Contributions to Mineralogy and Petrology最新文献

Tholeiitic basalts and picrites from the Deccan Traps were used to constrain the pressure and temperature conditions of mantle melting for their origin. Clinopyroxene thermobarometry indicates that all Deccan tholeiites crystallized at low pressures in the upper crust (< 6 kbar/1047–1221 °C). In comparison, the Deccan alkalic rocks crystallized at pressures up to ~ 12.7 kbar. Rare samples of the tholeiites plot on their low-pressure olivine-plagioclase-clinopyroxene (Ol-Pl-Cpx) cotectic boundaries or olivine control lines in phase diagrams. These samples represent unmodified magmatic liquids. Primary magmas of the basalts that plot on their cotectic boundaries were modeled through reverse fractionation by incrementally adding equilibrium Ol + Pl + Cpx, Ol + Pl and Ol ± spinel, until the liquid was multiply saturated with lherzolite at a high pressure. The high-Mg basalts are contaminated with continental crust. Hence, a crustal partial melt was simultaneously subtracted according to energy constraints at each reverse fractionation step for these samples. The results show that the high-Mg basalts are 41–53% fractionated and 1–6% contaminated, and the low-Mg basalts are 63–67% fractionated. Their primary magmas were last equilibrated with spinel lherzolite at 10–13 kbar/1289–1333 °C. A picrite and two very high-Mg basalts plot on their olivine control lines. So, their primary magmas were calculated by adding only equilibrium olivine. These samples are 9–25% fractionated, and their primary magmas were last equilibrated with garnet lherzolite at 25–36 kbar/1452–1531 °C. The estimated mantle potential temperatures are 1400–1500 °C for the Deccan tholeiites, consistent with their origin from a mantle plume.

Thermodynamic, experimental and field studies have suggested that organic compounds could be stable, and in some cases predominate over inorganic carbon species, within subduction zones under high pressure and high temperature (HP-HT) conditions. Beyond sedimentary organic matter of biological origin, solid organics can be inherited from hydrothermal circulation at mid-ocean ridges or abiotically formed by carbonate destabilization in the slab. To assess the fate of solid organic compounds during subduction, HP-HT experiments using piston-cylinder and multi-anvil presses have been performed at 700–1000 °C and 3–7 GPa. Different starting solids were tested, including either synthetic polycyclic aromatic hydrocarbons (PAHs) alone, with (i.e., 1-hydroxypyrene, 1-pyrenebutyric acid) or without (pyrene) oxygen-bearing functional groups, or a mixing of pyrene and antigorite. Our results show that increasing P–T conditions lead to the formation of hydrogenated (±oxygenated) graphitic carbon preserving a high level of structural disorder, far from graphite structure. We also observe the formation of aqueous fluids during experiments at 700 °C and 3 GPa with oxygen-functionalized PAHs, suggesting quick water release from solid organic compounds at HP-HT in subduction zones. Pyrene-antigorite experiments reveal various mineral assemblages depending on redox conditions. Oxidizing conditions favor the formation of magnesite-enstatite-coesite while reducing conditions promote forsterite-enstatite-graphitic carbon assemblages. Our results finally highlight the limited reactivity of solid organic compounds when exposed to aqueous fluids derived from serpentinite under reducing conditions which could facilitate the recycling of organic carbon into the deep mantle.

Understanding the primary controls on mineral deposit formation and size is essential for sourcing the metals required by our ever-growing economy. The tonnage of porphyry copper deposits ranges five orders of magnitude but the key mechanisms and processes that modulate the size of these deposits remain enigmatic. Here, we investigate the behemothian deposits of the Chuquicamata Intrusive Complex (CIC) in northern Chile employing high-precision U–Pb and Re–Os geochronology. We resolve a complex long-lived magmatic-hydrothermal activity that lasted over 3.3 Myr. High-precision zircon petrochronology data indicate two distinct porphyry emplacement episodes, separated by 0.5 Myr, with the younger generation closely tied to the main intervals of hydrothermal mineralization. High-precision Re–Os molybdenite dates reveal a prolonged hydrothermal mineralization interval (> 2.5 Myr) that progressively migrated southwards within the CIC and continued after the end of the (apparent) magmatic activity. We show that the rate of copper precipitation varies little in nature (0.025–0.10 Mt/kyr) and is independent of the size of the deposit. Consistent with evidence from smaller deposits, our findings provide unprecedented evidence that copper endowment in porphyry copper deposits positively correlates with the timescales of magmatic and hydrothermal activity. Supergiant to behemothian deposits require multi-million-year magmatic-hydrothermal activity, linking the largest porphyry copper systems to a simple metric – the duration of magmatic-hydrothermal activity.

Magmatism plays a key role in accommodating and localizing extension during continental breakup. However, how the crustal magmatic systems evolve at the continental-ocean transition is poorly understood. We address these questions by studying the evolution of the magmatic system in the rift of Central Afar (Ethiopia), currently marking the transition from continental rifting to oceanic spreading. We focus on the voluminous and widespread Upper Stratoid Series (2.6–1.1 Ma) and the following Central Afar Gulf Series (1.1–0.6 Ma), the latter corresponding to localization of volcanism in narrow magmatic segments. We carried out the first systematic study of major and trace element mineral chemistry for these two Series and integrated it with geothermobarometry estimates and geochemical modeling, to reconstruct the evolution of the magmatic system architecture during rift localization. The Upper Stratoid magmas evolved by fractional crystallization in a melt-rich, moderately zoned, middle-lower crustal (10–18 km) magmatic system, from where they rose directly to the surface. Polybaric plagioclase convection and dissolution of a plagioclase-rich crystal mush is recorded in the phenocryst texture and chemistry. The Central Afar Gulf magmas evolved at similar depth in a more complex and dynamic storage system, with magma rising and mixing through multiple, relatively small, crystal-rich and interconnected reservoirs. Our study documents the transition during the continental breakup, from an overall stable and melt-rich magmatic system feeding the voluminous and homogeneous Upper Stratoid eruptions to a more dynamic, interconnected and crystal-rich situation feeding small-volume eruption while the rift localizes.

The synthesis of the Al₂SiO₅ polymorphs kyanite, sillimanite and andalusite in a pure Al₂O₃–SiO₂–H₂O (ASH) system has long been known to be impeded. In order to decipher individual aspects of the reaction: corundum + SiO₂aq, which repeatedly fails to produce thermodynamically stable Al₂SiO₅, we conducted experiments within the stability fields of kyanite and sillimanite (500–800 ℃; 0.2–1 GPa) with the aim of forming reaction coronas on corundum. Results showed that metastable corundum + quartz assemblages form persistently in pure ASH, even in Al₂SiO₅ seeded experiments, despite the presence of catalyzing fluid and evidence of fast reaction kinetics. Coronas on corundum spontaneously formed when additional components (Na, K, N, and Mg) were added to the experiment. In a similar experiment with baddeleyite (ZrO₂) instead of corundum in silica saturated water, a zircon corona formed readily. This implies that nucleation and growth of Al₂SiO₅ is obstructed under conditions of Al and Si saturation in aqueous fluid, while both corundum and quartz saturated aqueous fluid are willing participants in other reactions towards stable corona formation. Instead of Al₂SiO₅ precipitation, an unexpected fluid-aided silica diffusion process into corundum was documented. The latter included the formation of nanometer wide hydrous silicate layers along the basal plane of the corundum host, which enhanced the silica diffusion rate drastically, leading to silica supersaturation in the host mineral, and ultimately to precipitation of quartz inside corundum. We conclude that the natural metastable assemblage of quartz and corundum is not necessarily the result of dry or fluid absent conditions, given that the aqueous fluid in experiments does not promote Al₂SiO₅ formation, but rather seems to support the formation and preservation of a metastable assemblage.

Mechanisms relating to growth and/or compositional modification of zircon occur at the atomic scale. For felsic igneous systems, processes responsible for growth patterns in zircon have previously remained elusive as the volume of material needed to analyze these compositional features using traditional in-situ methods is considerably larger than the typical sub-micron scale distribution of trace elements. To illuminate some of these driving forces, we characterize and quantify minor and trace element concentrations in igneous zircon grains by combining methods of cathodoluminescence (CL) imaging, electron microprobe microanalysis (EMPA) elemental maps for Hf, Y, Yb and U or Th, and atom probe tomography (APT). We focus on igneous zircon from the Chon Aike Silicic Large Igneous Province (Patagonia) that provide novel insights into (1) dissolution and re-crystallization during crustal anatexis, (2) crystallization to produce oscillatory zonation patterns that are typical of igneous zircons, and (3) the incorporation of trace element impurities (e.g., P, Be, and Al) at the nanoscale. Significantly, these APT volumes provide nanoscale sampling of boundaries between oscillatory growth zones in an igneous zircon to reveal compositional zoning of Y and, to a lesser extent P, which appear as high-angle, planar features. These concentration boundaries measured on the order of 10 to 12 nm are difficult to reconcile with proposed mechanisms for generating fine-scaled oscillations. Lastly, we fit diffusional profiles to measured Y concentrations to provide an estimate on the maximum timescales of zircon growth prior to eruption, as a function of the temperature at which diffusion occurred. When combined with known pressure-temperature-time paths for the magmatic system considered, these extremely short diffusion profiles that are resolvable by APT provide a powerful method to constrain timescales of crystal growth.

To develop new criteria to distinguish different crystal nucleation mechanisms in silicate melts, we performed crystallization experiments using a synthetic hydrous (2 wt% H₂O) trachybasalt and combined three-dimensional information from synchrotron X-ray computed microtomography with two-dimensional mapping of crystallographic orientation relationships (CORs) using electron backscatter diffraction. Crystallization experiments were performed at 400 MPa by cooling the melt from 1300 °C to resting temperatures of 1150 and 1100 °C and maintaining isothermal conditions for 30 min and 8 h. Three distinct titanomagnetite (Tmt) populations formed: (1) skeletal crystals, isolated or partially embedded in clinopyroxene (Cpx); (2) anhedral crystals, always attached to Cpx; (3) flattened needle-shaped crystals, embedded in Cpx. These morphologically different Tmt populations formed in response to one cooling event, with varying nucleation mechanisms and at different undercooling conditions. The clustered three-dimensional distribution of population 2 and 3 Tmt grains and the high proportion of Tmt-Cpx interfaces sharing CORs indicate that these Tmt grains heterogeneously nucleated on Cpx. The near-random three-dimensional distribution of (often isolated) population 1 Tmt grains, together with the low proportion of Tmt-Cpx interfaces sharing CORs, imply their isolated, possibly homogeneous nucleation, potentially followed by heterogeneous nucleation of Cpx on population 1 Tmt. Heterogeneous nucleation in slightly to moderately undercooled magmas should affect the sequence of crystallization as well as morphology and clustering of crystals, which may actively contribute to the variation of rheological parameters like viscosity. Finally, observed intra- and inter-sample variations in Tmt-Cpx COR frequencies indicate the potential for this parameter to record further petrological information.

The amount of water recycled during subduction is unclear. Water/Ce estimates in HIMU (high-²³⁸U/²⁰⁴Pb) basalts are variable, ranging from < 100 to > 250 in glasses and melt inclusions. Because clinopyroxene (cpx) is a common early liquidus phase and the cpx/melt partitioning of water is well constrained, cpx phenocrysts provide an additional constraint on magmatic water contents. We present water and trace element concentrations in HIMU-basalt-hosted cpx phenocrysts from the Austral Islands. Calculated melt [H₂O] (up to 4.3 wt.%) and H₂O/Ce ratios (22–825) are higher than in olivine-hosted inclusions, as are estimated equilibration pressures. Correlation between estimated melt [H₂O] and crystallization or entrapment pressure suggests significant water loss during magma ascent. Most ocean island basalts (OIBs) span a limited range in H₂O (~ 1–1.5 wt.%), and low (< 100) H₂O/Ce ratios are primarily observed in melts with unusually high [Ce] (up to 350 ppm). Additionally, [H₂O] and H₂O/Ce in some suites correlate with entrapment pressure despite having quench pressures high enough to prevent significant water loss from open- or closed-system degassing (< 100 MPa). Polybaric “sparging”, whereby low-P melts re-equilibrate with CO₂-rich fluids exsolved at higher pressure, may result in water loss at pressures less than CO₂ saturation. This may more accurately describe OIB degassing processes than open or closed system degassing. After correcting for degassing, primary Australs melts likely have H₂O/Ce of ~ 300–600. If applicable to OIB sources in general, this limits the total water budget of the mantle, including the mantle transition zone, to < 2.4 ocean masses.

Larnite (β-Ca₂SiO₄) has previously been reported as an inclusion in sub-lithospheric diamonds and is generally interpreted as a retrograde reaction product of calcium silicate perovskite. In this study, we review the controls on the stability of the Ca₂SiO₄ polymorphs and show that phosphorus is likely essential for the preservation of β-Ca₂SiO₄. We also report a detailed study of the solubility of water and its incorporation mechanisms in γ-Ca₂SiO₄ and phosphorus-doped β-Ca₂SiO₄ using FTIR spectroscopy on high-pressure experiments quenched from 4–9.5 GPa and 1000–1200 °C combined with ab initio calculations. The experimentally determined water solubilities are in the range of 107–178 ppm. Our FTIR spectra and ab initio calculations indicate that for phosphorus-free γ-Ca₂SiO₄ the incorporation mechanism involves protonated Si and Ca1 vacancies. For phosphorus-bearing β-Ca₂SiO₄, our preferred incorporation mechanism involves one Si⁴⁺ ion replaced by one P⁵⁺ ion with a single protonated Ca2 vacancy. The low water solubility observed here for larnite implies that if primary calcium silicate perovskite inclusions trap high water concentrations during diamond growth from a volatile-rich fluid, measurements of the concentration of water in larnite will not provide a useful record of the initial volatile concentration. Instead, water would be hosted in other retrograde reaction products, possibly including exsolved fluids.

Rhyolitic tuffs range widely in their crystal contents from nearly aphyric to crystal-rich, and their crystal cargoes inform concepts of upper crustal magma reservoirs. The Earthquake Flat pyroclastics (Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand) are 10 km³ of rhyolitic tuffs with abundant (~ 40 vol.%) plagioclase and quartz, minor biotite, hornblende, and orthopyroxene, and accessory Fe-Ti oxides, apatite, and zircon, set in high-silica rhyolitic glass. Major minerals form large, euhedral phenocrysts and abundant glomerocrysts with few disequilibrium textures excepting some faintly resorbed quartz. Plagioclase phenocrysts have thick rims of nearly constant composition near An₃₀, and hornblende is weakly zoned or unzoned. The abundant and texturally complex mineral assemblage contrasts with the nearby (~ 25 km), nearly synchronous, but more voluminous and crystal-moderate rhyolite tuffs from Rotoiti caldera. New H₂O-saturated phase-equilibria results on the erupted Earthquake Flat melt (glass) determine its co-saturation with the partial phenocryst assemblage of plagioclase, quartz, biotite, and Fe-Ti oxides at: 140 MPa, 755 ºC. These closely approximate the conditions of the pre-eruptive magma body assuming it was saturated with nearly pure H₂O and at an fO₂ of ~ Ni–NiO. Absence of hornblende and orthopyroxene from the synthesized assemblages may result from those minerals being in a peritectic reaction relation with melt to produce biotite, so they would not grow from the liquid used as starting material. Experimental results on Rotoiti rhyolite (Nicholls et al. 1992) show that the two bodies resided at similar pressures, temperatures, and fO₂s. Lower crystal abundance of the Rotoiti tuffs may result from slight compositional differences. We interpret that the Earthquake Flat pyroclastics were sourced from the crystal-rich periphery of a mushy reservoir system with the Rotoiti occupying a more melt-rich central location. Uncertain is whether this was a single intrusion zoned continuously in crystallinity, or discrete adjacent intrusions, but our results illustrate and quantify complexities of magma storage across relatively short distances.