Equilibration Pressures Research Articles

Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS. Part 2: application to Taupo Volcanic Zone rhyolites

Constraining the pressure of crystallisation of large silicic magma bodies gives important insight into the depth and vertical extent of magmatic plumbing systems; however, it is notably difficult to constrain pressure at the level of detail necessary to understand shallow magmatic systems. In this study, we use the recently developed rhyolite-MELTS geobarometer to constrain the crystallisation pressures of rhyolites from the Taupo Volcanic Zone (TVZ). As sanidine is absent from the studied deposits, we calculate the pressures at which quartz and feldspar are found to be in equilibrium with melt now preserved as glass (the quartz +1 feldspar constraint of Gualda and Ghiorso, Contrib Mineral Petrol 168:1033. doi: 10.1007/s00410-014-1033-3 . 2014). We use glass compositions (matrix glass and melt inclusions) from seven eruptive deposits dated between ~320 and 0.7 ka from four distinct calderas in the central TVZ, and we discuss advantages and limitations of the rhyolite-MELTS geobarometer in comparison with other geobarometers applied to the same eruptive deposits. Overall, there is good agreement with other pressure estimates from the literature (amphibole geobarometry and H2O–CO2 solubility models). One of the main advantages of this new geobarometer is that it can be applied to both matrix glass and melt inclusions—regardless of volatile saturation. The examples presented also emphasise the utility of this method to filter out spurious glass compositions. Pressure estimates obtained with the new rhyolite-MELTS geobarometer range between ~250 to ~50 MPa, with a large majority at ~100 MPa. These results confirm that the TVZ hosts some of the shallowest rhyolitic magma bodies on the planet, resulting from the extensional tectonic regime and thinning of the crust. Distinct populations with different equilibration pressures are also recognised, which is consistent with the idea that multiple batches of eruptible magma can be present in the crust at the same time and can be tapped simultaneously by large eruptive events.

Accretion and differentiation of the terrestrial planets with implications for the compositions of early-formed Solar System bodies and accretion of water

In order to test accretion simulations as well as planetary differentiation scenarios, we have integrated a multistage core–mantle differentiation model with N-body accretion simulations. Impacts between embryos and planetesimals are considered to result in magma ocean formation and episodes of core formation. The core formation model combines rigorous chemical mass balance with metal–silicate element partitioning data and requires that the bulk compositions of all starting embryos and planetesimals are defined as a function of their heliocentric distances of origin. To do this, we assume that non-volatile elements are present in Solar System (CI) relative abundances in all bodies and that oxygen and H2O contents are the main compositional variables. The primary constraint on the combined model is the composition of the Earth’s primitive mantle. In addition, we aim to reproduce the composition of the martian mantle and the mass fractions of the metallic cores of Earth and Mars. The model is refined by least squares minimization with up to five fitting parameters that consist of the metal–silicate equilibration pressure and 1–4 parameters that define the starting compositions of primitive bodies. This integrated model has been applied to six Grand Tack N-body accretion simulations. Investigations of a broad parameter space indicate that: (1) accretion of Earth was heterogeneous, (2) metal–silicate equilibration pressures increase as accretion progresses and are, on average, 60–70% of core–mantle boundary pressures at the time of each impact, and (3) a large fraction (70–100%) of the metal of impactor cores equilibrates with a small fraction of the silicate mantles of proto-planets during each core formation event. Results are highly sensitive to the compositional model for the primitive starting bodies and several accretion/core-formation models can thus be excluded. Acceptable fits to the Earth’s mantle composition are obtained only when bodies that originated close to the Sun, at <0.9–1.2AU, are highly reduced and those from beyond this distance are increasingly oxidized. Reasonable concentrations of H2O in Earth’s mantle are obtained when bodies originating from beyond 6–7AU contain 20wt% water ice (icy bodies that originated between the snow line and this distance did not contribute to Earth’s accretion because they were swept up by Jupiter and Saturn). In the six models examined, water is added to the Earth mainly after 60–80% of its final mass has accreted. The compositional evolution of the mantles of Venus and Mars are also constrained by the model. The FeO content of the martian mantle depends critically on the heliocentric distance at which the Mars-forming embryo originated. Finally, the Earth’s core is predicted to contain 8–9wt% silicon, 2–4wt% oxygen and 10–60ppm hydrogen, whereas the martian core is predicted to contain low concentrations (<1wt%) of Si and O.

Revisiting the last major eruptions at Stromboli volcano: inferences on the role of volatiles during magma storage and decompression

Abstract Stromboli is a unique open conduit volcano and a natural laboratory for investigating how volatiles migrate and concentrate under dynamic conditions. Fluid phases are involved in magma decompression and pressurization, modulate Strombolian activity and govern magma rise and fragmentation processes. Here, we have revisited the available data on the last two major eruptions at Stromboli volcano and concentrated our analysis on the 2007 eruption. First, we analysed petrological-geochemical data to assess equilibrium conditions by using standard thermobarometry; we then used a grid of selected reactions which involve solid-melt-fluid equilibria to better constrain the P – T regimes that adequately describe our system. Primitive hydrous basaltic melts, reported in literature and preserved as melt inclusions in olivine (with 2.3–3.8 wt% of H 2 O and 890–1590 ppm CO 2 ), are in equilibrium with forsteritic olivine and a diopsidic clinopyroxene at average pressures of 260 (±47) MPa for temperatures approaching 1170 (±17) °C and calculated (mole fraction of CO 2 within the melt) in the range 0.60–0.76. Ca-rich or ultracalcic melts are regarded as the result of decompression along a steep adiabatic and/or isothermal curve. During this process the magma will cross-cut the stability field of diopside and enter the liquidus field. The earlier crystallized diopside is destabilized and reacts with the coexisting liquid phase leading to the formation of ultracalcic melts. Ejected golden pumices (with 2–3 wt% H 2 O) are in equilibrium with Ca-pyroxene, forsteritic olivine and anorthitic plagioclase at 150–220 MPa and temperatures of 1120–1150 °C. Evolved melt inclusions (substantially degassed) in less magnesian olivine ( c. Fo 70 ) of the scorias show average equilibration pressures of 78 (±20) MPa and temperatures of 1138 (±14) °C. In summary, the higher P–T regimes associated with the origin of primitive melt inclusions are representative of the base of the chamber, where the ferromagnesian phases may crystallize and cumulate. The magma with a bulk composition typical of the pumices is stored in the middle and main part of the chamber (likely its axial sector) and these materials are erupted during paroxysmal and, more rarely, major explosions. Finally, more evolved melt inclusions found in the olivine of the scorias are indicative of crystallization within the conduit or its root zone connected to the upper part of the chamber. Pure extensional regimes and recent geophysical data suggest the existence of a prolate ellipsoidal magma chamber below Stromboli. To constrain its volume we estimated the magma volumes associated with SO 2 degassing (during the 2007 major eruption) by applying a refined petrological model that allowed us to estimate the magma fluxes in the subvolcanic region (i.e. the magma flux entering the degassing zone). The long-term trend of this magma flux follows an overall exponential decay, typical of pressurized magmatic systems, and indicates that magma rise was accompanied and followed by slow decompression. This trend was shown to be consistent with release of elastic strain accumulated either by pressurization of the rocks surrounding the magma reservoir, by pressurization of the magma itself or both. By analysing the reservoir elastic response during magma decompression, we found that the current Stromboli magma chamber volume may be adequately constrained to 1–2 km 3 .

Calculating melting temperatures and pressures of peridotite protoliths: Implications for the origin of cratonic mantle

The old, stable cores of continents – cratons – are underlain by thick and cold mantle keels, composed of melt-depleted and low density peridotite residues. The origins of these thick keels are debated. Were these thick keels formed in situ, by orogenic thickening, or by underplating of buoyant residual mantle? Key to this debate is determining the temperature and pressure at which the protoliths of cratonic peridotites melted (igneous protolith conditions) and comparing to their metamorphic (subsolidus) temperatures and pressures within the keel. This paper presents a method for explicit calculation of the temperatures and pressures at which the peridotite protoliths melted. The approach relies only on the bulk FeO and MgO of residual peridotites. A system of equations consisting of mass balance and new calibrations of Mg peridotite/melt partitioning and melt productivity is then solved simultaneously. The igneous protoliths of abyssal peridotites are found to have melted at effective pressures of 1–2 GPa and temperatures of 1300–1400 °C, within error of the magmatic temperatures and pressures of melt extraction inferred independently from the SiO2 and MgO contents of mid-ocean ridge basalts. Archean cratonic peridotites, after filtering for the secondary effects of refertilization and orthopyroxene-metasomatism, give igneous protolith pressures and temperatures of 1–5 GPa (30–150 km) and 1400–1750 °C, similar to magmatic temperatures and pressures determined for Archean basalts thought to be representative of the thermal state of the Archean ambient mantle. Most importantly, cratonic peridotite protolith pressures and temperatures are shallower and hotter than their subsolidus equilibration pressures (3–7.5 GPa; 90–200 km) and temperatures (900–1300 °C), which reflects the recent thermal state of the cratonic lithosphere. Specifically, for individual samples with both melting and subsolidus thermobarometric constraints, we find that subsolidus pressures are 1–2 GPa (30–60 km) higher than their igneous protolith pressures although some of the deepest samples experienced minor increases in pressure. Collectively, these results support the suggestion that the building blocks of cratons were generated by hot shallow melting with a mantle potential temperature 200–300 °C warmer than the present. This shallowly generated mantle was subsequently thickened during orogenic episodes, culminating in the formation of a thick, stable craton. Whether such thickening has any modern analogs cannot be answered from this work alone.

Partially melted, mica-bearing crust in Central Tibet

Surface wave tomography shows that the central Tibetan Plateau (the Qiangtang block) is characterized by S wave speeds as slow as 3.3 km/s at depths from 20–25 km to 45–50 km and S wave radial anisotropy of at least 4% (VSH > VSV) that is stronger in the west than the east. The depth of the Curie temperature for magnetite inferred from satellite magnetic measurements, the depth of the α-β quartz transition inferred from VP/VS ratios, and the equilibration pressures and temperatures of xenoliths erupted from the middle to deep crust indicate that the Qiangtang crust is hot, reaching 1000°C at the Moho. This inferred thermal gradient crosses the dehydration melting solidi for crustal rocks at 20–30 km depth, implying the presence or former presence of melt in the Tibetan middle to deep crust. These temperatures do not require the wholesale breakdown of mica at these depths, because F and Ti can stabilize mica to at least 1300°C. Petrology suggests, then, that the Qiangtang middle to deep crust consists of a mica-bearing residue from which melt has been extracted or is being extracted. Wave speeds calculated for mica-bearing rocks with a subhorizontal to gently dipping foliation and 2% silicate melt are a good match to the wave speeds and anisotropy observed by seismology.

Magma mixing and high fountaining during the 1959 Kīlauea Iki eruption, Hawai‘i

The 1959 Kīlauea Iki eruption provides a unique opportunity to investigate the process of shallow magma mixing, its impact on the magmatic volatile budget and its role in triggering and driving episodes of Hawaiian fountaining. Melt inclusions hosted by olivine record a continuous decrease in H2O concentration through the 17 episodes of the eruption, while CO2 concentrations correlate with the degree of post-entrapment crystallization of olivine on the inclusion walls. Geochemical data, when combined with the magma budget and with contemporaneous eruption observations, show complex mixing between episodes involving hot, geochemically heterogeneous melts from depth, likely carrying exsolved vapor, and melts which had erupted at the surface, degassed and drained-back into the vent. The drained-back melts acted as a coolant, inducing rapid cooling of the more primitive melts and their olivines at shallow depths and inducing crystallization and vesiculation and triggering renewed fountaining. A consequence of the mixing is that the melts became vapor-undersaturated, so equilibration pressures cannot be inferred from them using saturation models. After the melt inclusions were trapped, continued growth of vapor bubbles, caused by enhanced post-entrapment crystallization, sequestered a large fraction of CO2 from the melt within the inclusions. This study, while cautioning against accepting melt inclusion CO2 concentrations “as measured” in mixed magmas, also illustrates that careful analysis and interpretation of post-entrapment modifications can turn this apparent challenge into a way to yield novel useful insights into the geochemical controls on eruption intensity.

Burial and exhumation during Archean sagduction in the East Pilbara Granite-Greenstone Terrane

Archean granitic domes and intervening volcano-sedimentary basins are commonly interpreted as the product of “sagduction”, a process involving the gravitational sinking of surficial greenstone cover sequences into narrow belts and the coeval exhumation of deeper granitic crust into broad domes. Alternatives to the sagduction model that can account for the regional dome and basin pattern include fold interferences and extensional metamorphic core complexes. In order to provide quantitative constraints on the pressure–temperature–time (P–T–t) evolution experienced by greenstone–granite pairs we investigate the Warrawoona greenstone belt and adjacent Mount Edgar granitoid dome the East Pilbara craton (Western Australia). We adopt a multidisciplinary approach that includes structural, metamorphic, geochronological and numerical investigation of the 3.5–3.2 Ga Mount Edgar high-grade metamorphic rocks. Garnet-bearing metasediments and metabasalts collected along the SW and SE rims of the Mount Edgar Dome show higher pressure but lower temperature of equilibration (9–11 kbar and 450–550 °C) than enclaves collected in the core of the dome (6–7 kbar and 650–750 °C). In situ oxygen isotope analysis and U–Pb dating of zircons from the enclave indicate a metasedimentary origin (∂18O∼+13‰) for the protoliths and a metamorphic age of 3311.9±4.9 Ma. In addition, monazites included in garnet from the SW dome margin yield an age of 3443.4±4.5 Ma. These monazites suggest the existence of an older metamorphic cycle and imply a polymetamorphic evolution of the unit. The P–T–t data support fast, gravity-driven tectonics, wherein sedimentary rocks were buried to lower crustal conditions, metamorphosed and exhumed back to the surface during a cycle lasting only a few million years. Forward thermo-mechanical modeling confirms the P–T–t evolutions deduced from thermobarometry and geochronology. Our model shows a large range of possible apparent geothermal gradients during sagduction, including low apparent geothermal gradients that are similar to those proposed for Archean and modern subduction.

Ultramafic xenoliths from Damaping (Hannuoba region, NE-China): Petrogenetic implications from crystal chemistry of pyroxenes, olivine and Cr-spinel and trace element content of clinopyroxene

Olivine, orthopyroxene, clinopyroxene and spinel from 16 different lherzolite mantle xenoliths from Damaping (Hannuoba region, NE-China) have been analyzed by X-ray single crystal diffraction and electron microprobe to define their structure, chemistry and cation distribution. LA-ICP-MS analysis has been carried out on clinopyroxenes to determine their LILE (Large-Ion Lithophile Elements), HFSE (High Field Strength Elements) and REE (Rare Earth Elements) contents. These latter define Depleted, Enriched, U-shaped and Transitional CI-normalized patterns suggesting that the xenolith suite here studied experienced at least two metasomatic events related to the porous flow percolation of melts with tholeiitic and alkaline affinity, respectively. The cation distribution of the mineral phases allowed determination of their intra- and inter-crystalline temperatures of equilibration. The closure temperature of intra-crystalline reactions for the constituent phases is in the range 600–800°C, suggesting a relatively slow cooling rate, while the inter-crystalline temperature interval found out is in the range 866–1048°C. The pressure conditions estimated for Hannuoba xenoliths through structural considerations correspond to a depth of about 50–60km, consistent with the Moho depth beneath the Hannuoba area, which is estimated at about 42km. The pressures of equilibration, as estimated from the cell and T site volumes of the clinopyroxenes, have been compared with the trace element and REE signatures; they demonstrate that Enriched, Depleted, U-shaped and Transitional clinopyroxenes formed at different pressures and are not restricted to a specific region of the mantle, testifying that the metasomatism took place at different depths in the mantle.

Paragenesis and chemical characteristics of the celsian−hyalophane−K-feldspar series and associated Ba-Cr micas in barite-bearing strata of the Mesoarchaean Ghattihosahalli Belt, Western Dharwar Craton, South India

The upper greenschist - lower amphibolite facies, argillaceous to chemical-exhalative metasedimentary sequence of the Mesoarchaean Ghattihosahalli Schist Belt (GHSB), southern India, has been examined with a special focus on the paragenesis and solid solution characteristics of barian feldspars and associated dioctahedral Ba-Cr-bearing micas. Barian feldspars occur as untwinned porphyroblasts in a recrystallized finely banded matrix of barite, quartz and minor white mica. Idioblastic celsian (Cls98-76Or2-20Ab1-8) and hyalophane (Cls55-39Or35-51Ab10) predate the greenschist-facies foliation, whereas xenoblastic hyalophane (Cls44-35Or45-59Ab8–17) and mantles on celsian (Cls45-35Or42-60Ab13-5) as well as xenoblastic barian K-feldspar (Cls6Or90Ab2) postdate the last fabric-defining event. The preservation of extremely complex zoning patterns down to the micron-scale shows that diffusional homogenization did not operate at fluid-present low to medium-grade conditions (350–550 °C, 3–5 kb). Microstructures indicate that at these conditions barian feldspars deform exclusively by brittle fracturing and do not undergo recrystallization. Barian feldspar compositions confirm the positive correlation of Na-content with temperature and the existence of a narrow asymmetric compositional gap (Cls90-85↔Cls55, ~350 °C) which probably closes at lower amphibolite facies conditions (Xc ~Cls75; Tc ~550 °C). White micas are solid solutions of the end-members muscovite, ganterite (Ba0.5 K0.5)Al2(Al1.5Si2.5)O10(OH)2, paragonite, celadonite with a significant substitution of [VI]Al by Cr. Zoning is a common feature with cores being enriched in Ba. The data document extensive Ba substitution for K from muscovite to ganterite, exclusively controlled by the coupled substitution [XII]K + [IV]Si ↔ [XII]Ba + [IV]Al and strongly dependent on bulk composition. The extent of solid solution from (Ms+Gnt) towards paragonite and celadonite end-members is controlled by the miscibility gap in the (Ms+Gnt)–Pg–Cel pseudoternary, with the Pg-substitution depending on temperature and the Cel-substitution on pressure. [IV]Si values between 3.1 and 3.3 in Ba-poor micas indicate minimum pressures of chemical equilibration in the order of 3–5 kbar, while the most sodian compositions of low-celadonite micas provide an upper temperature estimate of ~550 °C, consistent with P-T estimates for assemblages of metapelites (500–550 °C, 4–5 kb).

Tracing mantle sources and Samoan influence in the northwestern Lau back‐arc basin

Helium isotopes are commonly used as a diagnostic fingerprint of Samoan mantle in the northern Lau Basin, but the extent of input from Samoan sources can only be clearly resolved by coupling 3He/4He with other geochemical tracers such as trace elements and other isotope systems. We present new major element, dissolved volatile (H2O, CO2, S, Cl, F), trace element, and Sr‐Nd‐Pb‐Hf isotope data for new samples from the NW Lau Basin from five distinct regions (Rochambeau Rifts (RR), Northwest Lau Spreading Center (NWLSC), Peggy Ridge (PR), Lau Extensional Transform Zone (LETZ), and Central Lau Spreading Center (CLSC)) that range from distinctively elevated to normal mid‐ocean ridge basalt3He/4He. Helium isotopes variations are not correlated with radiogenic isotopes or trace element abundances. Our new data suggest two‐component mixing of MORB‐like mantle with an enriched mantle source, similar to Samoa, although consideration of a complete regional data set suggests there may be other sources of heterogeneity in the mantle beneath NW Lau. Models of mantle potential temperature (Tp) and primary melt equilibration temperatures indicate similar Tp of ∼1400°C for NW Lau, suggesting no strong temperature gradient. The pressure of melt equilibration deepens toward the north (∼1.1–1.2 GPa at PR, LETZ, CLSC; ∼1.3–1.4 GPa at RR, NWLSC), consistent with melting mantle of a constant Tp but variable H2O content. Samoan and MORB‐like sources are clearly present beneath the NW Lau basin, but geochemical diversity among the existing data suggest that more than two mantle sources may contribute to mantle enrichment beneath NW Lau.

On the thermal evolution of the mantle wedge at subduction zones

We use a 2-dimensional numerical geodynamic model to investigate the evolution of the mantle wedge at subduction zones over a period of 300Myr following the onset of subduction. A variety of parameterizations of the overriding plate, as well as plate subduction rates and mantle potential temperatures, are considered systematically. The average temperature in the mantle wedge within 120km of the trench is found to decrease substantially (up to ∼100°C) over this period, with the most rapid cooling occurring during the first 100Myr. The observed cooling is not spatially uniform, but rather is concentrated in the uppermost 50km of the mantle wedge, immediately beneath the overriding plate. Temperatures in the mantle wedge in the vicinity of arc volcanism decrease by as much as >200°C over the 300Myr period. This decrease in temperature results in a decrease in the portion of mantle wedge beneath the arc in which hydrous melting can occur, impacting both the distribution of melting within the wedge and likely the composition of erupted melts. The observed variations in temperatures in the subarc portion of the mantle wedge with time are significantly larger than the changes in temperature resulting from inclusion of radiogenic heat production in the overriding plate or a zone of partial coupling between the slab and mantle. The results suggest that the mantle wedge is warmer than predicted by steady state thermal models, which may account in part for the differences between the petrologically determined pressure and temperature of equilibration for arc magmas and predictions of the thermal structure of the mantle wedge obtained from steady state thermal models.

Partitioning of Ru, Rh, Pd, Re, Ir and Pt between liquid metal and silicate at high pressures and high temperatures - Implications for the origin of highly siderophile element concentrations in the Earth’s mantle

The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal–silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5–18GPa and 2423–2773K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2–98.9 wt% (XFe=0.03–0.67) such that oxygen fugacities of IW−1.5 to IW+1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1–119ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized.The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ∼6GPa and much weaker in the range 6–18GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P–T conditions in a terrestrial magma ocean (peridotite liquidus at P⩽60–80GPa) we conclude that the P–T-induced decrease of D would not have been sufficient to explain HSE mantle abundances by metal–silicate equilibration at a common set of P–T-oxygen fugacity conditions. Therefore, the mantle concentrations of most HSEs cannot have been established during core formation. The comparatively less siderophile Pd might have been partly retained in the magma ocean if effective equilibration pressures reached 35–50GPa. To a much smaller extent this could also apply to Pt and Rh providing that equilibration pressures reached ⩾60GPa in the late stage of accretion. With most of the HSE partition coefficients at 60GPa still differing by 0.5–3 orders of magnitude, metal–silicate equilibration alone cannot have produced the observed near-chondritic HSE abundances of the mantles of the Earth as well as of the Moon or Mars. Our results show that an additional process, such as the accretion of a late veneer composed of some type of chondritic material, was required. The results, therefore, support recent hybrid models, which propose that the observed HSE signatures are a combined result of both metal–silicate partitioning as well as an overprint by late accretion.

Melting, Differentiation and Degassing at the Pantelleria Volcano, Italy

We present the results of the first systematic study of melt compositions at Pantelleria, based on both melt inclusions and matrix glasses in pantellerites from 10 eruptions during the last eruptive cycle (<45 kyr). We present major and trace element compositions, as well as data on the volatiles sulphur (S), fluorine (F), chlorine (Cl), water (H2O), carbon dioxide (CO2) and lithium (Li) Rare earth element (REE) compositions were inverted using the program INVMEL to establish the melt fraction vs depth relationship in the Pantellerian mantle source region. Inversion indicates that melts are generated by ∼1·7% melting of a light rare earth element (LREE)-enriched mantle source. The source lies principally within the spinel–garnet transition zone, which, on the basis of trace element ratios, shows some affinity to the source of North African magmatism. Major and trace element data indicate a gap in melt compositions at intermediate compositions, consistent with previously published whole-rock data. This gap rules out the possibility of explaining chemical variability in the Pantelleria lavas merely by changes in the crystal content of the magmas. Principal component analysis of major element glass compositions shows that the liquid line of descent for mafic melt compositions is controlled by clinopyroxene, plagioclase, magnetite and olivine crystallization. Alkali feldspar, clinopyroxene, ilmenite and olivine or aenigmatite crystallization controls the liquid line of descent for the silicic melt compositions, with aenigmatite broadly replacing olivine in the most evolved magmas. Trace element modelling indicates that 96% fractional crystallization is required to generate pantellerites from alkali basalts at Pantelleria (through trachytes, generated after 76% fractional crystallization). We have measured pantellerite volatile concentrations in melt inclusions and in matrix glasses from a variety of eruptions. Melt inclusions, on average, contain 350 ppm S, 3500 ppm F and 9000 ppm Cl. We have measured up to 4·9 wt % H2O and 150 ppm CO2 in melt inclusions. Li–H2O systematics and Cl abundances in melt inclusions are consistent with partitioning of Li and Cl into a subcritical hydrosaline fluid at low pressures. The volatiles H2O and CO2 are used to estimate melt equilibration pressures, which reach a maximum of 1·5 kbar. Temperatures of 800°C are calculated for the most evolved pantellerites, using published feldspar–melt geothermometers, and up to 870°C for the least evolved samples. Low melt viscosities are calculated for the range of pantellerite compositions observed and may account for rapid differentiation by crystal settling. Stable density stratification of the magma chamber is reflected in the eruption of generally progressively more fractionated compositions after the Green Tuff eruption during the last eruptive cycle. Some anomalies in this trend may be explained by variation in the relative rates of eruption vs fractionation. The density stratification is expected to be enhanced and further stabilized by the efficient migration of a fluid phase to the roof of the magma chamber. The sulphur data are used in combination with published experimental partitioning data for peralkaline rhyolites to estimate the sulphur yield to the atmosphere for a large pantelleritic eruption similar to the Green Tuff. This is expected to be markedly higher than for a similar-sized metaluminous rhyolitic or dacitic eruption, mainly owing to the higher bulk sulphur content, lower fluid–melt partition coefficients, and rapid differentiation and vapour phase segregation in the magma chamber.

The effects of polybaric partial melting on density and seismic velocities of mantle restites

Partial melting and melt extraction in the Earth's upper mantle can significantly modify the composition, and therefore the thermophysical properties, of the solid residues (restites). Seismic velocities have been by far the most used observable to infer such melt depletion anomalies in the lithospheric mantle. However, three fundamental issues that make such interpretations dubious are: i) previous studies addressing melt depletion effects have been based on isobaric batch (equilibrium) melting experiments at near-solidus temperatures instead of more realistic polybaric near-fractional models at different equilibration pressures, ii) the use of indicators such as VP/VS is strongly influenced by anelastic attenuation and phase stability, and iii) compositional effects tend to be of the order of uncertainties in seismic models.This paper presents the results of a systematic exploration of all these effects on seismic velocities in peridotites. Our results show that polybaric vs isobaric models of partial melting result in similar VP and VS trends with degree of melting (F) when they re-equilibrate at sub-solidus temperatures, but they differ from previous parameterizations based on isobaric experiments at near-solidus temperatures. For deep melting paths (i.e. high potential temperature), solid residues show maximum VP and VS increases of ∼1% and 1.7%with respect to their fertile counterparts. Shallow melting paths produce significantly smaller effects, even at F∼0.25. Moreover, in the case of VP, these effects are not linear and ∂VP/∂F can be either positive or negative depending on the melting path. We find that while the ∂(VPVS−1)/∂F of residues is strongly dependent on the melting history, ∂(ρVS−1)/∂F remains nearly constant regardless of the melting path or extent of melting. This confirms that ρ/VS is not only a reliable indicator of compositional variations in natural samples, but also of degree of melting. This indicator could therefore be used to inform joint inversions of gravity and seismic velocities to test plausible depletion effects in the lithospheric mantle.

A new Fe/Mn geothermometer for hydrothermal systems: Implications for high-salinity fluids at 13°N on the East Pacific Rise

Field and experimental investigations demonstrate the chemistry of mid-ocean ridge hydrothermal vent fluids reflects fluid–mineral reaction at higher temperatures than those typically measured at the seafloor. To account for this and, in turn, be able to better constrain sub-seafloor hydrothermal processes, we have developed an empirical geothermometer based on the dissolved Fe/Mn ratio in high-temperature fluids. Using data from basalt alteration experiments, the relationship; T (°C) = 331.24 + 112.41*log[Fe/Mn] has been calibrated between 350 and 450 °C. The apparent Fe–Mn equilibrium demonstrated by the experimental data is in good agreement with natural vent fluids, suggesting broad applicability. When used in conjunction with constraints imposed by quartz solubility, associated sub-seafloor pressures can be estimated for basalt-hosted systems. As an example, this methodology is used to interpret new data from 13°N on the East Pacific Rise, where high-temperature fluids both enriched and depleted in chloride (339–646 mmol/kg), relative to seawater, are actively venting within a close proximity. Accounting for these variable salinities, active phase separation is clearly taking place at 13°N, yet the fluid Fe/Mn ratios and the silica concentrations suggest equilibration at temperatures less than those coinciding with the two-phase region. These data show the chloride-enriched fluid reflects the highest temperature and pressure (∼432 °C, 400 bars) of equilibration, consistent with circulation near the top of the inferred magma chamber. This is in agreement with the elevated CO 2 concentration relative to the chloride-depleted fluids. The noted temperature derived from the Fe/Mn geothermometer is higher than the critical temperature for a fluid of equivalent salinity. This carries the important implication that, despite being chloride-enriched relative to seawater, these fluids evolved as the vapor component of even higher salinity brine.

The Origin of Intra-plate Ocean Island Basalts (OIB): the Lid Effect and its Geodynamic Implications

Based on an evaluation of major and trace element data for ocean island basalts (OIB), we demonstrate that oceanic lithosphere thickness variation, which we refer to as the lid effect, exerts the primary control on OIB geochemistry on a global scale. The lid effect caps the final depth (pressure) of melting or melt equilibration. OIB erupted on thick lithosphere have geochemical characteristics consistent with a low extent and high pressure of partial melting, whereas those erupted on thin lithosphere exhibit the reverse; that is, a high extent and low pressure of melting cessation. This observation requires that mantle melting beneath intra-plate volcanic islands takes place in the asthenosphere and results from dynamic upwelling and decompression. Melting beneath all ocean islands begins in the garnet peridotite facies, imparting the familiar 'garnet signature' to all OIB melts (e.g. [Sm/Yb](N) > 1); however, the intensity of this signature decreases with increasing extent of melting beneath thinner lithospheric lids as a result of dilution. The dilution effect is also recorded in the radiogenic isotope composition of OIB, consistent with the notion that their mantle source regions are heterogeneous with an enriched component of lower solidus temperature dispersed in a more refractory matrix. High-quality data on the compositions of olivine phenocrysts from mid-ocean ridge basalt and global OIB sample suites are wholly consistent with the lid effect without the need to invoke olivine-free pyroxenite as a major source component for OIB. Caution is necessary when using basalt-based thermobarometry approaches to estimate mantle potential temperatures and solidus depth because OIB do not unequivocally record such information. For plate ages up to similar to 80 Ma, we demonstrate that the geophysically defined base of the growing oceanic lithosphere corresponds to both an isotherm (similar to 1100 degrees C) and the pargasite (amphibole) dehydration solidus of fertile mantle peridotite. As pargasite in H2O-CO2-bearing mantle peridotite is stable under conditions of T 1100 degrees C and P 3 GPa (similar to 90 km), this solidus is essentially isothermal (i.e. dT/dP similar to 0 in P-T space) with T similar to 1100 degrees C) at depths 90 km, but becomes isobaric (i.e. dP/dT similar to 0 in P-T space) at the similar to 90 km depth. The latter explains why older (> 70 Ma) oceanic lithosphere cannot be thicker than similar to 90 km without the need to invoke physically complex processes such as convective removal.

Compositional trends among Kaapvaal Craton garnet peridotite xenoliths and their effects on seismic velocity and density

We examine the modes and compositions of garnet-bearing peridotite xenoliths from the Kaapvaal Craton to quantify factors governing density and seismic velocity variations within metasomatically altered cratonic mantle. Three distinct compositional trends are resolved by principal component analysis. The first reflects differences in residue composition resulting from partial melting. The second is associated with orthopyroxene (opx) enrichment, possibly due to silica addition by subduction zone fluids in the source region of the xenoliths. The third principal component reflects garnet and clinopyroxene enrichment possibly as a consequence of melt infiltration. More than half of the mineral mode variance among Kaapvaal Craton xenoliths can be accounted for by opx enrichment. Melt depletion effects can account for as much as 30% of the variance, while less than 20% of the variance is associated garnet and clinopyroxene enrichment. Using the parameterization of Schutt and Lesher (2006) we show that at cratonic mantle temperatures and pressures, orthopyroxene enrichment results in little change in bulk density ( ρ bulk ) and shear-wave velocity ( V S ), but decreases compressional wave velocities ( V P ) and V P /V S . In contrast, melt depletion has little effect on V P , but leads to an increase in V S and a decrease in ρ bulk and V P /V S . Garnet (gt) and clinopyroxene (cpx) enrichment cause an increase in ρ bulk , V P , V S , and V P /V S . The isolation of the major contributions to xenolith compositional variations among the Kaapvaal Craton suite helps to reconcile seeming discrepancies among previous studies that estimate the effects of composition on mantle density and seismic velocity based on either xenolith or laboratory data. Subtle variations in these properties with the pressure of equilibration may explain some of the fine scale structure in seismic tomograms for cratonic mantle, but overall differences among peridotite lithologies can only account for at most a 2–3% change in seismic velocities. Larger changes in lithospheric seismic properties are more likely associated with temperature differences or presence of mafic or hydrated lithologies. We also find that the density effects of melt depletion are insufficient to produce cratonic mantle that is neutrally buoyant with respect to fertile convecting mantle.

Evaluation of phase chemistry and petrochemical aspects of Samchampi-Samteran differentiated alkaline complex of Mikir Hills, northeastern India

The Samchampi-Samteran alkaline complex occurs as a plug-like pluton within the Precambrian granite gneisses of Mikir Hills, Assam, northeastern India and it is genetically related to Sylhet Traps. The intrusive complex is marked by dominant development of syenite within which ijolitemelteigite suite of rocks is emplaced with an arcuate outcrop pattern. Inliers of alkali pyroxenite and alkali gabbro occur within this ijolite-melteigite suite of rocks. The pluton is also traversed by younger intrusives of nepheline syenite and carbonatite. Development of sporadic, lumpy magnetite ore bodies is also recorded within the pluton. Petrographic details of the constituent lithomembers of the pluton have been presented following standard nomenclatorial rules. Overall pyroxene compositions range from diopside to aegirine augite while alkali feldspars are typically orthoclase and plagioclase in syenite corresponds to oligoclase species. Phase chemistry of nepheline is suggestive of Na-rich alkaline character of the complex. Biotite compositions are typically restricted to a uniform compositional range and they belong to ‘biotite’ field in the relevant classification scheme. Garnets (developed in syenite and melteigite) typically tend to be Ti-rich andradite, which on a closer scan can be further designated as melanites. Opaque minerals mostly correspond to magnetite. Use of Lindsley’s pyroxene thermometric method suggests an equilibration temperature from ∼450°–600°C for melteigite/alkali gabbro and ∼400°C for syenite. Critical assessment of other thermometric methods reveals a temperature of equilibration of ∼700°–1350°C for ijolite-melteigite suite of rocks in contrast to a relatively lower equilibration temperature of ∼600°C for syenite. Geobarometric data based on pyroxene chemistry yield an equilibration pressure of 5.32–7.72 kb for ijolite, melteigite, alkali pyroxenite, alkali gabbro and nepheline syenite. The dominant syenite member of the intrusive plug records a much higher (∼11 kb) equilibration pressure indicating a deeper level of intrusion. Major oxide variations of constituent lithomembers with respect to differentiation index (D.I.) corroborate a normal magmatic differentiation. A prominent role of liquid immiscibility is envisaged from field geological, petrographic and petrochemical evidences. Tectonic discrimination diagrams involving clinopyroxene chemistry strongly suggest within plate alkaline affinity for the parental magma which is in conformity with the regional plume tectonics.

Evidence for high-pressure core-mantle differentiation from the metal–silicate partitioning of lithophile and weakly-siderophile elements

Liquid Fe metal–liquid silicate partition coefficients for the lithophile and weakly-siderophile elements Ta, Nb, V, Cr, Si, Mn, Ga, In and Zn have been measured in multianvil experiments performed from 2 to 24 GPa, 2023–2873 K and at oxygen fugacities of −1.3 to −4.2 log units relative to the iron-wüstite buffer. Compositional effects of light elements dissolved in the metal liquid (S, C) have been examined and experiments were performed in both graphite and MgO capsules, specifically to address the effect of C solubility in Fe-metal on siderophile element partitioning. The results were used to examine whether there is categorical evidence that a significant portion of metal–silicate equilibration occurred under very high pressures during core-mantle fractionation on Earth. Although the depletion of V from the mantle due to core formation is significantly greater than that of Nb, our results indicate that both elements have similar siderophile tendencies under reducing conditions at low pressures. With increasing pressure, however, Nb becomes less siderophile than V, implying that average metal–silicate equilibration pressures of at least 10–40 GPa are required to explain the Nb/V ratio of the mantle. Similarly the moderately-siderophile, volatile element ratios Ga/Mn and In/Zn are chondritic in the mantle but both volatility and core-mantle equilibration at low pressure would render these ratios strongly sub-chondritic. Our results indicate that pressures of metal–silicate partitioning exceeding 30–60 GPa would be required to render these element ratios chondritic in the mantle. These observations strongly indicate that metal–silicate equilibration must have occurred at high pressures, and therefore support core-formation models that involve deep magma oceans. Moreover, our results allow us to exclude models that envisage primarily low-pressure (<1 GPa) equilibration in relatively small planetary bodies. We also argue that the core cannot contain significant U as this would require metal–silicate equilibration at oxygen fugacities low enough for significant amounts of Ta to have also been extracted from the mantle. Likewise, as In is more siderophile than Pb but similarly volatile and also quite chalcophile it would have been difficult for Pb to enter the core without reversing the relative depletions of these elements in the mantle unless metal–silicate equilibration occurred at high pressures >20 GPa.

An alternative model for silica enrichment in the Kaapvaal subcontinental lithospheric mantle

The Mg- and Si-rich nature of the sub-cratonic lithospheric mantle (SCLM) beneath the Kaapvaal Craton indicates extensive melt depletion, followed by a Si-enrichment process. Six highly silica enriched peridotites from Kimberley containing high amounts of orthopyroxene (Opx) or garnet (Grt) that are locally concentrated in clots, were investigated to constrain the timing and nature of the Si-enrichment process. A clinopyroxene-bearing lherzolite containing an Opx-clot was studied to quantify the effects of recent metasomatism on the Si-enriched samples. Minerals from the lherzolite, together with Opx from harzburgites and Opx- and Grt-clots have Hf–Nd isotope ratios at the time of kimberlite eruption, 90 Ma, comparable to group I kimberlites and are close to trace element equilibrium with kimberlitic melts. This implies the xenoliths underwent major interaction with kimberlitic melts close to the time of kimberlite eruption. Harzburgites and mineral clots record equilibration pressures and temperatures of, respectively, between 3.5–4.3 GPa and 930–1060 °C. The garnets in Opx-clots have low Lu/Hf and ε Hf(t) −15, whereas garnets from Grt-clots have high Lu/Hf and ε Hf(t) +10. In contrast, Grt from both Grt- and Opx-clots have low Sm/Nd and ε Nd −10. The whole rock platinum group element (PGE) concentrations are an order of magnitude higher in the Grt-clot than the Opx-clot. Measured 187Os/ 188Os range from 0.1085 to 0.1222. The Grt-clot bearing sample yields Nd–Hf–Os isotope model ages that suggest formation in the Neoproterozoic (∼650 Ma). In contrast, an Opx-clot yields T RD ages of 2.8 Ga, which is interpreted as the time of formation of the host harzburgite. The Opx-clots and host harzburgites have comparable Lu–Hf isotope systematics that imply Opx growth at ∼1.3 Ga and hence their formation is not related to the Grt-clots. Garnets from Opx- and Grt-clots have elevated high-field strength element (HFSE) concentrations, and lack HFSE depletion relative to other trace elements with comparable degrees of incompatibility in the mantle (La/Nb < 0.5). In addition, calculated melts in equilibrium with Grt have strongly fractionated REE (Nd/Yb > 300) and HREE depletion (Yb N < 0.1) suggesting equilibration with a hydrous melt that is more HREE depleted than a kimberlitic melt. Previous models that related Si-enrichment to subduction are inconsistent with the lack of HFSE depletion (La/Nb < 0.5). Therefore the favoured model for Opx- and Grt-clot formation is infiltration of a hydrous melt in a within plate geodynamical environment associated with volcanism in the Mid-proterozoic and Neoproterozoic, respectively. This implies that Si-enrichment of the Kaapvaal SCLM may be a consequence of numerous localised magmatic events rather than a single craton-wide process.