Overall, elemental substitutions and zonation patterns are related to periods of resorption and regrowth that are best explained by changes in melt composition. Based on calculated equilibrium melt compositions, the amphibole crystallisation is consistent with an incrementally grown andesitic to dacitic (SiO2 58–67 wt%) crystal mush that was periodically recharged with more mafic magma (SiO2 ∼ 55 wt%). The melts span a compositional gap (SiO2 ∼ 60–65 wt%) that is not represented in eruption products from the last 8 ka. Such melts were likely brief stages during ongoing fractional crystallisation and magma mixing. Each recharge event disrupted an evolving system and mixed crystals from different parts of it. This concept supports triggering of eruptions by recharge of mafic melts, as also inferred from plagioclase zonation for some eruptions from Taranaki. The outermost rims (0–5 μm) of many amphibole phenocrysts are enriched in fluorine (up to 1.9 wt%) and surrounded by a thick opacitic decomposition growths. We interpret this as the result of slow magmatic ascent and extensive crystallisation that produced a late-stage halogen-rich interstitial melt. This likely extended the conditions for amphibole stability to lower pressure. If F enrichment was accompanied by comparable enrichments in other halogens that preferentially partition into an aqueous phase, then extensive degassing would have occurred during the dome extrusions.

Genesis of Andesitic Magma Erupted at Yufu Volcano, Kyushu Island, Southwest Japan Arc: Evidence from the Chemical Compositions of Amphibole Phenocrysts

Abstract The major- and trace-element compositions of amphiboles in andesite from Quaternary Yufu Volcano, northeastern Kyushu, Japan were analysed to investigate the generation processes of andesitic magma from Yufu Volcano. The amphiboles in andesite from Yufu volcano can be divided into two groups based on major-element composition: pargasite and magnesio-hornblende. To estimate temperature, pressure, and major- and trace-element compositions of melts in equilibrium with amphiboles, we used the recently proposed methods that can calculate temperature, pressure, major element compositions, and partition coefficients of trace-element between amphibole and melt using only the major-element compositions of amphibole. The estimated temperature, pressure, and major-element composition of melt in equilibrium with the amphibole phenocrysts indicate that each group crystallised under different conditions. These differences suggest that two magma chambers at different depths existed beneath Yufu Volcano and that the andesitic magma of Yufu Volcano was formed by mixing of the two magmas. The trace-element compositions of melts in equilibrium with the pargasite and magnesio-hornblende, estimated by applying the partition coefficients calculated from major-element compositions of amphibole to trace-element compositions of amphiboles, indicate magma derived from slab melt and the partial melting of crustal material, respectively. Because magma is a mixture of minerals and melt, we estimate the chemical compositional ranges of the two end-member magmas on the Y versus SiO2 diagram from the mixing relationship between amphibole and estimated melt, as well as phenocrysts of plagioclase, clinopyroxene, and orthopyroxene. The overlap of the estimated compositional range with the trend of whole-rock composition represents the chemical compositions of the end-members of magma mixing, yielding estimates of the mafic (SiO2 ≈ 45 wt %) and felsic (SiO2 ≈ 68 wt %) end-member magmas. Furthermore, we estimate the concentrations of other elements in the end-member magmas by substituting the estimated SiO2 concentrations of the magmas into linear regression equations between the whole-rock contents of other elements and SiO2. The trace-element compositions of the mafic and felsic end-member magmas, as estimated in this study, have similar features to those of gabbroids and Cretaceous granitic rocks, respectively, that are presumed to lie beneath Yufu Volcano. These similarities could be explained by the possibility that the compositions of the end-member magmas were influenced by basement rocks.

The Temperature and Composition of the Mantle Sources of Martian Basalts

AbstractThe composition of basaltic melts in equilibrium with the mantle can be determined for several Martian meteorites and in‐situ rover analyses. We use the melting model MAGMARS to reproduce these primary melts and estimate the bulk composition and temperature of the mantle regions from which they originated. We find that most mantle sources are depleted in CaO and Al2O3 relative to models of the bulk silicate Mars and likely represent melting residues or magma ocean cumulates. The concentrations of Na2O, K2O, P2O5, and TiO2 are variable and often less depleted, pointing to the re‐fertilization of the sources by fluids and low‐degree melts, or the incorporation of residual trapped melts during the crystallization of the magma ocean. The mantle potential temperatures of the sources are 1400–1500°C, regardless of the time at which they melted and within the range of the most recent predictions from thermochemical evolution models.

Crystal vs. melt compositional effects on the partitioning of the first-row transition and high field strength elements between clinopyroxene and silicic, alkaline, aluminous melts

Abstract The first-row transition element (FRTE) and high field strength element (HFSE) systematics are powerful tools for tracking the source and evolution of mantle-derived magmas. Clinopyroxene is generally considered a key fractionating mineral controlling the partitioning of trace elements between melt and residual solid during mantle melting. Although partitioning of FRTE and HFSE between clinopyroxene and basaltic melts has been well-studied, experimental constraints on their partitioning behavior in the presence of siliceous, aluminous, and alkali-rich melts are still lacking. Here we present clinopyroxene-silicic melt (67–69 wt% SiO2) partitioning experiments at 1 bar pressure and 1070–1100 °C for Co, Mn, Ni, Cu, Zn, Fe, Sc, Cr, V, Ti, Zr, Hf, Nb, and Ta. Run products consist of diopsidic clinopyroxene coexisting with various melt compositions with non-bridging oxygen to tetrahedral cation ratio (NBO/T) ranging from 0.10 to 0.22. Using our new partition coefficients (Ds) and combined with literature data, we assess some of the effects of crystal chemistry and the melt composition on the partitioning of FRTE and HFSE in this simple system. We show that partitioning of FRTE varies from mildly incompatible (e.g., D = ~0.1−1 for V, Cu, and Zn) to highly compatible (e.g., D &amp;gt; 10 for Cr and Ni), with the highest compatibilities observed for Ni (DNi = 13−34). The partitioning of HFSE varies from highly incompatible (D = 0.01−0.08) for Nb and Ta to mildly incompatible (D = 0.18−0.82) for Zr, Hf, and Ti. Our measured clinopyroxene-melt Ds are consistent with the theoretical predictions of the lattice strain model. Ds data for most tri-, tetra-, and pentavalent elements tend to increase with increasing tetrahedrally coordinated Al content, in agreement with those anticipated from crystal-chemical considerations. In contrast to ivAl concentrations, the clinopyroxene Na concentration has very little effect on trace element partitioning due to its low concentrations in clinopyroxene at relatively low-pressure conditions. These data further support a significant control of melt composition/structure on partitioning for highly polymerized melts. In general, measured Ds roughly increase to different extents with increasing polymerization of the melt (i.e., lower NBO/T or higher ASI). For our equilibrium melt compositions, Ds for several FRTE, such as Co and Ni, correlate well with the melt molar Mg2+/(M+ + M2+), whereas Ds for HFSE vary as a function of the melt alkali concentration. These well-defined trends support the role of melt NBO species (e.g., Mg2+) or complexing ligands (e.g., Na+ and K+) in controlling the partitioning of these elements. Overall, our new Ds data demonstrate that even very small changes in melt major-element compositions can greatly affect element partitioning in strongly polymerized silicic systems. These findings have important implications relevant to petrogenetic studies of the interaction between silicic melt and peridotite that occurs at shallow mantle conditions in various tectonic settings.

Trace Elements in Chromian Spinels from Four Siberian Kimberlites

We analysed the major, minor and trace elements chemistry of forty-two Cr-spinels from four Siberian kimberlites. They showed a wide range in Mg# (Mg/(Mg + Fe2+); 0.42–0.78) and Cr# (Cr/(Cr + Al); 0.32–0.92) and a common trend of increasing Cr# with decreasing Mg#. The major element classification schemes suggested that there were spinels deriving from a peridotitic source (Xen) and spinels crystallised from kimberlitic melts (Chr). Laser-Ablation Inductively Coupled Plasma Mass Spectrometry on both groups showed that the trace elements with the highest abundance were Mn (985–3390 ppm), Ni (531–3162 ppm), V (694–2510 ppm) and Zn (475–2230 ppm). Testing the effectiveness of trace elements in determining the source for Cr-spinels, we found out that Cr-spinels crystallised directly from a kimberlitic melt usually showed higher Mn, Ni, Sc and V concentrations with respect to those of peridotitic origin. In addition, using the available partitioning models, we found that the correlations between major elements and Ni, Co, Sc and Ga in the Xen group could be explained by subsolidus equilibration between spinel, olivine and clinopyroxene at 800–1000 °C, thus supporting a peridotitic source for this group. Finally, we calculated the composition of the possible melts in equilibrium with the Cr-spinels of the Chr group, using a selected set of partition coefficients. Calculated abundances of Cu, Ga and Zr were comparable to those of the kimberlite, while V was never close to the kimberlite composition. This simulation highlighted the need for new data on the trace elements partition coefficients between kimberlitic melts and Cr-spinel.

Formation of Late Paleoproterozoic Gaositai Hornblendite in Northern North China Craton: Evidence from Zircon U-Pb Isotopes and Amphibole Trace Elements

Paleoproterozoic tectonic evolution of the northern North China Craton has been a hot research topic. We firstly identified a 1.85 Ga hornblendite from the Gaositai mafic–ultramafic complex, in northern Hebei. Systematic studies of petrology, zircon U-Pb geochronology, and in situ mineral major and trace elements of hornblendite are the key to revealing the petrogenesis of the Paleoproterozoic ultramafic rock and the tectonic evolution of northern North China Craton. LA-ICP-MS zircon U-Pb dating suggests the Gaositai hornblendite formed at 1851 ± 44 Ma. The late Paleoproterozoic ultramafic rocks, together with coeval post-collisional granites, formed a bimodal igneous assemblage. Both hornblende and its equilibrium melt compositions show strongly fractionated HREE patterns, relative enrichments in LREEs and LILEs, and depletions in HREEs and HFSEs. The phlogopite-bearing hornblendite magma could have originated from a hydrous garnet-facies mantle source metasomatized by slab-derived silicate melt. Furthermore, the variations of major and trace elements in hornblende from core to rim also reveal the mineral fractional crystallization and magma recharge. Zircon trace elements, melt composition equilibrium with hornblendes, and the bimodal igneous assemblage suggest that the generation of the Gaositai Paleoproterozoic hornblendite was likely the product of post-collisional extension related to the collision between eastern and western North China blocks.

Mixing dry and wet magmas in the lower crust of a continental arc: new petrological insights from the Bear Valley Intrusive Suite, southern Sierra Nevada, California

Exposures of arc crustal sections represent rare opportunities to directly evaluate lower crustal magmatic processes and their link to arc products in the middle and upper crust. Within the southernmost Sierra Nevada batholith, the Bear Valley Intrusive Suite (BVIS) exposes a contemporaneously constructed ~ 30 km thick intrusive suite, and thus is ideal for this type of examination. Here we present detailed petrography and mineral major and trace element data for the BVIS. The deepest exposed portion of the BVIS (8–9 kbars) is composed of heterogeneous mafic igneous intrusions of olivine metagabbro, olivine-hornblende orthopyroxenite, olivine-bearing hornblende norite, hornblende norite, hornblende gabbronorite, hornblendite and hornblende gabbro. Shallower crustal intrusions (3–7 kbars) are comparatively homogeneous and dominated by hypersthene-bearing and hypersthene-free tonalites. Using amphibole-plagioclase geothermometry, we show that the mafic lower crustal intrusions crystallized over a wide temperature range from 850 to 1070 °C, highlighting mafic igneous fractionation during isobaric cooling in the lower crust of the Sierran arc, while tonalitic liquids were emplaced at temperatures < 800 °C in the middle and upper crust. Calculated trace element melt compositions in equilibrium with amphibole in lower crustal gabbros are similar to measured tonalite bulk compositions and support the generation of tonalites through fractionation of the observed gabbros. Further, petrography and mineral chemistry suggest multiple distinct crystallization sequences recorded in the different types of gabbro, requiring the presence of coexisting parental melts with contrasting compositions and H2O contents. Using available experimental data, we develop a model by which mixing of variably fractionated dry and wet magmas with similar viscosities followed by crystallization-differentiation in the deep crust to explain the formation of uniform tonalitic melts at shallower crustal levels in the BVIS. This process also explains the unusual predominance of orthopyroxene in the BVIS, and the limited aluminum enrichment compared to experimental differentiation sequences of hydrous basalts. Considering the similar geochemical characteristics of intermediate and felsic igneous rocks from the Sierra Nevada batholith and the Cascades, mixing magmas of variable H2O contents in the lower crust represents a viable petrological process to produce SiO2-rich liquids that may be more common than previously recognized.

Cr-poor and Cr-rich clinopyroxene and garnet megacrysts from southern African Group 1 and Group 2 kimberlites: Clues to megacryst origins and their relationship to kimberlites

Controversies surround the origin of kimberlite megacrysts, including whether and how they are genetically related to their host kimberlites, the relationship between the Cr-poor and Cr-rich suites and the dominant processes responsible for elemental and isotopic variations of megacrysts from a given kimberlite. We present new in-situ major and trace element and Sr isotopic results for clinoyroxene and garnet megacrysts from four southern African kimberlites: Colossus and Orapa (Group 1 kimberlites on the Zimbabwe craton), and Kalkput and Bellsbank (Group 2 kimberlites on the western Kaapvaal craton), that include both Cr-poor and Cr-rich megacryst varieties. Cr-poor megacrysts are present at Colossus, Orapa and Kalkput and the data exhibit tight, well-defined trends on major element diagrams as well as incompatible and rare earth element abundances similar to those previously reported for Cr-poor megacrysts. Cr-rich megacrysts, which are also present at Orapa and are the only variety present at Bellsbank, generally have higher Mg# values, lack well-defined major element trends and show stronger incompatible element enrichments as well as more radiogenic 87Sr/86Sri ratios than Cr-poor megacrysts from the same kimberlite group. Thermobarometry indicates that the Cr-poor megacrysts equilibrated at temperatures of ≈1200 to 1450 °C and pressures of 4.5 to 7.5 GPa. Cr-rich megacrysts, in contrast, extend to temperatures and pressures as low as 700 °C and 3 GPa, respectively. This indicates that, in the studied suites, Cr-poor megacrysts equilibrated at high temperatures in the lower lithosphere (>135 km), whereas Cr-rich megacrysts typically equilibrated at lower temperatures and pressures. Within the Cr-poor megacrysts from Group 1 and Group 2 kimberlites, there is a clear correspondence between kimberlite group, diagnostic incompatible element ratios (e.g., Nb/La) and Sr isotope ratios that parallel the differences noted between whole-rock Group 1 and Group 2 kimberlites. In the case of Cr-poor megacrysts, similar calculated melt compositions in equilibrium with garnet and clinopyroxene from the same kimberlite were obtained using recent high-pressure mineral‑carbonated melt partition coefficients. This suggests formation in conditions close to trace element equilibrium, and is consistent with crystallization from primitive melts with kimberlite-like trace element compositions. In the case of Cr-rich megacrysts, differences in the compositions of melts in equilibrium with clinopyroxene and garnet tend to be larger, and melts in equilibrium with Cr-rich clinopyroxene tend to show significantly greater incompatible element enrichments than those of estimated near-primary kimberlite melts. This could be due to the different behaviour of clinopyroxene and garnet during metasomatic melt-rock interaction, but the apparent disequilibrium between clinopyroxene and garnet could also be due to some of the Cr-rich megacrysts actually being peridotitic xenocrysts. We propose a model for the origin of southern African megacrysts in which carbonated protokimberlite melts formed stockwork-like bodies of variable size in the deep lithosphere (>130 km), which fed networks of melt-filled veins extending into the surrounding and overlying mantle. Crystallization of larger melt bodies resulted in megacryst assemblages dominated by Cr-poor megacrysts, and the incompatible element and isotopic characteristics of these dominantly reflect those of the protokimberlite melt. In contrast, crystallization of smaller melt bodies and their vein networks resulted in megacryst assemblages dominated by Cr-rich megacrysts, which formed as a result of extensive assimilation and metasomatic melt-rock interaction between protokimberlite and peridotite wallrock at low melt/rock ratios, particularly in the middle to shallow lithosphere where pre-existing potassic metasomatic heterogeneities are prevalent. The Cr-rich nature and enrichments in incompatible elements and radiogenic Sr in the Cr-rich megacrysts reflect extensive interaction of their parental magmas with this metasomatized peridotite.

The stability and composition of sulfate melts in arc magmas

The stability field and composition of immiscible sulfate melts in equilibrium with silicate magmas has been determined using experiments over a range of crustal pressures, allowing an assessment of their possible role in transporting sulfur into the sub-volcanic arc and porphyry copper deposit systems. Experimental starting materials were based on natural trachyandesite and trachydacite compositions, with 3.5–7 wt% H2O and 3.5–5.5 wt% sulfur added to produce large, analyzable amounts of sulfate phases. Conditions ranged over 800–1200 °C, 0.2-1GPa and ƒO2 > NNO + 2.5. Sulfate melts formed at temperatures above 1000 °C at 0.75 and 1 GPa and above 900 °C at 0.2 GPa, suggesting some pressure dependence on their stability. At temperatures below 1100 °C sulfate melts and anhydrite crystals commonly coexist. Sulfate melts quenched to an intergrowth that was difficult to prepare for analysis. However, the composition was approximated by EPMA and further constrained by mass balance calculations. Sulfate melts were dominated by CaO and SO3, but also contained, in order of decreasing abundance, Na2O, K2O, MgO, FeO, Cl and P2O5. Chlorine showed a particular preference for the sulfate melt relative to the coexisting silicate melt, and calculated partition coefficients for sulfate/silicate melts were 5–13 at 1200 °C, 0.75–1 GPa. Experimental data show that, in the absence of an exsolved, hydrous fluid phase, sulfate melts can form in natural arc magmas at near-liquidus temperatures ≥ 1000 °C, assuming that magmas are oxidized and contain sufficient sulfur (> 2000–3000 ppm S). These results suggest that sulfate melt could be an important component in transporting sulfur as well as chlorine to shallow levels in the crust for hydrous magmas under a specific range of conditions. Both the non-quenchable and water-soluble nature of sulfate melts (and anhydrite) make them difficult to identify, unless trapped as mineral inclusions similar to the “wormy anhydrite” trapped in high-temperature amphiboles from Yanacocha, Peru.

Major and trace element partitioning between majoritic garnet, clinopyroxene, and carbon dioxide-rich liquid in model carbonated peridotite at 10 GPa and interpretations of the element chemistry of majoritic garnet inclusions in diamonds from the subcontinental mantle of Brazil and Guinea

Experimentally determined major and trace element partition coefficients between majoritic garnet, clinopyroxene, and carbon dioxide-rich liquid are reported at 10 GPa and 1800 °C in a model carbonated peridotite composition in the system CaO-MgO-Al2O3-SiO2-CO2. Besides majoritic garnet, the liquid coexists with forsterite, orthopyroxene, and clinopyroxene, making melting phase relations invariant at fixed pressure and temperature conditions. Partition coefficients span a wide range of values - for instance, Sr, Nb, Ba, La, and Ce are highly incompatible in majoritic garnet, while Ca, Y, Nb, and Ho are moderately incompatible, and Lu, Si, Al, and Mg are compatible. Strong fractionation of light rare earth elements (e.g., La, Ce, Nd, Sm) and high field strength elements (e.g., Nb, Ta, Zr, Hf, Th) is seen between majoritic garnet and liquid. The experimentally determined partitioning values are used to calculate compositions of melts in equilibrium with majoritic garnet inclusions in diamonds from select localities in Brazil and Guinea. The calculated melts largely straddle those between documented carbonatites, kimberlites, and alkali basalts, low-degree mantle melting products from carbonated peridotite. This resemblance firmly suggests that majoritic garnet inclusions in diamonds from Brazil and Guinea can simply be interpreted as precipitates from such melts, thereby offering an alternative to the hypothesis that the element chemistry of such inclusions in diamonds can largely, and sometimes only, be ascribed to subducted oceanic crust, and further that, fusion of this crust may limit the terrestrial 'carbon recycling' at depths much beyond corresponding to those of Earth's transition zone.

The ~500 Ma Asaji ultramafic–mafic intrusion in Kyushu, southwest Japan: Implications for boninitic magmatism in a late Cambrian nascent arc

It is thought that the continental crust that ultimately became Japan (i.e., proto-Japan) formed during the early Cambrian near the margin of the South China block following its separation from the Australian block. However, the onset of timing of subduction and details of the magmatic evolution of the region are poorly understood, due mainly to the sporadic occurrence of Cambrian rocks. A high-temperature metamorphic complex is distributed throughout eastern Kyushu island, Japan. At the northeastern end of the complex, a narrow zone of ultramafic–mafic rocks includes a late Cambrian ophiolitic assemblage, namely the Asaji ultramafic–mafic intrusion. The ultramafic cumulates in the intrusion consist of harzburgite (spinel–olivine–orthopyroxene), lherzolite–olivine websterite (olivine–orthopyroxene–clinopyroxene ± spinel), and websterite (orthopyroxene–clinopyroxene ± olivine), which formed in that order during differentiation of a parental magma. The chemical compositions of clinopyroxene and spinel from the cumulates show strongly depleted features (e.g., spinel Cr# [= atomic Cr/(Cr + Al)] ≤ 0.91 and TiO2 < 0.3 wt%, and clinopyroxene YbN < 2) and comparable to those of spinel in boninites. In addition, the calculated trace element composition of melts in equilibrium with clinopyroxene from the ultramafic rocks closely resembles the composition of the North Tongan boninite. These petrological and geochemical features suggest that the Asaji ultramafic–mafic intrusion consists of cumulates from a boninitic magma. The presence of boninitic magmatism suggests that the Asaji ultramafic–mafic intrusion was the result of subduction initiation and the infiltration of water into hot asthenosphere during the formation of nascent arc crust.

Ultra-magnesian olivine-bearing ultramafic lava blocks within Cenozoic accretionary sediments at Shizuoka, Japan: Implications for young, hot plume activity beneath the western Pacific Plate

Ultra-magnesian igneous olivine is thought to crystallize from ultramafic melts and can therefore provide information about physicochemical conditions and the geochemistry and lithology of the source in the context of extremely hot mantle activity. This study focuses on the petrology and mineralogy of the Shizuoka meimechites, a series of ultra-magnesian olivine-bearing ultramafic lava blocks embedded in middle Eocene–early Miocene accretionary sediments at Shizuoka, Japan. Olivine phenocrysts within the Shizuoka meimechites have Fo compositions of ca. 81–92.8 mol%, where Fo = 100 Mg/(Mg + Fe). These ultra-magnesian olivines have trace-element compositions that are indicative of derivation from ultramafic melts that were in equilibrium with peridotitic mantle olivine. Al-in-olivine geothermometry yielded crystallization temperatures of ~1450 °C for Fo92.5–92.8 olivine, higher than the potential temperature of present-day mid-ocean ridge basalt source mantle material and similar to the potential temperatures of some large igneous provinces and ocean island basalts. Primary melt compositions in equilibrium with Fo92.5–92.8 olivine were estimated using the whole-rock compositions of the ultramafic lavas and are meimechitic, with MgO concentrations of ~21.4–27.0 wt% and SiO2 concentrations of 45.4–44.5 wt%. The potential temperature of the source mantle region for these meimechites (Tp) is estimated to be ~1486 °C–1705 °C, which is consistent with the Al-in-olivine geothermometry when considering adiabatic cooling during magma ascent. The relationship between Tp and Al-in-olivine temperature estimates for these lavas is consistent with global examples of ultra-magnesian olivine-bearing lavas. These lavas provide evidence of hitherto unknown Late Cretaceous–early Miocene deep mantle activity beneath the western Pacific region.

New geochemical constraints on the origins of MARID and PIC rocks: Implications for mantle metasomatism and mantle-derived potassic magmatism

MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) and PIC (Phlogopite-Ilmenite-Clinopyroxene) rocks are unusual mantle samples entrained by kimberlites and other alkaline volcanic rocks. The formation of MARID rocks remains hotly debated. Although the incompatible element (for example, large ion lithophile element) enrichment in these rocks suggests that they formed by mantle metasomatism, the layered textures of some MARID samples (and MARID veins in composite xenoliths) are more indicative of formation by magmatic processes. MARID lithologies have also been implicated as an important source component in the genesis of intraplate ultramafic potassic magmas (e.g., lamproites, orangeites, ultramafic lamprophyres), due to similarities in their geochemical and isotopic signatures. To determine the origins of MARID and PIC xenoliths and to understand how they relate to alkaline magmatism, this study presents new mineral major and trace element data and bulk-rock reconstructions for 26 MARID and PIC samples from the Kimberley-Barkly West area in South Africa. Similarities between compositions of PIC minerals and corresponding phases in metasomatised mantle peridotites are indicative of PIC formation by pervasive metasomatic alteration of peridotites. MARID genesis remains a complicated issue, with no definitive evidence precluding either the magmatic or metasomatic model. MARID minerals exhibit broad ranges in Mg# (e.g., clinopyroxene Mg# from 82 to 91), which may be indicative of fractionation processes occurring in the MARID-forming fluid/melt. Finally, two quantitative modelling approaches were used to determine the compositions of theoretical melts in equilibrium with MARID rocks. Both models indicate that MARID-derived melts have trace element patterns resembling mantle-derived potassic magma compositions (e.g., lamproites, orangeites, ultramafic lamprophyres), supporting inferences that these magmas may originate from MARID-rich mantle sources.

Immature intra-oceanic arc-type volcanism on the Izanagi Plate revealed by the geochemistry of the Daimaruyama greenstones in the Hiroo Complex, southern Hidaka Belt, central Hokkaido, Japan

The Izanagi Plate is assumed to have underlain the western Panthalassa Ocean to the east of Eurasia, and to have been subducting under the Eurasian continent. Although the Izanagi Plate has been lost to subduction, the subduction complexes of the circum-Panthalassa continental margins provide evidence that subduction-related volcanism occurred within the Panthalassa Ocean, and not just along its margins. The Daimaruyama mass is a kilometer-sized allochthonous greenstone body in the Hiroo Complex in the southeastern part of the Nakanogawa Group in the southern Hidaka Belt, northern Japan. The Hiroo Complex is a subduction complex that formed within the Paleo-Kuril arc–trench system at 57–48 Ma. The Daimaruyama greenstones consist mainly of coarse volcaniclastic rocks with lesser amount of lava. Red bedded chert, red shale, and micritic limestone are also observed as blocks associated with the greenstones. The presence of Early Cretaceous (Aptian–Albian) radiolaria in red bedded cherts within the greenstones indicates that the Daimaruyama greenstones formed after this time. An integrated major and trace element geochemical dataset for whole-rocks and clinopyroxenes of the greenstones indicates a calc-alkaline magmatic trend with low TiO2 contents and increases in SiO2 and decreases in FeO* with increasing differentiation. Negative anomalies of Nb, Ta, and Ti in normal mid-ocean-ridge basalt type normalized patterns are interpreted as “arc-signatures”. Using “rhyolite-MELTS”, we conducted a numerical simulation of magmatic differentiation under conditions of 1.5 kbar and H2O = 3 wt% to reproduce the liquid line of descent of the Daimaruyama greenstones. Back-calculations of the equilibrium melt compositions from the trace element chemistry of the clinopyroxenes generally agree with the whole-rock rare earth element compositions of the Daimaruyama greenstones, therefore providing support for the conditions used for the rhyolite-MELTS calculations as well as the actual results. Clinopyroxene trace element compositions indicate substantial enrichment of Ba in the magma, reflecting the participation of shallow subduction components such as aqueous fluids. Geochemical investigations reveal that the Daimaruyama greenstones were probably submarine volcanic rocks that formed as a result of the subduction of the Izanagi Plate within the Thalassa Ocean (the Thalassa Ocean was the eastern realm of Panthalassa, and represents the proto-Pacific Ocean) after the Early Cretaceous (Aptian–Albian; 125–101 Ma), and they were eventually accreted onto the Paleo-Kuril arc–trench system at 57–48 Ma to form an allochthonous block as part of the mélange facies of the Hiroo Complex on the landward slope of the trench.

Petrogenesis of basaltic shergottite Northwest Africa 8657: Implications for fO2 correlations and element redistribution during shock melting in shergottites

AbstractNorthwest Africa (NWA) 8657 is an incompatible trace element‐enriched, low‐Al basaltic shergottite, similar in texture and chemistry to Shergotty, Zagami, and NWA 5298. It is composed of zoned pyroxene, maskelynite, merrillite, and Ti‐oxide minerals with minor apatite, silica, and pyrrhotite. Pyroxene grains are characterized by patchy zoning, with pigeonite or augite cores zoned to Fe‐rich pigeonite mantles. The cores have rounded morphologies and irregular margins. Combined with the low Ti/Al of the cores, the morphology and chemistry of the pyroxene grains are consistent with initial crystallization at depth (30–70 km) followed by partial resorption en route to the surface. Enriched rare earth element (REE) equilibrium melt compositions and calculated oxygen fugacities (fO2) conditions for pigeonite cores indicate that the original parent melts were enriched shergottite magmas that staged in chambers at depth within the Martian crust. NWA 8657 does not represent a liquid but rather entrained a proportion of pyroxene crystals from magma chambers where fractional crystallization was occurring at depth. Variation between fO2 and bulk‐rock (La/Yb)N of the enriched and intermediate shergottites suggests that oxidation conditions and degree of incompatible element enrichment in the source may not be correlated, as thought previously. Shock melt pockets are characterized by an absence of phosphates and oxide minerals. It is likely that these phases were melted during shock. REEs were redistributed during this process into maskelynite and to a lesser extent the shock melt; however, the overall normalized REE profile of the shock melt is like that of the bulk‐rock, but at lower absolute concentrations. Overall, shock melting has had a significant effect on the mineralogy of NWA 8657, especially the distribution of phosphates, which may be significant for geochronological applications of this meteorite and other Martian meteorites with extensive shock melt.

Magma mush chemistry at subduction zones, revealed by new melt major element inversion from calcic amphiboles

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 Ridolfi and Renzulli (2012), 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 Stamper et al. (2014). 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.

In situ major and trace element analysis of amphiboles in quartz monzodiorite porphyry from the Tonglvshan Cu–Fe (Au) deposit, Hubei Province, China: insights into magma evolution and related mineralization

The Tonglvshan deposit is the largest Cu–Fe (Au) skarn deposit in the Edong district, which is located in the westernmost part of the Middle and Lower Yangtze River metallogenic belt, China. In this study, we performed a detailed in situ analysis of major and trace elements in amphiboles from the ore-related Tonglvshan quartz monzodiorite porphyry using electron microprobe (EMPA) analysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Two distinct populations of amphiboles, which can be distinguished by their aluminum content, are found in the quartz monzodiorite porphyry. The low-aluminum (Low-Al) amphiboles are subhedral or anhedral and formed at 46.3–73.5 MPa and 713–763 °C. In contrast, the high-aluminum (High-Al) amphiboles are euhedral and formed at 88–165 MPa and 778–854 °C. Some euhedral amphiboles are partially or completely replaced by Low-Al amphibole. The compositions of parental melts in equilibrium with the High-Al amphibole (Melt 1) and Low-Al amphibole (Melt 2) were computed by applying solid/liquid partition coefficients. This modeling shows that magma in equilibrium with High-Al amphibole (Melt 1) underwent 40% fractional crystallization of amphibole, plagioclase and apatite at a depth of ~5 km to evolve to magma in equilibrium with Low-Al amphibole (Melt 2). Copper enrichment occurred in the magma after undergoing fractional crystallization. The magma had a high oxygen fugacity, increasing from NNO + 1 (Melt 1) through NNO + 2 to HM (Melt 2), which could have prevented the loss of Cu (and possibly Au) to sulfide minerals during crystallization. Finally, the evolved magma intruded to shallower depths, where it presumably exsolved aqueous ore-forming fluids. Therefore, the large Cu–Fe–Au reserves of the Tonglvshan deposit can likely be attributed to a combination of controlling factors, including high oxygen fugacity, fractional crystallization, fluid exsolution, and a shallow emplacement depth.

New constraints on the origin of the ophiolitic rocks within sinorogenic turbiditic sequences at Cilento region (southern Italy)

Mafic igneous rocks (pillow lavas and gabbros) embedded as olistoliths within Miocene turbiditic sequences crop out in the Cilento area at the Mount Centaurino (Campania region, Southern Italy). The concentration of major oxides, as well as trace element ratios (Nb/Yb, Nb/Ta, Th/Nb) and the chondrite-normalized Rare Earth Elements (REE) patterns suggest a tholeiitic character with Mid Oceanic Ridge Basalts (MORB) affinity. The chemical composition of pillow lavas is consistent with magmas generated by 10% degrees of non-modal fractional partial melting, of a spinel-bearing MORB-type asthenospheric mantle. Regarding gabbros, the calculated composition of parental melts in equilibrium with the clinopyroxenes show a wide compositional range, and there are very different from the pillow basalts of the Mount Centaurino, suggesting that the clinopyroxenes might have derived from more evolved melts compared to those that produced the basalts. The origin of these olistoliths is not yet understood. Here we suggest that these rocks represent fragment of a dismantled accretionary wedge embedded during the deposition of the Cilento group sedimentary successions in a thrust top basin.

Composition of a carbonatitic melt in equilibrium with lherzolite at 5.5–6.3 GPa and 1350°C

Generation of ultra-alkaline melts by the interaction of lherzolite with cardonatites of various genesis was simulated at the P–T parameters typical of the base of the subcratonic lithosphere. Experiments with a duration of 150 h were performed at 5.5 and 6.3 GPa and 1350°C. The concentrations of CaO and MgO in melts are buffered by the phases of peridotite, and the concentrations of alkalis and FeO depend on the composition of the starting carbonatite. Melts are characterized by a low (<7 wt %) concentration of SiO2 and Ca# from 0.40 to 0.47. It is demonstrated that only high-Mg groups of carbonatitic inclusions in fibrous diamonds have a composition close to that of carbonatitic melts in equilibrium with lherzolite. Most likely, the formation of kimberlite-like melts relatively enriched in SiO2 requires an additional source of heat from mantle plumes and probably H2O fluid.