Amphibole as an archivist of magmatic crystallization conditions: problems,potential, and implications for inferring magma storage prior to the paroxysmal 2010 eruption of Mount Merapi,Indonesia

Amphibole is widely employed to calculate crystallization temperature and pressure, although its potential as a geobarometer has always been debated. Recently, Ridolfi et al. (Contrib Mineral Petrol 160:45–66, 2010) and Ridolfi and Renzulli (Contrib Mineral Petrol 163:877–895, 2012) have presented calibrations for calculating temperature, pressure, fO₂, melt H₂O, and melt major and minor oxide composition from amphibole with a large compositional range. Using their calibrations, we have (i) calculated crystallization conditions for amphibole from eleven published experimental studies to examine the problems and the potential of the new calibrations; and (ii) calculated crystallization conditions for amphibole from basaltic–andesitic pyroclasts erupted during the paroxysmal 2010 eruption of Mount Merapi in Java, Indonesia, to infer pre-eruptive conditions. Our comparison of experimental and calculated values shows that calculated crystallization temperatures are reasonable estimates. Calculated fO₂ and melt SiO₂ content yields potentially useful estimates at moderately reduced to moderately oxidized conditions and intermediate to felsic melt compositions. However, calculated crystallization pressure and melt H₂O content are untenable estimates that largely reflect compositional variation in the crystallizing magmas and crystallization temperature and not the calculated parameters. Amphibole from Merapi’s pyroclasts yields calculated conditions of ~200–800 MPa, ~900–1,050 °C, ~NNO + 0.3–NNO + 1.1, ~3.7–7.2 wt% melt H₂O, and ~58–71 wt% melt SiO₂. We interpret the variations in calculated temperature, fO₂, and melt SiO₂ content as reasonable estimates, but conclude that the large calculated pressure variation for amphibole from Merapi and many other arc volcanoes is evidence for thorough mixing of mafic to felsic magmas and not necessarily evidence for crystallization over a large depth range. In contrast, bimodal pressure estimates obtained for other arc magmas reflect amphibole crystallization from mafic and more evolved magmas, respectively, and should not necessarily be taken as evidence for crystallization in two reservoirs at variable depth.     

Temporal evolution and compositional signatures of two supervolcanic systems recorded in zircons from Mangakino volcanic centre,New Zealand

Mangakino, the oldest rhyolitic caldera centre delineated in the Taupo Volcanic Zone of New Zealand, generated two very large (super-sized) ignimbrite eruptions, the 1.21 ± 0.04 Ma >500 km³ Ongatiti and ~1.0 Ma ~1,200 km³ Kidnappers events, the latter of which was followed after a short period of erosion by the ~200 km³ Rocky Hill eruption. We present U/Pb ages and trace-element analyses on zircons from pumice clasts from these three eruptions by Secondary Ion Mass Spectrometry (SIMS) using SHRIMP-RG instruments to illustrate the evolution of the respective magmatic systems. U–Pb age spectra from the Ongatiti imply growth of the magmatic system over ~250 kyr, with a peak of crystallisation around 1.32 Ma, ~100 kyr prior to eruption. The zircons are inferred to have then remained stable in a mush with little crystallisation and/or dissolution before later rejuvenation of the system at the lead-in to eruption. The paired Kidnappers and Rocky Hill eruptions have U–Pb zircon ages and geochemical signatures that suggest they were products of a common system grown over ~200 kyr. The Kidnappers and Rocky Hill samples show similar weakly bimodal age spectra, with peaks at 1.1 and 1.0 Ma, suggesting that an inherited antecrystic population was augmented by crystals grown at ages within uncertainty of the eruption age. In the Kidnappers, this younger age peak is dominantly seen in needle-shaped low U grains with aspect ratios of up to 18. In all three deposits, zircon cores show larger ranges and higher absolute concentrations of trace elements than zircon rims, consistent with zircon crystallisation from evolving melts undergoing crystal fractionation involving plagioclase and amphibole. Abundances and ratios of many trace elements frequently show variations between different sectors within single grains, even where there is no visible sector zoning in cathodoluminescence (CL) imaging. Substitution mechanisms, as reflected in the molar (Sc + Y + REE³⁺)/P ratio, differ in the same growth zone between the sides (along a-axis and b-axis: values approaching 1.0) and tips (c-axis: values between 1.5 and 5.0) of single crystals. These observations have implications for the use of zircons for tracking magmatic processes, particularly in techniques where CL zonation within crystals is not assessed and small analytical spot sizes cannot be achieved. These observations also limit applicability of the widely used Ti-in-zircon thermometer. The age spectra for the Ongatiti and Kidnappers/Rocky Hill samples indicate that both magmatic systems were newly built in the time-breaks after respective previous large eruptions from Mangakino. Trace element variations defining three-component mixing suggest that zircons, sourced from multiple melts, contributed to the population in each system.     

Building zoned ignimbrites by recycling silicic cumulates: insight from the 1,000 km<Superscript>3</Superscript> Carpenter Ridge Tuff,CO

The ~1,000 km³ Carpenter Ridge Tuff (CRT), erupted at 27.55 Ma during the mid-tertiary ignimbrite flare-up in the western USA, is among the largest known strongly zoned ash-flow tuffs. It consists primarily of densely welded crystal-poor rhyolite with a pronounced, highly evolved chemical signature (high Rb/Sr, low Ba, Zr, Eu), but thickly ponded intracaldera CRT is capped by a more crystal-rich, less silicic facies. In the outflow ignimbrite, this upper zone is defined mainly by densely welded crystal-rich juvenile clasts of trachydacite composition, with higher Fe–Ti oxide temperatures, and is characterized by extremely high Ba (to 7,500 ppm), Zr, Sr, and positive Eu anomalies. Rare mafic clasts (51–53 wt% SiO₂) with Ba contents to 4,000–5,000 ppm and positive Eu anomalies are also present. Much of the major and trace-element variations in the CRT juvenile clasts can be reproduced via in situ differentiation by interstitial melt extraction from a crystal-rich, upper-crustal mush zone, with the trachydacite, crystal-rich clasts representing the remobilized crystal cumulate left behind by the melt extraction process. Late recharge events, represented by the rare mafic clasts and high-Al amphiboles in some samples, mixed in with parts of the crystal cumulate and generated additional scatter in the whole-rock data. Recharge was important in thermally remobilizing the silicic crystal cumulate by partially melting the near-solidus phases, as supported by: (1) ubiquitous wormy/sieve textures and reverse zoning patterns in feldspars and biotites, (2) absence of quartz in this very silicic unit stored at depths of >4–5 km, and (3) heterogeneous melt compositions in the trachydacite fiamme and mafic clasts, particularly in Ba, indicating local enrichment of this element due mostly to sanidine and biotite melting. The injection of hot, juvenile magma into the upper-crustal cumulate also imparted the observed thermal gradient to the deposits and the mixing overprint that partly masks the in situ differentiation process. The CRT provides a particularly clear perspective on processes of in situ crystal-liquid separation into a lower crystal-rich zone and an upper eruptible cap, which appears common in incrementally built upper-crustal magma reservoirs of high-flux magmatic provinces.     

Vanadium and niobium behavior in rutile as a function of oxygen fugacity: evidence from natural samples

Vanadium occurs in multiple valence states in nature, whereas Nb is exclusively pentavalent. Both are compatible in rutile, but the relationship of V–Nb partitioning and dependence on oxygen fugacity (expressed as fO₂) has not yet been systematically investigated. We acquired trace-element concentrations on rutile grains (n = 86) in nine eclogitic samples from the Dabie-Sulu orogenic belt by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and combined them with published results in order to assess the direct and indirect effects of oxygen fugacity on the partitioning of V and Nb into rutile. A well-defined negative correlation between Nb (7–1,200 ppm) and V concentrations (50–3,200 ppm) was found, documenting a competitive relationship in the rutile crystal that does not appear to be controlled by bulk rock or mineral compositions. Based on the published relationship of ^RtD_V and V valence with ?QFM, we suggest that the priority order of V incorporation into rutile is V⁴⁺ > V³⁺ > V⁵⁺. The inferred Nb–V competitive relationship in rutile from the Dabie-Sulu orogenic belt could be explained by decreasing fO₂ due to dehydration reactions involving loss of oxidizing fluids during continental subduction: The increased proportion of V³⁺ (expressed as V³⁺/∑V) and attendant decrease in ^RtD_V is suggested to lead to an increase in rutile lattice sites available for Nb⁵⁺. A similar effect may be observed under more oxidizing conditions. When V⁵⁺/∑V increases, ^RtD_V shows a dramatic decline and Nb concentration increases considerably. This is possibly documented by rutile in highly metasomatized and oxidized MARID-type (MARID: mica–amphibole–rutile–ilmenite–diopside) mantle xenoliths from the Kaapvaal craton, which also show a negative V–Nb covariation. In addition, their Nb/Ta covaries with V concentrations: For V concentrations <1,250 ppm, Nb/Ta ranges between 35 and 45, whereas for V > 1,250 ppm, Nb/Ta is considerably lower (5–15). This relationship is mainly controlled by a change in Nb concentrations, suggesting that the indirect dependence of ^RtD_Nb on fO₂, which is not mirrored in ^RtD_Ta, can exert considerable influence on rutile Nb–Ta fractionation.     

Jurassic plume-origin ophiolites in Japan: accreted fragments of oceanic plateaus

The Mikabu and Sorachi–Yezo belts comprise Jurassic ophiolitic complexes in Japan, where abundant basaltic to picritic rocks occur as lavas and hyaloclastite blocks. In the studied northern Hamamatsu and Dodaira areas of the Mikabu belt, these rocks are divided into two geochemical types, namely depleted (D-) and enriched (E-) types. In addition, highly enriched (HE-) type has been reported from other areas in literature. The D-type picrites contain highly magnesian relic olivine phenocrysts up to Fo_93.5, and their Fo–NiO trend indicates fractional crystallization from a high-MgO primary magma. The MgO content is calculated as high as 25 wt%, indicating mantle melting at unusually high potential temperature (T _p) up to 1,650 °C. The E-type rocks represent the enrichment in Fe and LREE and the depletion in Mg, Al and HREE relative to the D-type rocks. These chemical characteristics are in good accordance with those of melts from garnet pyroxenite melting. Volcanics in the Sorachi–Yezo belts can be divided into the same types as the Mikabu belt, and the D-type picrites with magnesian olivines also show lines of evidence for production from high T _p mantle. Evidence for the high T _p mantle and geochemical similarities with high-Mg picrites and komatiites from oceanic and continental large igneous provinces (LIPs) indicate that the Mikabu and Sorachi–Yezo belts are accreted oceanic LIPs that were formed from hot large mantle plumes in the Late Jurassic Pacific Ocean. The E- and D-type rocks were formed as magmas generated by garnet pyroxenite melting at an early stage of LIP magmatism and by depleted peridotite melting at the later stage, respectively. The Mikabu belt characteristically bears abundant ultramafic cumulates, which could have been formed by crystal accumulation from a primary magma generated from Fe-rich peridotite mantle source, and the HE-type magma were produced by low degrees partial melting of garnet pyroxenite source. They should have been formed later and in lower temperatures than the E- and D-type rocks. The Mikabu and Sorachi Plateaus were formed in a low-latitude region of the Late Jurassic Pacific Ocean possibly near a subduction zone, partially experienced high P/T metamorphism during subduction, and then uplifted in association with (or without, in case of Mikabu) the supra-subduction zone ophiolite. The Mikabu and Sorachi Plateaus may be the Late Jurassic oceanic LIPs that could have been formed in brotherhood with the Shatsky Rise.     

Emplacement ages and sources of kimberlites and related rocks in southern Africa: U–Pb ages and Sr–Nd isotopes of groundmass perovskite

Groundmass perovskite has been dated by LA-ICPMS in 135 kimberlites and related rocks from 110 localities across southern Africa. Sr and/or Nd isotopes have been analysed by LA-MC-ICPMS in a subset of these and integrated with published data. The age distribution shows peaks at 1,600–1,800, 1,000–1,200, 500–800 and 50–130 Ma. The major “bloom” of Group I kimberlites at ca 90 ± 10 Ma was preceded by a slow build-up in magmatic activity from ca 180 Ma. The main pulse of Group II kimberlites at 120–130 Ma was a distinct episode within this build-up. Comparison of the isotopic data with seismic tomography images suggests that metasomatized subcontinental lithospheric mantle (SCLM) with very low ε _Nd and high ⁸⁷Sr/⁸⁶Sr, (the isotopic signature of Group II kimberlites) was focused in low-Vs zones along translithospheric structures. Such metasomatized zones existed as early as 1,800 Ma, but were only sporadically tapped until the magmatic build-up began at ca 180 Ma, and contributed little to the kimberlitic magmas after ca 110 Ma. We suggest that these metasomatized volumes resided in the deep SCLM and that their low-melting point components were “burned off” by rising temperatures, presumably during an asthenospheric upwelling that led to SCLM thinning and a rise in the ambient geotherm between 120 and 90 Ma. The younger Group I kimberlites therefore rarely interacted with such SCLM, but had improved access to shallower volumes of differently metasomatized, ancient SCLM with low ⁸⁷Sr/⁸⁶Sr and intermediate ε _Nd (0–5). The kimberlite compositions therefore reflect the evolution of the SCLM of southern Africa, with metasomatic-enrichment events from as early as 1.8 Ga, through a major thermal and compositional change at ca 110 Ma, and the major kimberlite “bloom” around 90 Ma.     

An Analytical Solution for Mechanical Responses Induced by Temperature and Air Pressure in a Lined Rock Cavern for Underground Compressed Air Energy Storage

Mechanical responses induced by temperature and air pressure significantly affect the stability and durability of underground compressed air energy storage (CAES) in a lined rock cavern. An analytical solution for evaluating such responses is, thus, proposed in this paper. The lined cavern of interest consists of three layers, namely, a sealing layer, a concrete lining and the host rock. Governing equations for cavern temperature and air pressure, which involve heat transfer between the air and surrounding layers, are established first. Then, Laplace transform and superposition principle are applied to obtain the temperature around the lined cavern and the air pressure during the operational period. Afterwards, a thermo-elastic axisymmetrical model is used to analytically determine the stress and displacement variations induced by temperature and air pressure. The developments of temperature, displacement and stress during a typical operational cycle are discussed on the basis of the proposed approach. The approach is subsequently verified with a coupled compressed air and thermo-mechanical numerical simulation and by a previous study on temperature. Finally, the influence of temperature on total stress and displacement and the impact of the heat transfer coefficient are discussed. This paper shows that the temperature sharply fluctuates only on the sealing layer and the concrete lining. The resulting tensile hoop stresses on the sealing layer and concrete lining are considerably large in comparison with the initial air pressure. Moreover, temperature has a non-negligible effect on the lined cavern for underground compressed air storage. Meanwhile, temperature has a greater effect on hoop and longitudinal stress than on radial stress and displacement. In addition, the heat transfer coefficient affects the cavern stress to a higher degree than the displacement.     

Spalling Experiments on Large Hard Rock Specimens

Specimens of coarse-grained Äspö diorite were axially compressed to observe stress-induced spalling. The specimens had a novel design characterized by two manufactured large radius notches on opposite sides. The tangential stress occurring in the notches aimed to represent the tangential loading around a circular opening. Fracture stages were monitored by acoustic emission measurements. Rock chips were formed similar to those found in situ, which indicates a similar fracture process. Slabs were cut out from the specimens and impregnated using a fluorescent material to visualize the cracks. The cracks were subsequently examined by the naked eye and by means of microscopy images, from which fracture paths could be identified and related to different minerals and their crystallographic orientations. The microscopy analyses showed how the stress field and the microstructure interact. Parallel cracks were formed 2–4 mm below the surface, sub-parallel to the direction of the maximum principal stress. The crack initiation, the roles of minerals such as feldspar, biotite and quartz and their grain boundaries and crystallographic directions are thoroughly studied and discussed in this paper. Scale effects, which relate to the stress gradient and microstructure, are discussed.     

Strenulagus (Mammalia: Lagomorpha) from the Middle Eocene Irdin Manha Formation of the Erlian Basin, Nei Mongol, China

New material of Strenulagus solaris, a stem lagomorph, from the lower part of the Middle Eocene Irdin Manha Formation at the Irdin Manha and Huheboerhe localities, Erlian Basin, Nei Mongol, China includes remains of isolated cheek teeth, fragmentary upper incisors(d I2) and postcranial elements, reported from the species for the first time. The tarsal bones display advanced features, such as a wide calcaneofibular articulation surface and, along with an increase in hypsodonty, the new data document the early stage of lagomorph evolution in the Middle Eocene of the Erlian Basin. This finding is stratigraphically well constrained and probably predates that of the type material of S. solaris from the Khaychin Formation, Bugin-Tsav Basin, Mongolia.     

Geostatistics as a groundwater exploration planning tool: case of a brackish-saline aquifer

This paper discusses a geostatistical approach to model a groundwater aquifer in 3-D. The study aims at utilizing geostatistics as a tool for characterizing zones of better-water quality in a brackish-saline aquifer. In particular, the geostatistical model was constructed to characterize the aquifer’s salinity, represented by total dissolved solids (TDS), using logs of porosity and resistivity. Quality-checked estimated TDS vertical profiles were employed to construct and model horizontal and vertical semivariograms. Parameters of semivariogram models were used to develop both the kriging plan and the generated model. Results of this modeling process are shown in the form of horizontal salinity distribution maps. The aquifer was sliced into 20 layers, each 20 m thick, to represent its overall thickness. Salinity layers maps reflect vertical stratification of TDS concentrations in the aquifer and show that water quality deteriorates with depth and toward the northern part of the aquifer. Relatively better-quality water (TDS ≤10,000 mg/l) can be found at depths between 100 and 250 m below the aquifer’s top in both eastern and southeastern parts. Water in the same interval to the western and southwestern parts reflects the presence of higher TDS concentration. From a planning point of view, it is more feasible to target the eastern part of the aquifer for pumping and desalination purposes. In addition, the generated model could be utilized as an initial condition for flow simulation.