Tetrahedral Plots of the Phase Relations for Basalts

The phase relations of quaternary systems are generally represented by projections onto ternary compositional planes. Such projections often obscure relationships that would only be evident in a three-dimensional tetrahedral plot. The tetrahedral plot requires that compositions of the minerals and melts be transformed into Cartesian coordinates. It is shown here how this transformation is carried out. The application is demonstrated by tetrahedral plots of experimental melt compositions of partially molten lherzolite. Furthermore, the plot can be used to evaluate whether or not a particular basaltic composition represents a primary melt. The methods are applicable to any four-component system.     

Pumpellyite in Low-grade Metamorphism

The regional metamorphism of the Kant? Mountains in Japan producedrocks of the following facies, with rising temperature: chloritefacies, pumpellyite-chlorite facies, glauco-phane-schist facies,and greenschist facies. This relationship is compared with theprogressive metamorphic zones in other regions where pumpellyitehas been found. Almost similar relations appear to hold in manymetamorphic terrains. Pumpellyites in glaucophanitic metamorphicterrains have, generally, low Fe'/R'R ratios. Physical andchemical conditions responsible for the formation of pumpellyiteare also discussed.     

Pre- and syn-eruptive degassing and crystallisation processes of the 2010 and 2006 eruptions of Merapi volcano,Indonesia

The 2010 eruption of Merapi (VEI 4) was the volcano’s largest since 1872. In contrast to the prolonged and effusive dome-forming eruptions typical of Merapi’s recent activity, the 2010 eruption began explosively, before a new dome was rapidly emplaced. This new dome was subsequently destroyed by explosions, generating pyroclastic density currents (PDCs), predominantly consisting of dark coloured, dense blocks of basaltic andesite dome lava. A shift towards open-vent conditions in the later stages of the eruption culminated in multiple explosions and the generation of PDCs with conspicuous grey scoria and white pumice clasts resulting from sub-plinian convective column collapse. This paper presents geochemical data for melt inclusions and their clinopyroxene hosts extracted from dense dome lava, grey scoria and white pumice generated during the peak of the 2010 eruption. These are compared with clinopyroxene-hosted melt inclusions from scoriaceous dome fragments from the prolonged dome-forming 2006 eruption, to elucidate any relationship between pre-eruptive degassing and crystallisation processes and eruptive style. Secondary ion mass spectrometry analysis of volatiles (H₂O, CO₂) and light lithophile elements (Li, B, Be) is augmented by electron microprobe analysis of major elements and volatiles (Cl, S, F) in melt inclusions and groundmass glass. Geobarometric analysis shows that the clinopyroxene phenocrysts crystallised at depths of up to 20 km, with the greatest calculated depths associated with phenocrysts from the white pumice. Based on their volatile contents, melt inclusions have re-equilibrated during shallower storage and/or ascent, at depths of ~0.6–9.7 km, where the Merapi magma system is interpreted to be highly interconnected and not formed of discrete magma reservoirs. Melt inclusions enriched in Li show uniform “buffered” Cl concentrations, indicating the presence of an exsolved brine phase. Boron-enriched inclusions also support the presence of a brine phase, which helped to stabilise B in the melt. Calculations based on S concentrations in melt inclusions and groundmass glass require a degassing melt volume of 0.36 km³ in order to produce the mass of SO₂ emitted during the 2010 eruption. This volume is approximately an order of magnitude higher than the erupted magma (DRE) volume. The transition between the contrasting eruptive styles in 2010 and 2006 is linked to changes in magmatic flux and changes in degassing style, with the explosive activity in 2010 driven by an influx of deep magma, which overwhelmed the shallower magma system and ascended rapidly, accompanied by closed-system degassing.     

A Raman spectroscopic study on the structural disorder of monazite–(Ce)

This study addresses whether Raman spectra can be used to estimate the degree of accumulated radiation damage in monazite-(Ce) samples whose chemical composition was previously determined. Our results indicate that the degree of disorder in monazite–(Ce), as observed from increasing Raman band broadening, generally depends on both the structural state (i.e., radiation damage) and the chemical composition (i.e., incorporation of non-formula elements). The chemical effects were studied on synthetic orthophosphates grown using the Li-Mo flux method, and non radiation-damaged analogues of the naturally radiation-damaged monazite–(Ce) samples, produced by dry annealing. We found that the “chemical” Raman-band broadening of natural monazite–(Ce) can be predicted by the empirical formula, $$ {\hbox{FWHM}} {\hbox{[c}}{{\hbox{m}}^{ - {1}}}{]} = {3}{.95} + {26}{.66} \times {\hbox{(Th}} + {\hbox{U}} + {\hbox{Ca}} + {\hbox{Pb)}} {\hbox{[apfu]}} $$ where, FWHM = full width at half maximum of the main Raman band of monazite–(Ce) (i.e., the symmetric PO₄ stretching near 970?cm^?1), and (Th+U+Ca+Pb) = sum of the four elements in apfu (atoms per formula unit). Provided the chemical composition of a natural monazite–(Ce) is known, this “chemical band broadening” can be used to estimate the degree of structural radiation damage from the observed FWHM of the ν₁(PO₄) band of that particular sample using Raman spectroscopy. Our annealing studies on a wide range of monazite–(Ce) reference materials and other monazite–(Ce) samples confirmed that this mineral virtually never becomes highly radiation damaged. Potential advantages and the practical use of the proposed method in the Earth sciences are discussed.     

Fluid inclusion studies of the Abawso gold prospect,near the Ashanti Belt,Ghana

The major Ghanaian lode gold deposits are preferentially aligned along the western and eastern contacts of the Kumasi Basin with the Ashanti and Sefwi Belts, respectively. The investigated area of the Abawso small-scale concession, covering the workings of the old Ettadom mine, is situated 3 km west of the lithological contact of the Birimian metavolcanic rocks of the Akropong Belt in the east with the Birimian metasedimentary rocks of the Kumasi Basin in the west. The rocks of the Abawso concession represent a steeply NW-dipping limb of a SE-verging anticline with an axis plunging to the SW. Quartz veining occurs predominantly in the form of en échelon dilatational veins along NNE–SSW-striking shear zones of a few metres width and shows evidence of brittle and ductile deformation. Also stockwork-style quartz veining occurs in the vicinity of the main shaft of the old Ettadom mine. Hydrothermal alteration includes sericitisation, sulphidation and locally carbonatisation. The auriferous quartz veins mainly follow the trend of brittle to ductile deformed quartz veins; however, some occur in stockwork. Fluid inclusion studies reveal a large number of H₂O inclusions along intragranular trails in auriferous quartz vein samples, as well as an overall dominance of H₂O and H₂O-CO₂ inclusions over CO₂ inclusions. Textural observations and physico-chemical fluid inclusion properties indicate post-entrapment modifications for all quartz vein samples due to grain boundary migration recrystallisation. This process is interpreted to be responsible for the generation of the CO₂ inclusions from a H₂O-CO₂ parent fluid. In comparison with mineralisation at the Ashanti and Prestea deposits, which are characterised by CO₂±N₂ inclusions, the observed inclusion assemblage may be due to a shallower crustal level of mineralisation, or different degrees and styles of recrystallisation, or a less pronounced development of laminated quartz veins due to comparably restricted pressure fluctuations. Furthermore, the microthermometric observations allow the reconstruction of a possible retrograde P-T path, depicting near-isothermal decompression in the P-T range of the brittle/ductile transition.Editorial handling: E. Frimmel     

Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue

Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO₂ at 830 °C, while chemical activation was achieved by using KOH and ZnCl₂ as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl₂, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl₂-oil shale sorbents.     

Cognate clinopyroxene from Paleogene mantle xenolith-bearing basanite lavas (East Serbia, SE Europe): the role of dissolution of mantle orthopyroxene

The study focuses on clinopyroxene from mantle xenolith-bearing East Serbian basanites and suggests that dissolution of mantle orthopyroxene played an important role in at least some stages of the crystallization of these alkaline magmas. Five compositional types of clinopyroxene are distinguished, some of them having different textural forms: megacrysts (Type-A), green/colourless-cored phenocrysts (Type-B), overgrowths and sieve-textured cores (Type-C), rims and matrix clinopyroxene (Type-D), and clinopyroxene from the reaction rims around orthopyroxene xenocrysts (Type-E). Type-A is high-Al diopside that probably crystallized at near-liquidus conditions either directly from the host basanite or from compositionally similar magmas in previous magmatic episodes. Type-B cores show high ^VIAl/^IVAl≥1 and low Mg# of mostly <75 and are interpreted as typical xenocrysts. Type-C, D and E are interpreted as typical cognate clinopyroxene. Type-D has Mg#<78, Al₂O₃?=?6–13?wt.%, TiO₂?=?1.5–4.5?wt.%, and Na₂O?=?0.4–0.8?wt.% and compositionally similar clinopyroxene is calculated by MELTS as a phase in equilibrium with the last 30?% of melt starting from the average host lava composition. Type-C has Mg#?=?72–89, Al₂O₃?=?4.5–9.5?wt.%, TiO₂?=?1–2.5?wt.%, Na₂O?=?0.35–1?wt.% and Cr₂O₃?=?0.1–1.5?wt.%. This clinopyroxene has some compositional similarities to Type-E occurring exclusively around mantle orthopyroxene. Cr/Al vs Al/Ti and Cr/Al vs Na/Ti plots revealed that Type-C clinopyroxene can crystallize from a mixture of the host basanite magma and 2–20?wt.% mantle orthopyroxene. Sieve-textured Type-C crystals show characteristics of experimentally produced skeletal clinopyroxene formed by orthopyroxene dissolution suggesting that crystallization of Type-C was both texturally and compositionally controlled by orthopyroxene breakdown. According to FeO/MgO^cpx/melt modelling the first clinopyroxene precipitating from the host basanite was Type-A (T?~?1250?°C, p?~?1.5?GPa). Dissolution of orthopyroxene produced decreasing FeO/MgO^melt and crystallization of Type-E and sieve-textured Type-C clinopyroxene (0.3–0.8?GPa and 1200–1050?°C). The melt composition gradually shifted towards higher FeO/MgO^melt ratios precipitating more evolved Type-C and Type-D approaching near-solidus conditions (<0.3?GPa; ~950?°C).     

Dauphiné twinning and texture memory in polycrystalline quartz. Part 3: texture memory during phase transformation

Samples of quartz-bearing rocks were heated above the α (trigonal)–β (hexagonal) phase transformation of quartz (625–950°C) to explore changes in preferred orientation patterns. Textures were measured both in situ and ex situ with neutron, synchrotron X-ray and electron backscatter diffraction. The trigonal–hexagonal phase transformation does not change the orientation of c- and a-axes, but positive and negative rhombs become equal in the hexagonal β-phase. In naturally deformed quartzites measured by neutron diffraction a perfect texture memory was observed, i.e. crystals returned to the same trigonal orientation they started from, with no evidence of twin boundaries. Samples measured by electron back-scattered diffraction on surfaces show considerable twinning and memory loss after the phase transformation. In experimentally deformed quartz rocks, where twinning was induced mechanically before heating, the orientation memory is lost. A mechanical model can explain the memory loss but so far it does not account for the persistence of the memory in quartzites. Stresses imposed by neighboring grains remain a likely cause of texture memory in this mineral with a very high elastic anisotropy. If stresses are imposed experimentally the internal stresses are released during the phase transformation and the material returns to its original state prior to deformation. Similarly, on surfaces there are no tractions and thus texture memory is partially lost.     

A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions

Diffusion of Al in synthetic forsterite was studied at atmospheric pressure from 1100 to 1500 °C in air along [100] with activities of SiO₂, MgO and Al₂O₃ (a_SiO2, a_MgO and a_Al2O3) buffered. At low a_SiO2, the buffer was forsterite + spinel + periclase (fo + sp + per) at all temperatures, while at high a_SiO2 and subsolidus conditions a variety of three-phase assemblages containing forsterite and two other phases from spinel, cordierite, protoenstatite or sapphirine were used at 1100–1350 °C. Experiments at high a_SiO2 and 1400 °C used forsterite + protoenstatite + melt (fo + en + melt), and at 1500 °C, fo + melt. The resulting diffusion profiles were analysed by LA–ICP–MS in scanning mode. Diffusion profiles in the high a_SiO2 experiments were generally several hundred microns in length, but diffusion at low a_SiO2 was three orders of magnitude slower than in high a_SiO2 experiments carried out at the same temperature, producing short profiles only a few microns in length and close to the spatial resolution of the analytical method. Interface concentrations of Al in the forsterite, obtained by extrapolating the diffusion profiles to the crystal/buffer interface, were only a fraction of those expected at equilibrium, and varied among the differing buffer assemblages according to (a_Al2O3)^1/2 and (a_SiO2)^3/4, pointing to the substitution of Al in forsterite by an octahedral-site, vacancy-coupled (OSVC) component with the stoichiometry Al _4/3 ³⁺ vac_2/3SiO₄, whereas the main substitution expected from previous equilibrium studies would be the coupled substitution of 2 Al for Mg + Si, giving the stoichiometry MgAl₂O₄. It is proposed that this latter substitution is not seen on the length scales of the present experiments because it requires replacement of Si by Al on tetrahedral sites, and is accordingly rate-limited by the slow diffusivity of Si. Instead, diffusion of Al by the OSVC mechanism is relatively fast, and at high a_SiO2, even faster than Fe–Mg interdiffusion.