Synthesis of monticellite–forsterite and merwinite–forsterite symplectites in the CaO–MgO–SiO<Subscript>2</Subscript> model system: influence of temperature and water content on microstructure evolution

Homogeneous single crystals of synthetic monticellite with the composition \({\text{Ca}}_{0.88}{\text{Mg}}_{1.12}{\text{SiO}}_4\) (Mtc I) were annealed in a piston-cylinder apparatus at temperatures between 1000 and \(1200\,^{\circ }\hbox {C}\), pressures of 1.0–1.4 GPa, for run durations from 10 min to 24 h and applying bulk water contents ranging from 0.0 to 0.5 wt% of the total charge. At these conditions, Mtc I breaks down to a fine-grained, symplectic intergrowth. Thereby, two types of symplectites are produced: a first symplectite type (Sy I) is represented by an aggregate of rod-shaped forsterite immersed in a matrix of monticellite with end-member composition (Mtc II), and a second symplectite type (Sy II) takes the form of a lamellar merwinite–forsterite intergrowth. Both symplectites may form simultaneously, where the formation of Sy I is favoured by the presence of water. Sy I is metastable with respect to Sy II and is successively replaced by the latter. For both symplectite types, the characteristic spacing of the symplectite phases is independent of run duration and is only weeakly influenced by the water content, but it is strongly temperature dependent. It varies from about 400 nm at \(1000\,^{\circ }\hbox {C}\) to 1200 nm at \(1100\,^{\circ }\hbox {C}\) in Sy I, and from 300 nm at \(1000\,^{\circ }\hbox {C}\) to 700 nm at \(1200\,^{\circ }\hbox {C}\) in Sy II. A thermodynamic analysis reveals that the temperature dependence of the characteristic spacing of the symplectite phases is due to a relatively high activation energy for chemical segregation by diffusion within the reaction front as compared to the activation energy for interface reactions at the reaction front. The temperature dependence of the characteristic lamellar spacing and the temperature-time dependence of overall reaction progress have potential for applications in geo-thermometry and geo-speedometry.     

Magma evolution beneath Bequia,Lesser Antilles,deduced from petrology of lavas and plutonic xenoliths

Extrusive and intrusive igneous rocks represent different parts of a magmatic system and ultimately provide complementary information about the processes operating beneath volcanoes. To shed light on such processes, we have examined and quantified the textures and mineral compositions of plutonic and cumulate xenoliths and lavas from Bequia, Lesser Antilles arc. Both suites contain assemblages of iddingsitized olivine, plagioclase, clinopyroxene and spinel with rare orthopyroxene and ilmenite. Mineral zoning is widespread, but more protracted in lavas than xenoliths. Plagioclase cores and olivine have high anorthite (An?≤?98) and low forsterite (Fo?≤?84) compositions respectively, implying crystallisation from a hydrous mafic melt that was already fractionated. Xenolith textures range from adcumulate to orthocumulate with variable mineral crystallisation sequences. Textural criteria are used to organize the xenoliths into six groups. Amphibole, notably absent from lavas, is a common feature of xenoliths, together with minor biotite and apatite. Bulk compositions of xenoliths deviate from the liquid line of descent of lavas supporting a cumulate origin with varying degrees of reactive infiltration by evolved hydrous melts, preserved as melt inclusions in xenolith crystals. Volatile saturation pressures in melt inclusions indicate cumulate crystallization over a 162–571 MPa pressure range under conditions of high dissolved water contents (up to 7.8 wt% H₂O), consistent with a variety of other thermobarometric estimates. Phase assemblages of xenoliths are consistent with published experimental data on volatile-saturated low-magnesium and high-alumina basalts and basaltic andesite from the Lesser Antilles at pressures of 200–1000 MPa, temperatures of 950–1050 °C and dissolved H₂O contents of 4–7 wt%. Once extracted from mid-crustal mushes, residual melts ascend to higher levels and undergo H₂O-saturated crystallization in shallow, pre-eruptive reservoirs to form phenocrysts and glomerocrysts. The absence of amphibole from lavas reflects instability at low pressures, whereas its abundance in xenoliths testifies to its importance in mid-crustal differentiation processes. A complex, vertically extensive (6 to at least 21 km depth) magmatic system is inferred beneath Bequia. Xenoliths represent fragments of the mush incorporated into ascending magmas. The widespread occurrence of evolved melts in the mush, but the absence of erupted evolved magmas, in contrast to islands in the northern Lesser Antilles, may reflect the relative immaturity of the Bequia magmatic system.     

Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS. Part 4: Plagioclase,orthopyroxene, clinopyroxene,glass geobarometer,and application to Mt. Ruapehu,New Zealand

A new phase equilibria geobarometer determines magmatic storage and crystallization conditions, including pressure, temperature, oxygen fugacity (\({f_{{{\text{o}}_2}}}\)), and the presence of a fluid phase for glass-bearing rocks containing the assemblage plagioclase?+?pyroxene(s). This newly developed geobarometer can better constrain crystallization conditions of shallow (<?500 MPa; <~?20 km), glass-bearing andesites to dacites. The geobarometer utilizes rhyolite-MELTS to determine crystallization conditions in natural pumice and scoria samples. The validity of the geobarometer is tested by comparing it to results from experiments. Uncertainties are assessed using Monte Carlo simulations. We apply the geobarometer to the plag?+?opx?+?cpx-bearing system of Mt. Ruapehu, in the southern Taupo Volcanic Zone, New Zealand. The samples from Mt. Ruapehu are tested from ~?5 to ~?400 MPa and from super-liquidus to 90% crystalline (~ 1200 to ~ 700 °C). Mt. Ruapehu serves as a methodological testing ground for the geobarometer, and results from our geobarometer agree with recent Mt. Ruapehu studies. Results show a distribution of crystallization pressures ranging from 50 to 150 MPa (~?2.0 to 5.9 km) for different eruptions, with modes of 110 MPa (~ 4.3 km) and 130 MPa (~ 5.1 km). These are consistent with field interpretations of different eruptive styles based on juvenile clast textures and previous knowledge of the magma plumbing system. Mt. Ruapehu magmas are fluid saturated, with \({f_{{{\text{o}}_2}}}\) of ΔQFM ~ + 1 (NNO).     

Crystal nucleation and growth produced by continuous decompression of Pinatubo magma

High-temperature decompression experiments demonstrate that crystal textures preserve a record of the style and rate of magmatic ascent. To reinforce this link, we performed a suite of isothermal decompression experiments using starting material from the climactic 1991 Pinatubo eruption. We decompressed experiments from 220 MPa to final, quench pressures of 75 or 30 MPa using continuous decompression rates of 100, 30, 10, 3, 1, and 0.3 MPa h^?1. Amphibole, clinopyroxene, and plagioclase crystallized during the experiments, with plagioclase microlites dominating the assemblage. Total microlite number densities range from 10^7.6±0.4 up to 10^8.2±0.2 cm^?3, with plagioclase accounting for up to 65% of the total number. Plagioclase microlite area increased systematically from 19?±?8 to 937?±?487 µm² with increasing experiment duration. Our textures provide time-integrated records of crystal kinetics. Average nucleation and areal growth rates of plagioclase are highest in the fastest decompressions (~?10^7.5 cm^?3 h^?1 and 10.1?±?4.1 µm² h^?1, respectively) and more than an order of magnitude lower in the slowest experiments (~?10^5.5 cm^?3 h^?1 and 0.8?±?0.2 µm² h^?1, respectively). Both nucleation and growth rates are highest at high degrees of disequilibrium. We find that peak supersaturation-dependent instantaneous rates are generally more than an order of magnitude faster than average rates. We use those instantaneous nucleation and growth rates to introduce an iterative model to evaluate the effects of different decompression rates, decompression paths (continuous, single-step or multistep), and the presence of phenocrysts on final crystallinity and microlite size distribution.     

Zoning and exsolution in alkali feldspars from Laacher See volcano (Western Germany): constraints on temperature history prior to eruption

Compositional zoning and exsolution patterns of alkali feldspars in carbonatite-bearing cognate syenites from the 6.3 km³ (D.R.E) phonolitic Laacher See Tephra (LST) deposit in western Germany (12.9 ka) are reported. These rocks represent the cooler outer portion and crystal-rich products of a cooling magma reservoir at upper crustal levels. Major and trace-element difference between cores and rims in sanidine crystals represent two generations of crystal growth separated by unmixing of a carbonate melt. Trace-element differences measured by LA–ICP–MS are in accordance with silicate–carbonate unmixing. Across the core–rim boundary, we extracted gray-scale profiles from multiple accumulations of back-scattered electron images. Gray scales directly represent K/Na ratios owing to low concentrations of Ba and Sr (<?30 ppm). Diffusion gradients are modeled to solve for temperature using known pre-eruptive U–Th zircon ages (0–20 ky) of each sample (Schmitt et al., J Petrol 51:1053–1085, 2010). Estimated temperatures range from 630 °C to 670 °C. For the exsolution boundaries, a diffusive homogenization model is constrained by the solvus temperature of ~ 712^_725 °C and gives short time scales of only 15–50 days. Based on our results, we present a model for the temperature–time history of these rocks. The model also constrains the thermal variation across the cooling crystal-rich carapace of the magma reservoir over 20 ka and suggests a thermal reactivation of cumulates, the cooling carapace, and probably the entire system only a few years prior to the explosive eruption of the remaining molten core of the phonolitic magma reservoir.     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

The Hissar–Alay and the Pamirs: Deep-Seated Structure,Geodynamic Model,and Experimental Evidence

The structural and geodynamic features of the Pamirs and the Hissar–Alay have been revealed based on geological and geophysical evidence supplemented by experimental data. It has been shown that both the Pamirs and the Hissar–Alay are geodynamic systems, the formation of which is related to interference of two geodynamic regimes: (i) global orogeny covering extensive territories of Eurasia and determining their similarity and (ii) regional regimes differing for the Pamirs and the Alay, which act independently within Central Asian and Apline–Himalayan mobile belts, respectively. The Pamirs do not act as an indentor during the formation of structure of the Hissar–Alay and areas to the north. It is stated that the Pamir–Alay segment of Asia is a reflection of the geodynamic countermotion setting (3D flow of mountain masses) of several distinct segments of the continental lithosphere, while the Pamirs are an intracontinental subduction domain at the surface, which represents a special tectonic–geodynamic type of structures.     

Composition,Age, and Origin of Cretaceous Granitic Magmatism on the Eastern Chukchi Peninsula

New geochronological and isotopic geochemical data are given, which make it possible to recognize two types of granitic rocks on the eastern Chukchi Peninsula. Early Cretaceous Tkachen and Dolina granitic plutons with zircon ages (U–Pb SIMS) of 119–122 and 131–136 Ma are related to the first type. They cut through Devonian–Lower Carboniferous basement rocks and are overlain by the Aptian–Albian Etelkuyum Formation. Basal units of the latter contain fragments of granitic rocks. Late Cretaceous Provideniya and Rumilet granitic plutons, which contain zircons with ages of 94 and 85 Ma (U–Pb SIMS), respectively, belong to the second type. They cut through volcanic–sedimentary rocks of the Etelkuyum and Leurvaam formations pertaining to the Okhotsk–Chukotka Volcanic Belt. In petrographic and geochemical features, the Early Cretaceous granitic rocks of the Tkachen Pluton are commensurable with I-type granites, while Late Cretaceous granite of the Rumilet Pluton is comparable to A₂-type granite. The Sr–Nd isotopic data provide evidence that from the Early Cretaceous Tkachen and Dolina plutons to the Late Cretaceous Provideniya and Rumilet plutons, the degree of crustal assimilation of suprasubduction mantle-derived melts increases up to partial melting of heterogeneous continental crust enriched in rubidium. An unconformity and various degrees of secondary alteration of volcanic–sedimentary rocks have been established in the Okhotsk–Chukotka Volcanic Belt, and this was apparently caused by transition of the tectonic setting from suprasubduction to a transform margin with local extension.     

Deformations and Manifestations of Degassing in the Sedimentary Cover of the Equatorial Segment of the West Atlantic: Implications for Lithospheric Geodynamics

Manifestations of fluids and deformations in the sedimentary cover, which are both factors of brightening (blanking anomalies) in seismoacoustic records, in the equatorial segment of the Atlantic coincide with the sublatitudinal zones of the activated passive parts of transform faults and with zones of lower gravity anomalies and higher values of remnant magnetization, which form as a result of serpentinization. The cause-and-effect sequence of intraplate phenomena includes: the contrasting geodynamic state → horizontal movements that form macrofractures → water supply to the upper mantle → serpentinization of rocks in the upper mantle → deformations associated with vertical uplift of basement and sedimentary cover blocks, coupled with fluid generation → and fluid accumulation in the sedimentary cover, accompanied by the formation of anomalies in seismoacoustic records. Based on the seismic data, we have identified imbricate-thrust deformations, diapir structures, stamp folds, and positive and negative flower structures, indicating the presence of strike-slip faults in the passive parts of transform faults. The general spatial distribution of deformation structures shows their concentration in cold mantle zones. Correlative comparison of the structural characteristics of deformations shows the direct relationship between the heights of structures and the development of serpentinization processes. As per the age of the basement, deformations range from 27–38 to 43–53 Ma; a quite thick sedimentary cover makes it possible to reveal them based on the characteristic types of seismoacoustic records. The formation of the Antilles arc ca. 10 Ma ago affected the equatorial segment of the Atlantic; it formed kink bands where lithospheric blocks underwent displacements with counterclockwise rotations, deformations related to compression and vertical uplift of crustal fragments, and local extension that favored degassing of endogenous fluids. Sublatitudinally oriented imbricate-thrust deformations with different vergences indicate irregularity and alternating strike-slip directions as blocks between fractures were laterally influenced.