Showing papers in "Contributions to Mineralogy and Petrology in 2016"

An experimental study of amphibole stability in low-pressure granitic magmas and a revised Al-in-hornblende geobarometer

Abstract: We report new experimental data on the composition of magmatic amphiboles synthesised from a variety of granite (sensu lato) bulk compositions at near-solidus temperatures and pressures of 0.8–10 kbar. The total aluminium content (Al^(tot)) of the synthetic calcic amphiboles varies systematically with pressure (P), although the relationship is nonlinear at low pressures (<2.5 kbar). At higher pressures, the relationship resembles that of other experimental studies, which suggests of a general relationship between Al^(tot) and P that is relatively insensitive to bulk composition. We have developed a new Al-in-hornblende geobarometer that is applicable to granitic rocks with the low-variance mineral assemblage: amphibole + plagioclase (An_(15–80)) + biotite + quartz + alkali feldspar + ilmenite/titanite + magnetite + apatite. Amphibole analyses should be taken from the rims of grains, in contact with plagioclase and in apparent textural equilibrium with the rest of the mineral assemblage at temperatures close to the haplogranite solidus (725 ± 75 °C), as determined from amphibole–plagioclase thermometry. Mean amphibole rim compositions that meet these criteria can then be used to calculate P (in kbar) from Al^(tot) (in atoms per formula unit, apfu) according to the expression: P (kbar)=0.5+0.331(8)×Al^(tot) +0.995(4)×(Al^(tot))^2. This expression recovers equilibration pressures of our calibrant dataset, comprising both new and published experimental and natural data, to within ±16 % relative uncertainty. An uncertainty of 10 % relative for a typical Al^(tot) value of 1.5 apfu translates to an uncertainty in pressure estimate of 0.5 kbar, or 15 % relative. Thus the accuracy of the barometer expression is comparable to the precision with which near-solidus amphibole rim composition can be characterised.

Changes in magma storage conditions following caldera collapse at Okataina Volcanic Center, New Zealand

Abstract: Large silicic volcanic centers produce both small rhyolitic eruptions and catastrophic caldera-forming eruptions. Although changes in trace element and isotopic compositions within eruptions following caldera collapse have been observed at rhyolitic volcanic centers such as Yellowstone and Long Valley, much still remains unknown about the ways in which magma reservoirs are affected by caldera collapse. We present 238U–230Th age, trace element, and Hf isotopic data from individual zircon crystals from four eruptions from the Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand, in order to assess changes in trace element and isotopic composition of the reservoir following the 45-ka caldera-forming Rotoiti eruption. Our data indicate that (1) mixing of magmas derived from crustal melts and mantle melts takes place within the shallow reservoir; (2) while the basic processes of melt generation likely did not change significantly between pre- and post-caldera rhyolites, post-caldera zircons show increased trace element and isotopic heterogeneity that suggests a decrease in the degree of interconnectedness of the liquid within the reservoir following collapse; and (3) post-caldera eruptions from different vents indicate different storage times of the amalgamated melt prior to eruption. These data further suggest that the timescales needed to generate large volumes of eruptible melt may depend on the timescales needed to increase interconnectedness and achieve widespread homogenization throughout the reservoir.

Amphibole–melt trace element partitioning of fractionating calc-alkaline magmas in the lower crust: an experimental study

Abstract: Amphibole is one of the most important hydrous minerals of the middle and lower continental crust and plays a key role in the formation of intermediate to silica-rich magmas. This study reports a consistent set of amphibole trace element partition coefficients derived from fractional crystallization experiments at 0.7 GPa in a piston cylinder apparatus. Starting materials were doped with trace elements on the 20–40 ppm level and measured using laser ablation (LA)-ICP-MS. Amphibole is stable from 1010 to 730 °C and systematically changes its composition from pargasite to magnesiohornblende to cummingtonite, while coexisting liquids vary from andesite to dacite and rhyolite. Amphibole–liquid partition coefficients increase systematically with decreasing temperature and increasing SiO2 in the liquid. Potassium displays an inverse behavior and partitioning decreases with decreasing temperature. Rare earth element (REE) partition coefficients, assumed to occupy the M4 site within the amphibole structure, increase continuously up to one order of magnitude. The calculated lattice parameters, ideal cation radius (r 0) and Young’s modulus (E) remain nearly constant with decreasing temperature. The high-field strength elements Zr and Hf that occupy the M2 site of the amphibole structure reveal a fivefold increase in partition coefficients with decreasing temperature and constant lattice parameters r 0 and E. Partition coefficients correlate with edenite, tschermaks and cummingtonite exchange vectors indicating that the maximum partition coefficient (D 0) for an ideal cation radius increases with decreasing edenite component, while the latter decreases linearly with temperature. Regressing Amph/L D Ca against trace elements results in fair to excellent correlations (r 2 0.55–0.99) providing a predictive tool to implement the trace element partition coefficients in numerical geochemical modeling. Our data result in positive correlations between Amph/L D Nb/Ta and Amph/L D Ca, and Mg#. Spoon-shaped REE patterns and subchondritic Nb/Ta ratios in tonalitic to granodioritic plutonic rocks and andesitic to rhyolitic magmas directly constrained by measured trace element compositions of coexisting liquids are consistent with hornblende gabbro fractionation in the middle to lower crust. The systematic change of the measured trace element composition of fractionating calc-alkaline liquids indicates that hornblende gabbro formation in the middle to lower crust also exerts an important control on some commonly used trace element ratios such as Sr/Y, Sr/Ba or Nb/Zr.

The effect of pressure on sulphur speciation in mid- to deep-crustal arc magmas and implications for the formation of porphyry copper deposits

Abstract: Piston cylinder experiments are used to investigate the effect of oxygen fugacity (ƒO2) on sulphur speciation and phase relations in arc magmas at 0.5–1.5 GPa and 840–950 °C. The experimental starting composition is a synthetic trachyandesite containing 6.0 wt% H2O, 2880 ppm S, 1500 ppm Cl and 3800 ppm C. Redox conditions ranging from 1.7 log units below the Ni–NiO buffer (NNO − 1.7) to NNO + 4.7 were imposed by solid-state buffers: Co–CoO, Ni–NiO, Re–ReO2 and haematite–magnetite. All experiments are saturated with a COH fluid. Experiments produced crystal-bearing trachydacitic melts (SiO2 from 60 to 69 wt%) for which major and volatile element concentrations were measured. Experimental results demonstrate a powerful effect of oxidation state on phase relations. For example, plagioclase was stable above NNO, but absent at more reduced conditions. Suppression of plagioclase stability produces higher Al2O3 and CaO melts. The solid sulphur-bearing phases and sulphur speciation in the melt are strong functions of ƒO2, as expected, but also of pressure. At 0.5 GPa, the anhydrite stability field is intersected at NNO ≥ +2, but at 1.0 and 1.5 GPa, experiments at the same ƒO2 produce sulphides and the stability field of sulphate moves towards higher ƒO2 by ~1 log unit at 1.0 GPa and ~1.5 log units at 1.5 GPa. As a result, models that appeal to high oxidation state as an important control on the mobility of Cu (and other chalcophiles) during crustal differentiation must also consider the enhanced stability of sulphide in deep- to mid-crustal cumulates even for relatively oxidized (NNO + 2) magmas. Experimental glasses reproduce the commonly observed minimum in sulphur solubility between the S2− and S6+ stability fields. The solubility minimum is not related to the Fe content (Fe2+/Fe3+ or total) of the melt. Instead, we propose this minimum results from an unidentified, but relatively insoluble, S-species of intermediate oxidation state.

Experimental study of REE, Ba, Sr, Mo and W partitioning between carbonatitic melt and aqueous fluid with implications for rare metal mineralization

Abstract: Carbonatites host some unique ore deposits, especially rare earth elements (REE). Hydrothermal fluids have been proposed to play a significant role in the concentration and transport of REE and other rare metals in carbonatites, but experimental constraints on fluid–melt equilibria in carbonatitic systems are sparse. Here we present an experimental study of trace element (REE, Ba, Sr, Mo and W) partitioning between hydrous fluids and carbonatitic melts, bearing on potential hydrothermal activity associated with carbonatite ore-forming systems. The experiments were performed on mixtures of synthetic carbonate melts and aqueous fluids at 700–800 °C and 100–200 MPa using rapid-quench cold-seal pressure vessels and double-capsule assemblages with diamond traps for analyzing fluid precipitates in the outer capsule. Starting mixtures were composed of Ca, Mg and Na carbonates spiked with trace elements. Small amounts of F or Cl were added to some of the mixtures to study the effects of halogens on the element distribution. The results show that REE, Ba, Sr, Mo and W all preferentially partition into carbonatite melt and have fluid–melt distribution coefficients (D f/m) below unity. The REE partitioning is slightly dependent on the major element (Ca, Mg and Na) composition of the starting mixtures, and it is influenced by temperature, pressure, and the presence of halogens. The fluid–melt D values of individual REE vary from 0.02 to 0.15 with $$D_{\text{Lu}}^{{{{\text{f}} \mathord{\left/ {\vphantom {{\text{f}} {\text{m}}}} \right. \kern-0pt} {\text{m}}}}}$$ being larger than $$D_{\text{La}}^{{{{\text{f}} \mathord{\left/ {\vphantom {{\text{f}} {\text{m}}}} \right. \kern-0pt} {\text{m}}}}}$$ by a factor of 1.1–2. The halogens F and Cl have strong and opposite effects on the REE partitioning. Fluid–melt D REE are about three times higher in F-bearing compositions and ten times lower in Cl-bearing compositions than in halogen-free systems. $$D_{\text{W}}^{{{{\text{f}} \mathord{\left/ {\vphantom {{\text{f}} {\text{m}}}} \right. \kern-0pt} {\text{m}}}}}$$ and $$D_{\text{Mo}}^{{{{\text{f}} \mathord{\left/ {\vphantom {{\text{f}} {\text{m}}}} \right. \kern-0pt} {\text{m}}}}}$$ are the highest among the studied elements and vary between 0.6 and 0.7; $$D_{\text{Ba}}^{{{{\text{f}} \mathord{\left/ {\vphantom {{\text{f}} {\text{m}}}} \right. \kern-0pt} {\text{m}}}}}$$ is between 0.05 and 0.09, whereas $$D_{\text{Sr}}^{{{{\text{f}} \mathord{\left/ {\vphantom {{\text{f}} {\text{m}}}} \right. \kern-0pt} {\text{m}}}}}$$ is at about 0.01–0.02. The results imply that carbonatite-related REE deposits were probably formed by fractional crystallization of carbonatitic melts rather than from exsolved hydrothermal fluids. The same appears to be true for a carbonatite-related Mo deposit recently discovered in China.

Zircon saturation in silicate melts: a new and improved model for aluminous and alkaline melts

Abstract: The importance of zircon in geochemical and geochronological studies, and its presence not only in aluminous but also in alkaline rocks, prompted us to think about a new zircon saturation model that can be applied in a wide range of compositions. Therefore, we performed zircon crystallization experiments in a range of compositions and at high temperatures, extending the original zircon saturation model proposed by Watson and Harrison (Earth Planet Sci Lett 64:295–304, 1983) and Boehnke et al. (Chem Geol 351:324–334, 2013). We used our new data and the data from previous studies in peraluminous melts, to describe the solubility of zircon in alkaline and aluminous melts. To this effect, we devised a new compositional parameter called G $$ \left[ {\left( {3 \cdot {\text{Al}}_{2} {\text{O}}_{3} + {\text{SiO}}_{2} )/({\text{Na}}_{2} {\text{O}} + {\text{K}}_{2} {\text{O}} + {\text{CaO}} + {\text{MgO}} + {\text{FeO}}} \right)} \right] $$ (molar proportions), which enables to describe the zircon saturation behaviour in a wide range of rock compositions. Furthermore, we propose a new zircon saturation model, which depends basically on temperature and melt composition, given by (with 1σ errors): $$ \ln \left[ {\text{Zr}} \right] = \left( {4.29 \pm 0.34} \right) - \left( {1.35 \pm 0.10} \right) \cdot \ln G + \left( {0.0056 \pm 0.0002} \right) \cdot T\left( {^\circ C} \right) $$ where [Zr] is the Zr concentration of the melt in µg/g, G is the new parameter representing melt composition and T is the temperature in degrees Celsius. The advantages of the new model are its straightforward use, with the G parameter being calculated directly from the molar proportions converted from electron microprobe measurements, the temperature calculated given in degrees Celsius and its applicability in a wider range of rocks compositions. Our results confirm the high zircon solubility in peralkaline rocks and its dependence on composition and temperature. Our new model may be applied in all intermediate to felsic melts from peraluminous to peralkaline compositions.

Clinopyroxene in postshield Haleakala ankaramite: 1. Efficacy of thermobarometry

Abstract: Magma storage depth is a fundamental aspect of a volcano’s magmatic plumbing system that may be resolved using mineral-melt thermobarometry, assuming crystal growth occurs at near-equilibrium conditions. We acquire major and minor element compositional analyses of whole rock, groundmass separates, and clinopyroxene in ankaramite erupted ca. 214 ka at Haleakala volcano to evaluate the efficacy of thermobarometry. Using various thermometer and barometer combinations, we obtain values of crystallization pressure (60–1500 MPa) that are generally consistent with those of previous studies, but find that the models most successful at recovering the conditions of relevant equilibrium experiments yield values at the low end of this range (≤950 MPa). We use quantitative EPMA spot analyses to transform X-ray element intensity maps into metal oxide concentrations maps and to produce qualitative pressure maps of whole crystals. The spatial context provided by this procedure reveals two compositionally distinct domain types not evident in the spot analysis data set, with median Na2O contents differing by up to 26 % between domains. Na-rich domains represent putative crystallization pressures that are up to 365 MPa higher than Na-poor domains, within individual crystals. The presence of Na-rich domains associated with euhedral facets in contact with matrix is not consistent with concentric growth at near-equilibrium conditions of decreasing pressure, but rather co-crystallization of both domains under conditions of partial disequilibrium. Conservatively assuming that low-Na regions are less prone to kinetic partitioning, crystallization pressures for the Haleakala ankaramite correspond to crustal levels. We conclude that the reservoir supplying postshield eruptions at Haleakala has not deepened into the mantle, as was reported in a previous application of clinopyroxene thermobarometry to Haleakala’s postshield magma (Chatterjee et al. 2005).

The composition of nanogranitoids in migmatites overlying the Ronda peridotites (Betic Cordillera, S Spain): the anatectic history of a polymetamorphic basement

Abstract: The study of the composition of primary melts during anatexis of high-pressure granulitic migmatites is relevant to understand the generation and differentiation of continental crust. Peritectic minerals in migmatites can trap droplets of melt that forms via incongruent melting reactions during crustal anatexis. These melt inclusions commonly crystallize and form nanogranitoids upon slow cooling of the anatectic terrane. To obtain the primary compositions of crustal melts recorded in these nanogranitoids, including volatile concentrations and information on fluid regimes, they must be remelted and rehomogenized before analysis. A new occurrence of nanogranitoids was recently reported in garnets of mylonitic metapelitic gneisses (former high pressure granulitic migmatites) at the bottom of the prograde metamorphic sequence of Jubrique, located on top of the Ronda peridotite slab (Betic Cordillera, S Spain). Nanogranitoids within separated chips of cores and rims of large garnets from these migmatites were remelted at 15 kbar and 850, 825 or 800 °C and dry (without added H2O), during 24 h, using a piston cylinder apparatus. Although all experiments show glass (former melt) within melt inclusions, the extent of rehomogenization depends on the experimental temperature. Experiments at 850–825 °C show abundant disequilibrium microstructures, whereas those at 800 °C show a relatively high proportion of rehomogenized nanogranitoids, indicating that anatexis and entrapment of melt inclusions in these rocks likely occurred at pressures ≤1.5 GPa and temperatures close to 800 °C. Electron microprobe and NanoSIMS analyses show that experimental glasses are leucogranitoid and peraluminous, though define two distinct compositional groups. Type I melt inclusions correspond to K-rich, Ca- and H2O-poor leucogranitic melts, whereas type II melt inclusions represent K-poor, Ca- and H2O-rich granodioritic to tonalitic melts. Type I and II melt inclusions are found in most cases at the cores and rims of large garnets porphyroclasts, respectively. We tentatively interpret these two distinct melt compositions as suggesting that these former migmatites underwent two melting events under contrasting fluid regimes, possibly during two different orogenic periods. This study demonstrates the strong potential of melt inclusions studies in migmatites and granulites in order to unravel their anatectic history, particularly in strongly deformed rocks where most of the classical anatectic microstructures and macrostructures have been erased during deformation.

Experimental melting of phlogopite-peridotite in the garnet stability field

Abstract: Melting experiments have been performed at 3 GPa, between 1150 and 1450 °C, on a phlogopite-peridotite source in the garnet stability field. We succeeded to extract and determine the melt compositions of both phlogopite-bearing lherzolite and harzburgite from low to high degrees of melting (ϕ = 0.008–0.256). Accounting for the presence of small amounts of F in the mantle, we determined that phlogopite coexists with melt >150 °C above the solidus position (1150–1200 °C). Fluorine content of phlogopite continuously increases during partial melting from 0.2 to 0.9 wt% between 1000 and 1150 °C and 0.5 to 0.6 wt% between 1150 and 1300 °C at 1 and 3 GPa, respectively. The phlogopite continuous breakdown in the lherzolite follows the reaction: 0.59 phlogopite + 0.52 clinopyroxene + 0.18 garnet = 0.06 olivine + 0.23 orthopyroxene + 1.00 melt. In the phlogopite-harzburgite, the reaction is: 0.93 phlogopite + 0.46 garnet = 0.25 olivine + 0.14 orthopyroxene + 1.00 melt. Melts from phlogopite-peridotite sources at 3 GPa are silica-undersaturated and are foiditic to trachybasaltic in composition from very low (0.8 wt%) to high (25.6 wt%) degrees of melting. As observed at 1 GPa, the potassium content of primary mantle melts is buffered by the presence of phlogopite, but the buffering values are higher, from 6.0 to 8.0 wt% depending on the source fertility. We finally show that phlogopite garnet-peridotite melts are very close to the composition of the most primitive post-collisional lavas described worldwide.

A systematic evaluation of the Zr-in-rutile thermometer in ultra-high temperature (UHT) rocks

Abstract: The Zr-in-rutile geothermometer is potentially a widely applicable tool to estimate peak metamorphic temperatures in rocks from diverse geological settings. In order to evaluate its usefulness and reliability to record and preserve high temperatures in granulite facies rocks, rutile from UHT rocks was investigated to assess different mechanisms of Zr (re-)distribution following cooling from high temperature. Granulite facies paragneisses from the lowermost part of the Ivrea Zone, Italy, incorporated as thin sheets into the extensive basaltic body of the Mafic Complex were selected for this study. The results show that Zr-in-rutile thermometry, if properly applied, is well suited to identify and study UHT terranes as it preserves a record of temperatures up to 1190 °C, although the thermometer is susceptible to partial post-peak metamorphic resetting by Zr diffusion. Texturally homogeneous rutile grains preserve Zr concentrations corresponding to temperatures of prograde rutile growth. Diverse rutile textures and relationships between some rutile host grains and included or adjacent Zr-bearing phases bear testimony to varying mechanisms of partial redistribution and resetting of Zr in rutile during cooling and link Zr-in-rutile temperatures to different steps of the metamorphic evolution. Rutile grains that equilibrated their Zr concentrations at temperatures above 1070 °C (i.e. 1.1 wt% Zr) could not retain all Zr in the rutile structure during cooling and exsolved baddeleyite (ZrO2). By subsequent reaction of baddeleyite exsolution lamellae with SiO2, zircon needles formed before the system finally closed at 650–700 °C without significant net loss of Zr from the whole host rutile grain. By reintegration of zircon exsolution needles, peak metamorphic temperatures of up to 1190 °C are derived for the studied rocks, which demonstrates the suitability of this solution thermometer to record UHT conditions and also confirms the extraordinary geological setting of the lowermost part of the Ivrea Zone.

Sulfur isotope and trace element systematics of zoned pyrite crystals from the El Indio Au-Cu-Ag deposit, Chile

Abstract: We present a comparative study between early, massive pyrite preceding (Cu–Ag) sulfosalt mineralization in high-temperature feeder zones (‘early pyrite’) and late pyrite that formed during silicic alteration associated with Au deposition (‘late pyrite’) at the El Indio high-sulfidation Au–Ag–Cu deposit, Chile. We use coupled in situ sulfur isotope and trace element analyses to chronologically assess geochemical variations across growth zones in these pyrite crystals. Early pyrite that formed in high-temperature feeder zones shows intricate oscillatory zonation of Cu, with individual laminae containing up to 1.15 wt% Cu and trace Co, As, Bi, Ni, Zn, Se, Ag, Sb, Te, Au, Pb and Bi. Late pyrite formed after (Cu–Ag) sulfosalt mineralization. It contains up to 1.14 wt% As with trace Cu, Zn, Pb, V, Mn, Co, Ni, Ge, Se, Ag, Sb, Te, Pb and Bi, as well as colloform Cu-rich growth bands containing vugs toward the outer edges of some crystals. Plotting the trace element data in chronological order (i.e., from core to rim) revealed that Co and Ni were the only elements to consistently co-vary across growth zones. Other trace elements were coupled in specific growth zones, but did not consistently co-vary across any individual crystal. The δ34S of early pyrite crystals in high-temperature feeder zones range from −3.19 to 1.88 ‰ (±0.5 ‰), consistent with sublimation directly from a high-temperature magmatic vapor phase. Late pyrite crystals are distinctly more enriched in δ34S than early pyrite (δ34S = 0.05–4.77 ‰, ±0.5 ‰), as a consequence of deposition from a liquid phase at lower temperatures. It is unclear whether the late pyrite was deposited from a small volume of liquid condensate, or a larger volume of hydrothermal fluid. Both types of pyrite exhibit intracrystalline δ34S variation, with a range of up to 3.31 ‰ recorded in an early pyrite crystal and up to 4.48 ‰ in a late pyrite crystal. Variations in δ34Spyrite at El Indio did not correspond with changes in trace element geochemistry. The lack of correlation between trace elements and δ34S, as well as the abundance of microscale mineral inclusions and vugs in El Indio pyrite indicate that the trace element content of pyrite at El Indio is largely controlled by nanoscale, syn-depositional mineral inclusions. Co and Ni were the only elements partitioned within the crystal structure of pyrite. Cu-rich oscillatory zones in early pyrite likely formed by nanoscale inclusions of Cu-rich sulfosalts or chalcopyrite, evidence of deposition from a fluid cyclically saturated in ore metals. This process may be restricted to polymetallic high-sulfidation-like deposits.

Clinopyroxene in postshield Haleakala ankaramite: 2. Texture, compositional zoning and supersaturation in the magma

Abstract: We investigated the external morphologies and internal compositional zoning patterns of clinopyroxene phenocrysts in an ankaramite of Haleakala volcano (Hawaii) to constrain magma crystallization conditions in the volcano’s postshield stage. The phenocrysts are characterized by euhedral faceted morphologies and crystallographically coherent subcrystals. Quantitative EPMA and X-ray element mapping reveal two domains within the crystals: porous, Si–Mg–Ca–Cr-rich zones associated with the forms {100}, {010} and {110}, and nonporous, Al–Ti–Na-rich zones associated with the forms {−111}. The chemical variations, internal porosity and parallel subcrystals are consistent with nonconcentric crystal growth at varying degrees of supersaturation. We infer that initial growth occurred in a diffusion-limited regime to produce dendritic crystals; subsequent growth was markedly slower, with lesser supersaturation allowing dendrites to infill and produce polyhedral external morphologies. This sequence promoted the evolution of crystals from an hourglass shape with dominant {−111} forms, to sector-zoned euhedral crystals in which elements were partitioned according to: (Al + Ti + Na){−111} = (Si + Mg + Cr + Ca){110},{100},{010}. Infilling of dendritic crystals occurred to a greater extent on faster-growing sectors and was interrupted by the eruption, resulting in porosity of the slower-growing {hk0} sectors. Outermost Na-poor rims formed on all sectors due to slower growth rate under interface-limited conditions. Paradoxically, high levels of supersaturation producing large crystals of clinopyroxene (and olivine) are indicated in the volcano’s deep-seated reservoir and lower degrees of supersaturation characterize syn-eruptive crystal growth. The presence of vapor bubbles within the melt-filled crystal embayments and inclusions suggests rapid clinopyroxene growth caused volatile saturation and reservoir pressurization, leading to eruption of the ankaramite.

Dating prograde fluid pulses during subduction by in situ U–Pb and oxygen isotope analysis

Abstract: The Dora-Maira whiteschists derive from metasomatically altered granites that experienced ultrahigh-pressure metamorphism at ~750 °C and 40 kbar during the Alpine orogeny. In order to investigate the P–T–time–fluid evolution of the whiteschists, we obtained U–Pb ages from zircon and monazite and combined those with trace element composition and oxygen isotopes of the accessory minerals and coexisting garnet. Zircon cores are the only remnants of the granitic protolith and still preserve a Permian age, magmatic trace element compositions and δ18O of ~10 ‰. Thermodynamic modelling of Si-rich and Si-poor whiteschist compositions shows that there are two main fluid pulses during prograde subduction between 20 and 40 kbar. In Si-poor samples, the breakdown of chlorite to garnet + fluid occurs at ~22 kbar. A first zircon rim directly overgrowing the cores has inclusions of prograde phlogopite and HREE-enriched patterns indicating zircon growth at the onset of garnet formation. A second main fluid pulse is documented close to peak metamorphic conditions in both Si-rich and Si-poor whiteschist when talc + kyanite react to garnet + coesite + fluid. A second metamorphic overgrowth on zircon with HREE depletion was observed in the Si-poor whiteschists, whereas a single metamorphic overgrowth capturing phengite and talc inclusions was observed in the Si-rich whiteschists. Garnet rims, zircon rims and monazite are in chemical and isotopic equilibrium for oxygen, demonstrating that they all formed at peak metamorphism at 35 Ma as constrained by the age of monazite (34.7 ± 0.4 Ma) and zircon rims (35.1 ± 0.8 Ma). The prograde zircon rim in Si-poor whiteschists has an age that is within error indistinguishable from the age of peak metamorphic conditions, consistent with a minimum rate of subduction of 2 cm/year for the Dora-Maira unit. Oxygen isotope values for zircon rims, monazite and garnet are equal within error at 6.4 ± 0.4 ‰, which is in line with closed-system equilibrium fractionation during prograde to peak temperatures. The resulting equilibrium ∆18Ozircon-monazite at 700 ± 20 °C is 0.1 ± 0.7 ‰. The in situ oxygen isotope data argue against an externally derived input of fluids into the whiteschists. Instead, fluid-assisted zircon and monazite recrystallisation can be linked to internal dehydration reactions during prograde subduction. We propose that the major metasomatic event affecting the granite protolith was related to hydrothermal seafloor alteration post-dating Jurassic rifting, well before the onset of Alpine subduction.

Constraints on the magmatic evolution of the oceanic crust from plagiogranite intrusions in the Oman ophiolite

Abstract: We present major and trace element as well as Sr, Nd, and Hf isotope data on a suite of 87 plutonic rock samples from 27 felsic crustal intrusions in seven blocks of the Oman ophiolite. The rock compositions of the sample suite including associated more mafic rocks range from 48 to 79 wt% SiO2, i.e. from gabbros to tonalites. The samples are grouped into a Ti-rich and relatively light rare earth element (LREE)-enriched P1 group [(Ce/Yb)N > 0.7] resembling the early V1 lavas, and a Ti-poor and LREE-depleted P2 group [(Ce/Yb)N < 0.7] resembling the late-stage V2 lavas. Based on the geochemical differences and in agreement with previous structural and petrographic models, we define phase 1 (P1) and phase 2 (P2) plutonic rocks. Felsic magmas in both groups formed by extensive fractional crystallization of olivine, clinopyroxene, plagioclase, apatite, and Ti-magnetite from mafic melts. The incompatible element compositions of P1 rocks overlap with those from mid-ocean ridges but have higher Ba/Nb and Th/Nb trending towards the P2 rock compositions and indicating an influence of a subducting slab. The P2 rocks formed from a more depleted mantle source but show a more pronounced slab signature. These rocks also occur in the southern blocks (with the exception of the Tayin block) of the Oman ophiolite implying that the entire ophiolite formed above a subducting slab. Initial Nd and Hf isotope compositions suggest an Indian-MORB-type mantle source for the Oman ophiolite magmas. Isotope compositions and high Th/Nb in some P2 rocks indicate mixing of a melt from subducted sediment into this mantle.

Solving petrological problems through machine learning: the study case of tectonic discrimination using geochemical and isotopic data

Abstract: Machine-learning methods are evaluated to study the intriguing and debated topic of discrimination among different tectonic environments using geochemical and isotopic data. Volcanic rocks characterized by a whole geochemical signature of major elements (SiO2, TiO2, Al2O3, Fe2O3T, CaO, MgO, Na2O, K2O), selected trace elements (Sr, Ba, Rb, Zr, Nb, La, Ce, Nd, Hf, Sm, Gd, Y, Yb, Lu, Ta, Th) and isotopes (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, 87Sr/86Sr and 143Nd/144Nd) have been extracted from open-access and comprehensive petrological databases (i.e., PetDB and GEOROC). The obtained dataset has been analyzed using support vector machines, a set of supervised machine-learning methods, which are considered particularly powerful in classification problems. Results from the application of the machine-learning methods show that the combined use of major, trace elements and isotopes allows associating the geochemical composition of rocks to the relative tectonic setting with high classification scores (93 %, on average). The lowest scores are recorded from volcanic rocks deriving from back-arc basins (65 %). All the other tectonic settings display higher classification scores, with oceanic islands reaching values up to 99 %. Results of this study could have a significant impact in other petrological studies potentially opening new perspectives for petrologists and geochemists. Other examples of applications include the development of more robust geothermometers and geobarometers and the recognition of volcanic sources for tephra layers in tephro-chronological studies.

The Tynong pluton, its mafic synplutonic sheets and igneous microgranular enclaves: the nature of the mantle connection in I-type granitic magmas

Abstract: In the Lachlan Orogen of south-eastern Australia, the high-level, postorogenic, 368-Ma, I-type Tynong pluton contains granitic to granodioritic rocks that crystallised from a variety of mainly crustally derived magmas emplaced in the shallow crust, in an extensional regime. The isotopic characteristics of the main plutonic rocks are relatively unevolved (87Sr/86Sr t ~ 0.705–0.706 and eNd t ~ −0.4 to 0.6), suggesting source rocks not long separated from the mantle. We infer that arc mafic to intermediate rocks and associated immature greywackes formed the main crustal source rocks and that these are located in the largely unexposed Neoproterozoic–Cambrian Selwyn Block that forms the basement. As exposed near its southern margin, the pluton also contains minor, pillowed sheet-like intrusions of quartz dioritic rock that show mainly mingling structures with the enclosing granodiorites, as well as some hybrid pods and fairly abundant igneous microgranular enclaves that we infer to have been derived from the quartz dioritic sheets. Despite this evidence of direct mantle input into the Tynong magma system, the main granodioritic series do not appear to have been formed by magma mixing processes. Of any I-type granite in the region, the Tynong pluton has perhaps the most direct connection with mantle magmas. Nevertheless, the main mantle connection here is probably in the mantle-derived protolith for these crustal magmas and in the mantle thermal event that gave rise to melting of the deep crust in the Selwyn Block. This degree of mantle connectedness seems typical for I-type granitic rocks worldwide.

The evolution of calcite-bearing kimberlites by melt-rock reaction: evidence from polymineralic inclusions within clinopyroxene and garnet megacrysts from Lac de Gras kimberlites, Canada

Abstract: Megacrystic (>1 cm) clinopyroxene (Cr-diopside) and garnet (Cr-pyrope) xenocrysts within kimberlites from Lac de Gras (Northwest Territories, Canada) contain fully crystallized melt inclusions. These ‘polymineralic inclusions’ have previously been interpreted to form by necking down of melts at mantle depths. We present a detailed petrographical and geochemical investigation of polymineralic inclusions and their host crystals to better understand how they form and what they reveal about the evolution of kimberlite melt. Genetically, the megacrysts are mantle xenocrysts with peridotitic chemical signatures indicating an origin within the lithospheric mantle (for the Cr-diopsides studied here ~4.6 GPa, 1015 °C). Textural evidence for disequilibrium between the host crystals and their polymineralic inclusions (spongy rims in Cr-diopside, kelyphite in Cr-pyrope) is consistent with measured Sr isotopic disequilibrium. The preservation of disequilibrium establishes a temporal link to kimberlite eruption. In Cr-diopsides, polymineralic inclusions contain phlogopite, olivine, chromite, serpentine, and calcite. Abundant fluid inclusion trails surround the inclusions. In Cr-pyropes, the inclusions additionally contain Al-spinel, clinopyroxene, and dolomite. The major and trace element compositions of the inclusion phases are generally consistent with the early stages of kimberlite differentiation trends. Extensive chemical exchange between the host phases and the inclusions is indicated by enrichment of the inclusions in major components of the host crystals, such as Cr2O3 and Al2O3. This chemical evidence, along with phase equilibria constraints, supports the proposal that the inclusions within Cr-diopside record the decarbonation reaction: dolomitic melt + diopside → forsterite + calcite + CO2, yielding the observed inclusion mineralogy and producing associated (CO2-rich) fluid inclusions. Our study of polymineralic inclusions in megacrysts provides clear mineralogical and chemical evidence for an origin of kimberlite that involves the reaction of high-pressure dolomitic melt with diopside-bearing mantle assemblages producing a lower-pressure melt that crystallizes a calcite-dominated assemblage in the crust.

Orthopyroxene survival in deep carbonatite melts: implications for kimberlites

Abstract: Kimberlites are rare diamond-bearing volcanic rocks that originate as melts in the Earth’s mantle. The original composition of kimberlitic melt is poorly constrained because of mantle and crustal contamination, exsolution of volatiles during ascent, and pervasive alteration during and after emplacement. One recent model (Russell et al. in Nature 481(7381):352–356, 2012. doi: 10.1038/nature10740 ) proposes that kimberlite melts are initially carbonatitic and evolve to kimberlite during ascent through continuous assimilation of orthopyroxene and exsolution of CO2. In high-temperature, high-pressure experiments designed to test this model, assimilation of orthopyroxene commences between 2.5 and 3.5 GPa by a reaction in which orthopyroxene reacts with the melt to form olivine, clinopyroxene, and CO2. No assimilation occurs at 3.5 GPa and above. We propose that the clinopyroxene produced in this reaction can react with the melt at lower pressure in a second reaction that produces olivine, calcite, and CO2, which would explain the absence of clinopyroxene phenocrysts in kimberlites. These experiments do not confirm that assimilation of orthopyroxene for the entirety of kimberlite ascent takes place, but rather two reactions at lower pressures (<3.5 GPa) cause assimilation of orthopyroxene and then clinopyroxene, evolving carbonatitic melts to kimberlite and causing CO2 exsolution that drives rapid ascent.

How do olivines record magmatic events? Insights from major and trace element zoning

Abstract: Reconciling the diverse records of magmatic events preserved by multiple crystals and minerals in the same sample is often challenging. In the case of basaltic–andesites from Volcan Llaima (Chile), Mg zoning in olivine is always simpler than Ca zoning in plagioclase. A model that explains a number of chemical patterns is that Llaima magmas stall in the upper crust, where they undergo decompression crystallization and form crystal-mush bodies. Frequent magma inputs from deeper reservoirs provide the potential for remobilization and eruption. The records of multiple recharge events in Llaima plagioclase versus an apparent maximum of one such event in coexisting olivine are addressed by using trace element zoning in olivine phenocrysts. We have integrated elements that (1) respond to changes in magma composition due to recharge or mixing (Mg, Fe, Ni, Mn, ±Ca), with (2) elements that are incorporated during rapid, disequilibrium crystal growth (P, Ti, Sc, V, Al). A more complex history is obtained when these elements are evaluated considering their partition coefficients, diffusivities, and crystal growth rates. The olivine archive can then be reconciled with the plagioclase archive of magma reservoir processes. Olivine (and plagioclase) phenocrysts may experience up to three or more recharge events between nucleation and eruption. Diffusion modeling of major and trace element zoning in two dimensions using a new lattice Boltzmann model suggests that recharge events occur on the order of months to a couple of years prior to eruption, whereas crystal residence times are more likely to be on the order of a few years to decades.

Plutonic xenoliths from Martinique, Lesser Antilles: evidence for open system processes and reactive melt flow in island arc crust

Abstract: The Lesser Antilles Volcanic Arc is remarkable for the abundance and variety of erupted plutonic xenoliths. These samples provide a window into the deeper crust and record a more protracted crystallisation history than is observed from lavas alone. We present a detailed petrological and in situ geochemical study of xenoliths from Martinique in order to establish their petrogenesis, pre-eruptive storage conditions and their contribution to construction of the sub-volcanic arc crust. The lavas from Martinique are controlled by crystal–liquid differentiation. Amphibole is rarely present in the erupted lavas, but it is a very common component in plutonic xenoliths, allowing us to directly test the involvement of amphibole in the petrogenesis of arc magmas. The plutonic xenoliths provide both textural and geochemical evidence of open system processes and crystal ‘cargos’. All xenoliths are plagioclase-bearing, with variable proportions of olivine, spinel, clinopyroxene, orthopyroxene and amphibole, commonly with interstitial melt. In Martinique, the sequence of crystallisation varies in sample type and differs from other islands of the Lesser Antilles arc. The compositional offset between plagioclase (~An90) and olivine (~Fo75), suggests crystallisation under high water contents and low pressures from an already fractionated liquid. Texturally, amphibole is either equant (crystallising early in the sequence) or interstitial (crystallising late). Interstitial amphibole is enriched in Ba and LREE compared with early crystallised amphibole and does not follow typical fractionation trends. Modelling of melt compositions indicates that a water-rich, plagioclase-undersaturated reactive melt or fluid percolated through a crystal mush, accompanied by the breakdown of clinopyroxene, and the crystallisation of amphibole. Geothermobarometry estimates and comparisons with experimental studies imply the majority of xenoliths formed in the mid-crust. Martinique cumulate xenoliths are inferred to represent crystal mushes within an open system, through which melt can both percolate and be generated.

Site-specific hydrogen diffusion rates during clinopyroxene dehydration

Abstract: The rate of hydrogen diffusion in clinopyroxene is relevant to interpreting hydrogen (“water”) concentrations in xenoliths, phenocrysts, and clinopyroxene-hosted melt inclusions to provide insight into the deep-earth water cycle and volcanic explosivity. Here, we determine bulk and site-specific hydrogen diffusivities in two diopsides and an augite by heating initially homogeneous water-bearing samples in a 1-atm CO/CO2 gas-mixing furnace at 800–1000 °C and oxygen fugacity at the quartz–fayalite–magnetite buffer and observing H-loss profiles. The O–H stretching range between wavenumbers 3000 and 4000 cm−1 in FTIR spectra is resolved into 4–6 peaks, each of which is assumed to represent a distinct defect site for the hydrogen, to determine peak-specific diffusivities using our previously published whole-block method. For the diopside from the Kunlun Mts. in China, Arrhenius relations are reported for peaks at 3645, 3617, 3540, 3443, and 3355 cm−1 based on measurements at 816, 904, and 1000 °C. Bulk and site-specific diffusivities are determined for the same set of peaks at 904 °C for the second diopside (Jaipur). The augite (PMR-53) was a triangular thin slab, and hydrogen diffusivities were determined for bulk hydrogen and peaks at 3620, 3550, 3460, and 3355 cm−1 in the thickness direction at 800 °C. Bulk hydrogen diffusivity in the Jaipur diopside is consistent with previous work, and hydrogen diffusivity in augite PMR-53 is slightly lower than the fast direction diffusivities measured || [100] and [001]* in Jaipur diopside. Both diopsides show 1–2 orders of magnitude differences in the peaks-specific diffusivities, with the fastest diffusivities at 3450 cm−1 and the slowest at 3645 cm−1. However, the hydrogen diffusivities in Jaipur diopside are 2–4 orders of magnitude higher than those in Kunlun diopside for bulk hydrogen and all peaks. Thus, peak-specific differences cannot by themselves adequately explain the 5 orders of magnitude range in hydrogen diffusivities observed experimentally in different diopsides. The results are broadly consistent with a previously proposed increase in hydrogen diffusivity in diopside with Fe up to 0.6–0.8 a.p.f.u., although there may be an opposing relationship with Al(IV). The results of this study and others predict high water diffusivities in Fe-bearing mantle xenolith clinopyroxene, on the order of ~10−9 to 10−11 m2/s at 1000 °C. The common observation of hydrogen zonation in mantle xenolith olivine, but not in clinopyroxene implies that hydrogen diffusion is much faster in olivine than in pyroxene, which then requires the operation of the fastest diffusion mechanism quantified in olivine and diffusivities in clinopyroxene at the lower end of this 2 orders of magnitude range. Such high diffusivities strongly suggest that water in mantle xenoliths has at least partially equilibrated with the host magma, and that the diffusion profiles observed in mantle xenolith olivine reflect only the final stage of ascent after water begins to exsolve.

Element redistribution and mobility during upper crustal metamorphism of metasedimentary rocks: an example from the eastern Mount Lofty Ranges, South Australia

Abstract: We present a detailed study on element mobility during prograde metamorphism of metasedimentary rocks of the eastern Mt. Lofty Ranges, South Australia. Mineral and bulk rock compositions were monitored across a regional metamorphic gradient from ≈350–400 °C to migmatite grade (≈650–700 °C) at ≈0.3–0.5 GPa, where pervasive up-temperature fluid flow during metamorphism has been proposed previously. Major and most trace elements (including rare earth elements) are isochemical during metamorphism as they are effectively redistributed into newly formed major and/or accessory minerals. Monazite or allanite and xenotime control the whole rock concentration of rare earth elements (REEs), whereas apatite and titanite are minor REE hosts. The only non-volatile elements that are demonstrably mobilized by metamorphic fluids are Zn, Pb, Ag, Cs, Sb, Bi and As, whose concentrations decreased with increasing metamorphic grade. Depletion of Zn, Sb and Pb was progressive with increasing temperature in staurolite-absent psammopelites, with losses of ≈80 % of the original Zn and >80 % of the protolithic Sb and ≈50 % of the original Pb from the rocks from high-grade metamorphic zones. Pronounced depletion of As and Cs occurs at the greenschist/amphibolite facies boundary and the transition to migmatite grade, respectively, while Ag and Bi contents decrease between 500 and 550 °C where >50 % of the original Ag and Bi is lost. While for most elements, unmetamorphosed sedimentary sequences can be considered chemical equivalents of metasedimentary rocks occupying deeper crust levels, in some cases, such as the extensive flow of Cl-rich fluid documented here, metals such as Zn, Pb and Ag may be stripped and may serve as a metal source for orebody formation. The decrease of As, Bi and Sb contents during prograde metamorphism might be a more universal feature that is linked with sulphide phase transitions.

A chilled margin of komatiite and Mg-rich basaltic andesite in the western Bushveld Complex, South Africa

Abstract: A chill sequence at the base of the Lower Zone of the western Bushveld Complex at Union Section, South Africa, contains aphanitic Mg-rich basaltic andesite and spinifex-textured komatiite. The basaltic andesite has an average composition of 15.2 % MgO, 52.8 % SiO2, 1205 ppm Cr, and 361 ppm Ni, whereas the komatiite has 18.7 % MgO, 1515 ppm Cr, and 410 ppm Ni. Both rock types have very low concentrations of immobile incompatible elements (0.14–0.72 ppm Nb, 7–31 ppm Zr, 0.34–0.69 ppm Th, 0.23–0.27 wt% TiO2), but high PGE contents (19–23 ppb Pt, 15–16 ppb Pd) and Pt/Pd ratios (Pt/Pd 1.4). Strontium and S isotopes show enriched signatures relative to most other Lower Zone rocks. The rocks could represent a ~20 % partial melt of subcontinental lithospheric mantle. This would match the PGE content of the rocks. However, this model is inconsistent with the high SiO2, Fe, and Na2O contents and, in particular, the low K2O, Zr, Hf, Nb, Ta, Th, LREE, Rb, and Ba contents of the rocks. Alternatively, the chills could represent a komatiitic magma derived from the asthenosphere that underwent assimilation of the quartzitic floor accompanied by crystallization of olivine and chromite. This model is consistent with the lithophile elements and the elevated Sr and S isotopic signatures of the rocks. However, in order to account for the high Pt and Pd contents of the magma, the mantle must have been twice as rich in PGE as the current estimate for PUM, possibly due to a component of incompletely equilibrated late veneer.

Xenoliths in ultrapotassic volcanic rocks in the Lhasa block: direct evidence for crust-mantle mixing and metamorphism in the deep crust

Abstract: Felsic granulite xenoliths entrained in Miocene (~13 Ma) isotopically evolved, mantle-derived ultrapotassic volcanic (UPV) dykes in southern Tibet are refractory meta-granitoids with garnet and rutile in a near-anhydrous quartzo-feldspathic assemblage. High F–Ti (~4 wt.% TiO2 and ~3 wt.% F) phlogopite occurs as small inclusions in garnet, except for one sample where it occurs as flakes in a quartz-plagioclase-rich rock. High Si (~3.45) phengite is found as flakes in another xenolith sample. The refractory mineralogy suggests that the xenoliths underwent high-T and high-P metamorphism (800–850 °C, >15 kbar). Zircons show four main age groupings: 1.0–0.5 Ga, 50–45, 35–20, and 16–13 Ma. The oldest group is similar to common inherited zircons in the Gangdese belt, whereas the 50–45 Ma zircons match the crystallization age and juvenile character (eHf i +0.5 to +6.5) of Eocene Gangdese arc magmas. Together these two age groups indicate that a component of the xenolith was sourced from Gangdese arc rocks. The 35–20 Ma Miocene ages are derived from zircons with similar Hf–O isotopic composition as the Eocene Gangdese magmatic zircons. They also have similar steep REE curves, suggesting they grew in the absence of garnet. These zircons mark a period of early Miocene remelting of the Eocene Gangdese arc. By contrast, the youngest zircons (13.0 ± 4.9 Ma, MSWD = 1.3) are not zoned, have much lower HREE contents than the previous group, and flat HREE patterns. They also have distinctive high Th/U ratios, high zircon δ18O (+8.73–8.97 ‰) values, and extremely low eHf i (−12.7 to −9.4) values. Such evolved Hf–O isotopic compositions are similar to values of zircons from the UPV lavas that host the xenolith, and the flat REE pattern suggests that the 13 Ma zircons formed in equilibrium with garnet. Garnets from a strongly peraluminous meta-tonalite xenolith are weakly zoned or unzoned and fall into four groups, three of which are almandine-pyrope solid solutions and have low δ18O (+6 to 7.5 ‰), intermediate (δ18O +8.5 to 9.0 ‰), and high δ18O (+11.0 to 12.0 ‰). The fourth is almost pure andradite with δ18O 10–12 ‰. Both the low and intermediate δ18O groups show significant variation in Fe content, whereas the two high δ18O groups are compositionally homogeneous. We interpret these features to indicate that the low and intermediate δ18O group garnets grew in separate fractionating magmas that were brought together through magma mixing, whereas the high δ18O groups formed under high-grade metamorphic conditions accompanied by metasomatic exchange. The garnets record complex, open-system magmatic and metamorphic processes in a single rock. Based on these features, we consider that ultrapotassic magmas interacted with juvenile 35–20 Ma crust after they intruded in the deep crust (>50 km) at ~13 Ma to form hybridized Miocene granitoid magmas, leaving a refractory residue. The ~13 Ma zircons retain the original, evolved isotopic character of the ultrapotassic magmas, and the garnets record successive stages of the melting and mixing process, along with subsequent high-grade metamorphism followed by low-temperature alteration and brecciation during entrainment and ascent in a late UPV dyke. This is an excellent example of in situ crust–mantle hybridization in the deep Tibetan crust.

An experimental investigation of the stability of majoritic garnet in the Earth’s mantle and an improved majorite geobarometer

Abstract: The stability of the majorite component in garnet has been experimentally investigated at high pressure and high temperature, focusing on the effect of bulk composition and temperature. High-pressure experiments were performed in a multi-anvil apparatus, at pressures ranging from 6 to 14.5 GPa, and temperatures between 1400 and 1700 °C. Experiments were performed in a range of bulk compositions in the system SiO2–Al2O3–Cr2O3–CaO–MgO with varying Cr/(Cr + Al) ratios. The majorite content of garnet gradually increases with pressure, and the composition of the garnet, specifically the Cr/(Cr + Al) ratio, exerts a significant effect on the majorite substitution. We found no significant effect of temperature. We use the experimental results in combination with the literature data to derive two empirical geobarometers, which can be used to determine the equilibration pressure of natural majoritic garnets of peridotitic and eclogitic bulk compositions. The barometer for peridotitic compositions is $${\text{P}} = - 77.1 + 27.6 \times {\text{Si}} + 1.67 \times {\text{Cr}}$$ And the barometer for eclogitic compositions is $${\text{P}} = - 29.6 + 11.8 \times {\text{Si}} + 7.81 \times {\text{Na}} + 4.49 \times {\text{Ca}}.$$

Enriched continental flood basalts from depleted mantle melts: modeling the lithospheric contamination of Karoo lavas from Antarctica

Abstract: Continental flood basalts (CFBs) represent large-scale melting events in the Earth’s upper mantle and show considerable geochemical heterogeneity that is typically linked to substantial contribution from underlying continental lithosphere. Large-scale partial melting of the cold subcontinental lithospheric mantle and the large amounts of crustal contamination suggested by traditional binary mixing or assimilation-fractional crystallization models are difficult to reconcile with the thermal and compositional characteristics of continental lithosphere, however. The well-exposed CFBs of Vestfjella, western Dronning Maud Land, Antarctica, belong to the Jurassic Karoo large igneous province and provide a prime locality to quantify mass contributions of lithospheric and sublithospheric sources for two reasons: (1) recently discovered CFB dikes show isotopic characteristics akin to mid-ocean ridge basalts, and thus help to constrain asthenospheric parental melt compositions and (2) the well-exposed basaltic lavas have been divided into four different geochemical magma types that exhibit considerable trace element and radiogenic isotope heterogeneity (e.g., initial e Nd from −16 to +2 at 180 Ma). We simulate the geochemical evolution of Vestfjella CFBs using (1) energy-constrained assimilation-fractional crystallization equations that account for heating and partial melting of crustal wall rock and (2) assimilation-fractional crystallization equations for lithospheric mantle contamination by using highly alkaline continental volcanic rocks (i.e., partial melts of mantle lithosphere) as contaminants. Calculations indicate that the different magma types can be produced by just minor (1–15 wt%) contamination of asthenospheric parental magmas by melts from variable lithospheric reservoirs. Our models imply that the role of continental lithosphere as a CFB source component or contaminant may have been overestimated in many cases. Thus, CFBs may represent major juvenile crustal growth events rather than just recycling of old lithospheric materials.

First-principles calculations of equilibrium fractionation of O and Si isotopes in quartz, albite, anorthite, and zircon

Abstract: In this study, we used first-principles calculations based on density functional theory to investigate silicon and oxygen isotope fractionation factors among the most abundant major silicate minerals in granites, i.e., quartz and plagioclase (including albite and anorthite), and an important accessory mineral zircon. Combined with previous results of minerals commonly occurring in the crust and upper mantle (orthoenstatite, clinoenstatite, garnet, and olivine), our study reveals that the Si isotope fractionations in minerals are strongly correlated with SiO4 tetrahedron volume (or average Si–O bond length). The 30Si enrichment order follows the sequence of quartz > albite > anorthite > olivine ≈ zircon > enstatite > diopside, and the 18O enrichment follows the order of quartz > albite > anorthite > enstatite > zircon > olivine. Our calculation predicts that measurable fractionation of Si isotopes can occur among crustal silicate minerals during high-temperature geochemical processes. This work also allows us to evaluate Si isotope fractionation between minerals and silicate melts with variable compositions. Trajectory for δ30Si variation during fractional crystallization of silicate minerals was simulated with our calculated Si isotope fractionation factors between minerals and melts, suggesting the important roles of fractional crystallization to cause Si isotopic variations during magmatic differentiation. Our study also predicts that δ30Si data of ferroan anorthosites of the Moon can be explained by crystallization and aggregation of anorthite during lunar magma ocean processes. Finally, O and Si isotope fractionation factors between zircon and melts were estimated based on our calculation, which can be used to quantitatively account for O and Si isotope composition of zircons crystallized during magma differentiation.

Li zoning in zircon as a potential geospeedometer and peak temperature indicator

Abstract: Zircon Li concentrations and δ7Li values may potentially trace crustal recycling because continental and mantle-derived zircons yield distinct values. The usefulness of these differences may depend upon the retentivity of zircon to Li concentrations and isotopic ratios. Given the relatively high Li diffusivities measured by Cherniak and Watson (Contrib Mineral Petrol 160: 383–390, 2010), we sought to discover the scenarios under which Li mobility might be inhibited by charge-compensating cations. Toward this end, we conducted “in” diffusion experiments in which Li depth profiles of synthetic Lu-doped, P-doped, and undoped zircon were determined by nuclear reaction analysis. In separate experiments, Li was ion-implanted at depth within polished natural zircon slabs to form a Gaussian Li concentration profile. Diffusively relaxed concentration profiles were measured after heating the slabs to determine diffusivities. In all experiments, which ranged from 920 to 650 °C, calculated diffusivities are in agreement with a previously established Arrhenius relationship calibrated on trace-element-poor Mud Tank zircon. Our revised Arrhenius relationship that includes both datasets is: $$D_{\text{Li}} = 9.60 \times 10^{ - 7} \exp \left[ {\frac{{ - 278 \pm 8\;{\text{kJ}}\;{\text{mol}}^{ - 1} }}{\text{RT}}} \right]{\text{m}}^{ 2} \;{\text{s}}^{ - 1}$$ We also observed that synthetic sector-zoned zircon exhibits near-step-function Li concentration profiles across sectors that correlate with changes in the rare earth element (REE) and P concentrations. This allowed us to examine how Li diffusion might couple with REE diffusion in a manner different than that described above. In particular, re-heating these grains revealed significant Li migration, but no detectable migration of the rare earth elements. Thus, unlike most elements in zircon which are not mobile at the micrometer scale under most time–temperature paths in the crust, Li zoning, relaxation of zoning, or lack of zoning altogether could be used to reveal time–temperature information. Discrete ~10 μm concentration zones of Li within zircon may be partially preserved at 700 °C for tens to hundreds of years, and at 450 °C for millions of years. In this regard, Li zoning in zircon holds significant potential as a geospeedometer, and in some instances as a qualitative indicator of the maximum temperature experienced by the zircon.

Controls on the stability and composition of amphibole in the Earth’s mantle

Abstract: Presented here is a suite of new experiments aimed at quantifying the effects of pressure, temperature, bulk composition, and H2O content on the stability and composition of amphibole in the Earth’s mantle. Experiments have been performed from 2 to 4 GPa and 950 to 1100 °C on fertile and depleted mantle compositions. H2O contents of most experiments are 0.65 wt%. In the fertile mantle composition, pargasitic amphibole is stable up to ~3.8 GPa at 1000 °C, approximately 0.5 GPa higher than any previous study. The upper stability limit of amphibole in depleted mantle is 0.7 GPa and 40 °C lower than in fertile mantle. The addition of 3 wt% H2O to fertile mantle destabilizes amphibole by 0.5 GPa and 40 °C relative to the 0.65 wt% H2O experiments. Compared to existing experiments on amphibole stability, these experiments indicate that pargasitic amphibole may be stable in mantle lithosphere to almost 4 GPa (0.5 GPa higher (15 km deeper) than previously thought). The extremely strong destabilizing effect of H2O suggests that deeper portions of the strongly fluid-fluxed mantle wedge may be amphibole-free even at low temperatures near the slab–wedge interface. The molar alkali content of amphibole is shown to be a linear function (R 2 = 0.98) of pressure and temperature and is relatively insensitive to bulk compositional differences between fertile and depleted mantle. This relationship is used to produce an empirical thermobarometer for pargasite-bearing spinel and garnet lherzolites. Comparison to existing experimental data shows that this thermobarometer has predictive ability over the pressure range of 1–4 GPa. Comparisons with pressure–temperature estimates of garnet + amphibole peridotites further corroborate the applicability of this thermobarometer for natural samples. Pressure estimates are presented for four examples of metasomatized spinel peridotites otherwise lacking pressure information, and future avenues for refinement of the thermobarometer are discussed.

Fractional crystallization of Si-undersaturated alkaline magmas leading to unmixing of carbonatites on Brava Island (Cape Verde) and a general model of carbonatite genesis in alkaline magma suites

Abstract: The carbonatites of Brava Island, Cape Verde hot spot, allow to investigate whether they represent small mantle melt fractions or form through extreme fractionation and/or liquid immiscibility from CO2-bearing silicate magmas. The intrusive carbonatites on Brava Island are part of a strongly silica-undersaturated pyroxenite, ijolite, nephelinite, nepheline syenite, combeite–foiditite, carbonatite series. The major and trace element composition of this suite is reproduced by a model fractionating olivine, clinopyroxene, perovskite, biotite, apatite, titanite, sodalite and FeTi oxides, all present as phenocrysts in the rocks corresponding to their fractionation interval. Fractionation of ~90 wt% crystals reproduces the observed geochemical trend from the least evolved ultramafic dikes (bulk X Mg = 0.64) to syenitic compositions. The modelled fractional crystallization leads to alkali enrichment, driving the melt into the carbonatite–silicate miscibility gap. An initial CO2 content of 4000 ppm is sufficient to saturate in CO2 at the point where the rock record suggests continuing unmixing carbonatites from nephelinites to nepheline syenites after 61 wt% fractionation. Such immiscibility is also manifested in carbonatite and silicate domains on a hand-specimen scale. Furthermore, almost identical primary clinopyroxene, biotite and carbonate compositions from carbonatites and nephelinites to nepheline syenites substantiate their conjugate character and our unmixing model. The modelled carbonatite compositions correspond to the natural ones except for their much higher alkali contents. The alkali-poor character of the carbonatites on Brava and elsewhere is likely a consequence of the release of alkali-rich CO2 + H2O fluids during final crystallization, which cause fenitization in adjacent rocks. We propose a general model for carbonatite generation during alkaline magmatism, where the fractionation of heavily Si-undersaturated, alkaline parent melts results in alkali and CO2 enrichment in the evolving melt, ultimately leading to immiscibility between carbonatites and evolved Si-undersaturated alkaline melts. Early saturation in feldspathoids or feldspars would limit alkali enrichment preventing the formation of carbonatites. The complete and continuous fractionation line from almost primitive melts to syenitic compositions on Brava underlines the possibly important role of intrusives for hot spot volcanism.