Investigation of the photoluminescence properties of Urfa stone powder doped with chromium oxide

In this study, the structural properties of Urfa stone (US) doped with chromium oxide (Cr₂O₃) were investigated using X-ray diffraction (XRD) and FT-IR spectroscopy. The photoluminescence properties of US doped with varying amounts of Cr₂O₃ (5, 10, 20, 30, and 40%) were also investigated. US powder was obtained via grinding with an agate mortar, and Cr₂O₃ was then added as a dopant to the US powder. The samples were sintered at 1000 °C for 1 h. The XRD results of the US powder doped with Cr₂O₃ via mechanical alloying showed the presence of some crystalline phases: calcite (CaCO₃) and eskolate (Cr₂O₃). Furthermore, it was found that calcium oxide (CaO) and tongbaite (Cr₃C₂) were also present in the sintered samples. The photoluminescence analysis results indicated that the emission and excitation bands of the US-Cr complex shifted to longer and shorter wavelengths in the solid state (non-aqueous media), respectively.     

Effect of fuel molecules on properties and activity of KOH/calcium aluminate nanocatalyst for biodiesel production

New technologies such as microwaves have gained a large deal of attention from scientists and industries who sought increased rate of production processes. In this study, microwave irradiation was utilized to produce a novel KOH/Ca₁₂Al₁₄O₃₃ nanocatalyst used for biodiesel production. As support, calcium aluminate was prepared by microwave combustion method using different fuels including urea, glycine, sorbitol, and citric acid. The samples were then impregnated by KOH to improve their catalytic activities for microwave-enhanced transesterification of canola oil for biodiesel production. Results of XRD, BET, FTIR, TG, EDX, and FE-SEM analyses showed differences in physicochemical properties of the samples when using different fuels with different flame characteristics and combustion temperatures. Only the urea-fueled sample showed the crystalline structure of monocalcium aluminate (CaAl₂O₄), with the other samples exhibiting amorphous structure of CaO–Al₂O₃. However, all samples, except for that prepared by citric acid, transformed to crystalline structure of Ca₁₂Al₁₄O₃₃ by calcination during KOH impregnation. Among the samples, the KOH/Ca₁₂Al₁₄O₃₃ nanocatalyst prepared by sorbitol showed the highest activity in microwave-enhanced biodiesel production because of its large surface area, pore size, and basicity, converting 93.4% of canola oil to biodiesel at a methanol-to-oil molar ratio of 18, catalyst concentration of 4 wt%, and microwave output power of 450 W in 60 min of reaction time. Moreover, the sample showed well-distributed particle sizes without any agglomeration, so that it could easily maintain its level of activity for several rounds of use.     

Mineralogical and geochemical characteristics of coal ash from the Northwest Thrace region,Turkey: a case study

The first combined mineralogical and geochemical investigation of coal ashes from the Northwest Thrace Coal Basin, Turkey, was performed as a case study. The coal ash samples were obtained at 525 °C (group I), 750 °C (group II), and 1000 °C (group III) ashing temperatures from coal samples from the basin and were studied in terms of their mineralogical and geochemical composition using XRD and ICP-MS methods. The determination of the mineralogical composition was done for all of the groups; the geochemical analysis was carried out only for group II. In accordance with the high SiO₂, Fe₂O₃, CaO, and SO₃ content of the ash, quartz (SiO₂), hematite (Fe₂O₃), and anhydrite (CaSO₄) are the major crystalline phases for all of the ash groups. The other minerals are muscovite, thenardite, tridymite, calcite, wollastonite, anorthite, cristobalite, gibbsite, ternesite, mullite, nahcolite, and nacrite. High-temperature phases such as mullite, wollastonite, and anorthite were observed at 750 and 1000 °C. According to the (Fe₂O₃ + CaO + MgO+ K₂O+ Na₂O)/(SiO₂ + Al₂O₃+ TiO₂) ratios varying from 0.19 to 5.65, the ashes are highly prone to slagging. Compared to average values of low-rank coal ashes, the contents of V, Cr, Co, Ni, Zn, As, Rb, Sr, Mo, Cs, W, and U of the ash are higher, whereas the total content of rare earth elements (REEs) (Σ 163.7 ppm) are lower. Based on upper continental crust normalization, As, Se, Th, and U are enriched in all of the samples. The higher trace element contents in the ashes might be considered as a possible health hazard. The correlation analyses indicated that Ca is associated with anhydrite and As with hematite. The correlation analyses also showed that newly formed Al and Ca silicates may contain the elements such as Ti, K, Na, Cr, Sn, and Pb.     

Synthesis of rare earth-doped yttrium vanadate polyscale crystals and their enhanced photocatalytic degradation of aqueous dye solution

In this study, a series of RE³⁺:YVO₄ catalysts were successful synthesized by environmentally friendly mild hydrothermal and supercritical hydrothermal techniques. The rare earth-doped YVO₄ photocatalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, photoluminescence spectroscopy. The X-ray diffraction analysis reveals that the as-prepared YVO₄ crystals are of tetragonal phase. Further, the Fourier transform infrared spectroscopy result shows the absence of OH– molecules. The photoluminescence spectroscopy curves and UV–Vis spectra suggest that the band gap energy of YVO₄ is shifted to lower energy level due to doping of Nd³⁺ and Er³⁺ ions. The catalytic activities of the as-prepared RE³⁺:YVO₄ samples were tested for the photodegradation of amaranth aqueous dye solution under sunlight irradiation. Remarkably, the rare earth-doped YVO₄ nanocrystal sample showed outstanding photocatalytic degradation activities than undoped YVO₄ nanocrystal sample with good reusability. Under full spectrum irradiation, the as-prepared Nd³⁺-doped YVO₄ nanocrystals exhibited about 83% degradation efficiency. The apparent rate constant k for as-prepared Nd³⁺-doped YVO₄ nanocrystals with 50 mg of photocatalyst exhibits highest k value (0.32 min^?1), which is 2.9% higher than pure YVO₄ nanocrystals (0.11 min^?1).     

Stability of phengite and biotite in eclogites and characteristics of biotite- or orthopyroxene-bearing eclogites

Stability of phengite and biotite in eclogite is discussed using petrological data of natural eclogites, and the observational data are examined by thermodynamic calculations. Generally, phengite is a major K phase in natural eclogite and is stable in wide range of bulk composition. However, in eclogites from several localities of the Caledonides, biotite occurs as a stable eclogite-facies mineral, and is often associated with orthopyroxene. Bulk compositions of such biotite- or orthopyroxene-bearing eclogites are compared with those of eclogites from the Dabie–Sulu region, China, where phengite is a major K phase in eclogite. The biotite- or orthopyroxene-bearing eclogites from the Western Gneiss Region of the Caledonides are rich in MgO (10–15 wt%) and relatively poor in CaO (7–8 wt%) and Al₂O₃ (12–16 wt%). The CaO/MgO ratios of the biotite- or orthopyroxene-bearing eclogites are clearly lower than those of eclogites from the Dabie–Sulu region, indicating that MgO-rich and CaO-poor environments should be important for stabilizing of biotite and orthopyroxene in eclogite. Biotite-bearing eclogite from the North-East Greenland Eclogite Province is rich in MgO (≈16 wt%) and CaO (≈15.5 wt%) and extremely poor in Al₂O₃ (≈8 wt%). To stabilize biotite in eclogite, Al₂O₃-poor environments are also important. Bulk compositions of these biotite- or orthopyroxene-bearing eclogites are similar to picrite basaltic compositions. To examine these observational data, thermodynamic calculations were carried out in a seven-component system KH₂O_1.5–Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂, which includes garnet, kyanite, phengite, biotite, quartz, omphacite, orthopyroxene and olivine in conjunction with mass-balance calculations. Firstly, calculations were performed on the average bulk composition of eclogites from the Dabie–Sulu region to lherzolite (KLB-1). The calculation results confirmed that phengite should be stable in eclogite with 'ordinary' basaltic composition, whereas biotite and orthopyroxene should be stable in picrite basaltic compositions (e.g. MgO >11.0 wt%, CaO <9.8 wt%, Al₂O₃ <15.2 wt% at 700 °C, 2.5 GPa). Further calculations in basaltic system confirmed that increase of MgO content and decrease of CaO and Al₂O₃ contents were important to stabilize biotite and orthopyroxene in eclogite. Thus, mineral assemblage in picrite basalt system should be completely different from that in normal basaltic system.     

Uranium (U) concentration and its genetic significance in the phosphorites of the Paleoproterozoic Bijawar Group of the Lalitpur district,Uttar Pradesh,India

The paper presents the uranium (U) concentration and distribution pattern in the Paleoproterozoic phosphorites of Lalitpur district of Uttar Pradesh. The study of thin sections, SEM and XRD reveal that apatite is the essential phosphate mineral while quartz and feldspars are the dominant gangue in the phosphorites of the investigated area. The collophane is observed to be mostly oolitic in form and microspherulitic in texture. The major element geochemistry indicated that the phosphorite samples are rich in P₂O₅, CaO, SiO₂ and Fe₂O₃ whereas depletion of MgO, MnO, K₂O and Al₂O₃ was observed. The CaO/P₂O₅ ratio ranges from 1.13 to 1.46 which is slightly lower than that of cations and anions substituted francolite (1.621) and close to that of carbonate-fluorapatite (1.318). The trace element geochemistry indicates that the phosphorites of Lalitpur have the significant range of U concentration (1.67 to 129.67 μg/g) which is more than that of Th (0.69 to 0.09 μg/g) among the analysed trace elements in the phosphorite samples of the area. The positive correlation of U with P₂O₅, CaO and U/P₂O₅ indicates a close association of U with phosphate minerals like collophane (apatite), whereas negative correlation of U with SiO₂ and Fe₂O₃ may be due to mutual replacement. The antipathetic relationship of U with Ni may be an indication of high oxidizing conditions, whereas sympathetic relationship of U with K₂O points towards higher alkaline conditions of the basin of deposition during phosphatization. The variable concentration of U and its relationship with significant major and trace elements in most of the phosphorite samples lead one to believe that the deposition of these phosphorites might have taken place in highly alkaline medium during fairly oxidizing to weakly reducing environmental conditions of geosynclinal basin.     

Synthesis of cordierite using industrial waste fly ash

Fly ash is a product arising from coal combustion in thermal power plants. It represents a major source of environmental pollution. It is well known by its chemical composition rich of SiO₂ and Al₂O₃. With the aim of preserving the environment against this contamination, fly ash was used along with the starting materials for producing glass cordierite (2MgO, 2Al₂O₃, 5SiO₂). Four formulations were developed by mixing the silica gel, magnesium chloride (MgCl₂.6H₂O) and fly ash in the percentages enclosing the stoichiometry of cordierite (2MgO, 2Al₂O₃, 5SiO₂). Different experimental techniques (DTA/TGA, X-ray diffraction, FTIR and SEM) were used to characterise the prepared formulations. The results shown that for all formulations, a cordierite phase was obtained at 1200 °C along with several secondary phases such as mullite, cristobalite, silicon oxide, enstatite and spinel. At 1300 °C, pure indialite (α-cordierite) was obtained along with a small amount of spinel. The four formulations sintered at 1200 °C exhibit a homogenous morphology and high porosity. The acicular-shaped indialite grains were observed in both formulations with excess of alumina and excess of magnesia.     

The effects of K2O on the compositions of near-solidus melts of garnet peridotite at 3 GPa and the origin of basalts from enriched mantle

Enrichment in K₂O in oceanic island basalts (OIB) is correlated with high SiO₂, low CaO/Al₂O₃, and radiogenic isotopic signatures indicative of enriched mantle sources (EM1 and EM2). These are also chemical characteristics of the petit-spot lavas, which are highly enriched in K₂O (3–4 wt%) compared to other primitive oceanic basalts. We present experimentally derived liquids with varying concentrations of K₂O in equilibrium with a garnet lherzolite residue at 3 GPa to test the hypothesis that the major element characteristics of EM-type basalts are related to their enrichment in K₂O. SiO₂ is known to increase with K₂O at pressures less than 3 GPa, but it was previously unknown if this effect was significant at the high pressures associated with partial melting at the base of the lithosphere. We find that at 3 GPa for each 1 wt% increase in the K₂O content of a garnet lherzolite saturated melt, SiO₂ increases by ~0.5 wt% and CaO decreases by ~0.5 wt%. MgO and $K_{D}^{{{\text{Fe}} - {\text{Mg}}}}$ K D Fe - Mg each decrease slightly with K₂O concentration, as do Na₂O and Cr₂O₃. The effect of K₂O alone is not strong enough to account for the SiO₂ and CaO signatures associated with high-K₂O OIB. The SiO₂, CaO, and K₂O concentrations of experimentally derived partial melts presented here resemble those of petit-spot lavas, but the Al₂O₃ concentrations from the experimental melts are greater. Partitioning of K₂O between peridotite and melt suggests that petit spots, previously considered to sample ambient asthenosphere, require a source more enriched in K₂O than the MORB source.     

Petrogenesis of a Palaeoproterozoic S-type granite,central Wuyishan terrane,SE China: implications for early crustal evolution of the Cathaysia Block

We present zircon U–Pb ages, Hf isotopes, and whole-rock geochemistry of the Xiaochuan gneissic granite intrusion, SE China, to constrain its petrogenesis and provide insights into early crustal evolution of the Cathaysia Block. LA-ICP-MS zircon U–Pb dating of a representative sample yields a weighted mean ²⁰⁶Pb/²⁰⁷Pb age of 1839 ±16 Ma, interpreted as the emplacement age of the Xiaochuan granite. Zircons have ?_Hf(t) values ranging from –8.1 to 2.7 and T _DM2 model ages from 2.23 to 3.03 Ga. The granites are strongly peraluminious (A/CNK = 1.14–1.41), with relatively high FeO^t, TiO₂, and CaO/Na₂O, and low CaO, Al₂O₃/TiO₂, and Rb/Sr values. In addition, they show strongly negative Ba, Sr, Nb, and Ta and positive Th and Pb anomalies in the primitive mantle-normalized spider diagram, similar to other Cathaysia Palaeoproterozoic S-type granites. The geochemical and Hf isotopic signatures suggest that the Xiaochuan gneissic granites were generated by partial melting of Archaean crustal materials in an intraplate extensional setting. Our results, combined with existing geochronological data, further demonstrate that the Wuyishan terrane is underlain by Palaeoproterozoic crystalline basement.     

Identification and Simultaneous Optimisation of Tunisian Clay Properties: Preliminary Study for the Ceramic Products

The relationship between composition and physical parameters such as specific surface area, cationic exchange capacity and plasticity is studied with the aim of developing regression models that would permit the prediction of clay properties. These models could be useful for mineralogists and industrial applications. Nineteen representative clay samples were collected from Jebel Ressas in north-eastern Tunisia. Mineralogical data show that clay samples cover a very large variety of minerals. The main clay mineral is illite (50–60 wt%), secondary minerals including quartz, calcite and minor amounts of Na-feldspar. This study reveals that the average amount of silica (SiO₂) and alumina (Al₂O₃) are 51.9 and 19.6 wt%, respectively. The contents of lime (CaO) and iron (Fe₂O₃) vary between 4 and 8 wt% whereas the amount of alkalis (Na₂O + K₂O) is on average 4.1 wt%. The grain size data indicates a significant amount of silt fraction, and the fraction <2 µm varies between 23 and 35 wt%. Values for plasticity index range from 16 to 28 wt%. The cation exchange capacity and the specific surface values are 34.1–45.7 meq/100 g of air-dried clay and 302–374 m²/g, respectively. Lastly, regression models are used to correlate the properties with the mineralogical and chemical compositions. The significance and the validity of models were confirmed by statistical analysis and verification experiments. The regression models can be used to select the clay properties (plasticity index, cation exchange capacity and specific surface) in relation with clay minerals proportions and the finer fraction amounts.     

Geochemical assessment of Paleocene limestones of Sinn El-Kaddab Plateau,South Western Desert of Egypt,for industrial uses

The present work assesses the potential industrial uses of Paleocene limestone deposits, Garra Formation in Sinn El-Kaddab Plateau, South Western Desert of Egypt, based on their mineralogy and geochemical characteristics. Eighty-six limestone samples collected from ten stratigraphic columnar sections were analyzed using X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Petrographically, Garra limestone deposits consist dominantly of benthic foraminiferal wackestone and packstone microfacies. The XRD data revealed dominance of low-Mg calcite as essential carbonate mineral in the studied limestone. The bulk rock XRF results revealed CaO (29.28–55.75%) with an average of 52.74%. The CaO exhibits a strong negative correlation with MgO, SiO₂, TiO₂, Al₂O₃, and moderate negative correlation with Fe₂O₃ which indicates that the contribution of these elements is mainly due to detrital input. On the other hand, Al₂O₃ and Na₂O contents exhibit significant negative correlation with loss of ignition (LOI) wt% indicating their incorporation within terrigenous matrix. The average Sr content attains 1297 ppm indicating deposition in temperate marine environment. The average molar CaCO₃% values of bulk samples have been computed for individual columnar sections to determine the purity status of Garra limestone deposits. They range from impure (CaCO₃%?=?79.92%) to high-pure (CaCO₃%?=?97.76%) limestone. Therefore, Garra limestone deposits have extremely valuable uses in a wide spectrum of industrial applications including Portland cement, steel, ceramics, whiting, chemical uses, paper, and feed stuff.     

Petrogenetic and tectonic significance of Permian calc-alkaline lamprophyres,East Kunlun orogenic belt,Northern Qinghai-Tibet Plateau

We present new geochronological, mineralogical, geochemical, and isotopic data for recently recognized lamprophyre dikes in the East Kunlun orogenic belt of NW China. Based on euhedral amphibole phenocrysts and fine-grained, plagioclase-bearing groundmass with accessory magnetite, apatite, and titanite, these dikes are classified as spessartites. Plagioclase in these rocks is Ca-rich with An ranging from 45 to 82. Most of the amphibole phenocrysts are magnesiohastingsite or ferropargasite, with systematic ‘‘normal’ zoning in which Al₂O₃, CaO, and Mg# decrease from core to rim. The dikes have moderate Mg# (43–49) and high Al₂O₃ (17.5–18.0 wt.%), FeO_total (7.4–8.4 wt.%), and CaO (5.9–7.4 wt.%). Based on low total alkalis (Na₂O?+?K₂O?=?4.2%–5.0 wt.%), most samples plot in the low-K, calc-alkaline field. They are enriched in large-ion lithophile elements (e.g. K, Rb, Sr, and Ba) and light rare-earth elements, but are depleted in high-field-strength elements (e.g. Ta, Nb, P, and Ti), and have enriched Sr-Nd-Hf isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.70883–0.71045, ε_Nd(t) = –5.51–5.72, εHf(t)?=?–4.42–0.38). Zircon U–Pb geochronology indicates that the dikes were emplaced at 253 ± 2.5 Ma and are unrelated to their granite host, which has an age of 443 ± 1.7 Ma. The geochemical and isotopic data suggest derivation from an enriched lithospheric mantle source that had been metasomatized by subduction-related fluids. Low degrees of partial melting of a phlogopite-bearing, spinel peridotite, followed by fractional crystallization of olivine, amphibole, and Ti-bearing minerals, can account for the observed geochemical features of the dikes. Trace element geochemistry and regional geology suggest that the East Kunlun lamprophryes formed in a subduction-related setting.     

Geochemical assessment of a siliceous limestone sample for cement making

A low grade siliceous limestone sample from the Jayantipuram mine of Andhra Pradesh, India, has been investigated for its suitability for cement making. Petrological as well as X-ray diffraction pattern studies indicated that the limestone sample was crystalline and dominantly composed of calcite and quartz. They are simple in mineralogy, and yet they have variable silica and lime contents. Geochemical analysis results of twenty five hand picked samples indicated that the limestone from the Jayantipuram mine shows a wide range of variations in LOI (29.94% to 40.64%), SiO2 (6.14% to 27.18%), CaO (37.93% to 50.78%), Al2O3 (0.49% to 2.27%) and Fe2O3 (0.28% to 2.4%). MgO, K2O, Na2O, TiO2 and MnO2 are present in traces. CaO with LOI shows a strong positive correlation where as CaO with SiO2 shows a strong negative correlation because of mineralogical factors. The chemical composition of the limestone reflects its mineralogical composition. The distribution of various elements in the acid-soluble fraction has been studied by the factor analysis method in order to interpret in terms of their mineralogy, sedimentary environment and diagenesis. Mineralogy, recrystallization and other diagenetic changes are the main factors affecting the distribution of the elements and their mutual relationships in the limestone. The aim of this paper is also to analyze how significantly the two parameters, silica modulus and lime saturation factor, influence this low grade siliceous limestone sample from the Jayantipuram mine of Andhra Pradesh, India, for the cement making process from the geochemical data.     

Leaching of silica bands and concentration of magnetite in Archean BIF by hypogene fluids: Beebyn Fe ore deposit, Yilgarn Craton, Western Australia

The ~2,752-Ma Weld Range greenstone belt in the Yilgarn Craton of Western Australia hosts several Fe ore deposits that provide insights into the role of early hypogene fluids in the formation of high-grade (>55 wt% Fe) magnetite-rich ore in banded iron formation (BIF). The 1.5-km-long Beebyn orebody comprises a series of steeply dipping, discontinuous, <50-m-thick lenses of magnetite–(martite)-rich ore zones in BIF that extend from surface to vertical depths of at least 250 m. The ore zones are enveloped by a 3-km-long, 150-m-wide outer halo of hypogene siderite and ferroan dolomite in BIF and mafic igneous country rocks. Ferroan chlorite characterises 20-m-wide proximal alteration zones in mafic country rocks. The magnetite-rich Beebyn orebody is primarily the product of hypogene fluids that circulated through reverse shear zones during the formation of an Archean isoclinal fold-and-thrust belt. Two discrete stages of hypogene fluid flow caused the pseudomorphic replacement of silica-rich bands in BIF by Stage 1 siderite and magnetite and later by Stage 2 ferroan dolomite. The resulting carbonate-altered BIF is markedly depleted in SiO₂ and enriched in CaO, MgO, LOI, P₂O₅ and Fe₂O_3(total) compared with the least-altered BIF. Subsequent reactivation of these shear zones and circulation of hypogene fluids resulted in the leaching of existing hypogene carbonate minerals and the concentration of residual magnetite-rich bands. These Stage 3 magnetite-rich ore zones are depleted in SiO₂ and enriched in K₂O, CaO, MgO, P₂O₅ and Fe₂O_3(total) relative to the least-altered BIF. Proximal wall rock hypogene alteration zones in mafic igneous country rocks (up to 20 m from the BIF contact) are depleted in SiO₂, CaO, Na₂O, and K₂O and are enriched in Fe₂O_3(total), MgO and P₂O₅ compared with distal zones. Recent supergene alteration affects all rocks within about 100 m below the present surface, disturbing hypogene mineral and the geochemical zonation patterns associated with magnetite-rich ore zones. The key vectors for identifying hypogene magnetite-rich Fe ore in weathered outcrop include textural changes in BIF (from thickly to thinly banded), crenulated bands and collapse breccias that indicate volume reduction. Useful indicators of hypogene ore in less weathered rocks include an outer carbonate–magnetite alteration halo in BIF and ferroan chlorite in mafic country rocks.     

Nanogeochemistry of hydrothermal magnetite

Magnetite from hydrothermal ore deposits can contain up to tens of thousands of parts per million (ppm) of elements such as Ti, Si, V, Al, Ca, Mg, Na, which tend to either structurally incorporate into growth and sector zones or form mineral micro- to nano-sized particles. Here, we report micro- to nano-structural and chemical data of hydrothermal magnetite from the Los Colorados iron oxide–apatite deposit in Chile, where magnetite displays both types of trace element incorporation. Three generations of magnetites (X–Z) were identified with concentrations of minor and trace elements that vary significantly: SiO₂, from below detection limit (bdl) to 3.1 wt%; Al₂O₃, 0.3–2.3 wt%; CaO, bdl–0.9 wt%; MgO, 0.02–2.5 wt%; TiO₂, 0.1–0.4 wt%; MnO, 0.04–0.2 wt%; Na₂O, bdl–0.4 wt%; and K₂O, bdl–0.4 wt%. An exception is V₂O₃, which is remarkably constant, ranging from 0.3 to 0.4 wt%. Six types of crystalline nanoparticles (NPs) were identified by means of transmission electron microscopy in the trace element-rich zones, which are each a few micrometres wide: (1) diopside, (2) clinoenstatite; (3) amphibole, (4) mica, (5) ulvöspinel, and (6) Ti-rich magnetite. In addition, Al-rich nanodomains, which contain 2–3 wt% of Al, occur within a single crystal of magnetite. The accumulation of NPs in the trace element-rich zones suggest that they form owing to supersaturation from a hydrothermal fluid, followed by entrapment during continuous growth of the magnetite surface. It is also concluded that mineral NPs promote exsolution of new phases from the mineral host, otherwise preserved as structurally bound trace elements. The presence of abundant mineral NPs in magnetite points to a complex incorporation of trace elements during growth, and provides a cautionary note on the interpretation of micron-scale chemical data of magnetite.     

Origin of peraluminous minerals (corundum,spinel, and sapphirine) in a highly calcic anorthosite from the Sittampundi Layered Complex,Tamil Nadu,India

The highly calcic anorthosite (An_>95) from the Sittampundi Layered Complex (SLC) develops corundum, spinel and sapphirine that are hitherto not reported from any anorthositic rocks in the world. Petrological observations indicate the following sequence of mineral growth: plagioclase_matrix → corundum; clinopyroxene → amphibole; corundum + amphibole → plagioclase_corona + spinel; and spinel + corundum → coronitic sapphirine. Phase relations in the CaO–Na₂O–Al₂O₃–SiO₂–H₂O (CNASH) system suggest that corundum was presumably developed through vapour present incongruent melting of the highly calcic plagioclase during ultra-high temperature (UHT) metamorphism (T ≥ 1000 °C, P ≥ 9 kbar). Topological constraints in parts of the Na₂O–CaO–MgO–Al₂O₃–SiO₂–H₂O (NCMASH) system suggest that subsequent to the UHT metamorphism, aqueous fluid(s) permeated the rock and the assemblage corundum + amphibole + anorthite + clinozoisite was stabilized during high-pressure (HP) metamorphism (11 ± 2 kbar, 750 ± 50 °C). Constraints of the NCMASH topology and thermodynamic and textural modeling study suggest that coronitic plagioclase and spinel formed at the expense of corundum + amphibole during a steeply decompressive retrograde P–T path (7–8 kbar and 700–800 °C) in an open system. Textural modeling studies combined with chemical potential diagrams (μSiO₂–μMgO) in the MASH system support the view that sapphirine also formed from due to silica and Mg metasomatism of the precursor spinel ± corundum, on the steeply decompressive retrograde P–T path, prior to onset of significant cooling of the SLC. Extremely channelized fluid flow and large positive solid volume change of the stoichiometrically balanced sapphirine forming reaction explains the localized growth of sapphirine.     

Geochemistry of soils derived from black shales in the Ganziping mine area, western Hunan, China

The geochemistry of major and trace elements (including heavy metals and rare earth elements) of the fresh and weathered black shales, and the soils derived from black shales in the Ganziping mine area in western Hunan province (China) were studied using the following techniques: X-ray fluorescence (XRF), inductively coupled plasma mass spectrometer (ICP-MS) and X-ray diffraction (XRD). The results show that the black-shale soils are significantly enriched with Al₂O₃ and Fe₂O₃, and depleted of mobile elements CaO, Na₂O and K₂O. The soils are also highly enriched with heavy metals U, V, Ni, Ba, Cu, Zn and Pb, that may cause potential heavy-metal contamination of the soils. Composition of the soils is homogeneous compared to the weathered black shales, for which the concentrations of major elements except CaO and Na₂O, and trace elements except heavy metals (U, V, Ni, Ba, Cu, Zn and Pb) as well as the mobile Sr, show lower variations than in the weathered black shales. Ratios of Zr/Hf, Ta/Nb, Y/Ho, Nd/Sm, and Ti/(Ti + Zr), of the soils are also less variable, with values constantly similar to that of the fresh and weathered black shales correspondingly. Thus, components of the soils are believed to be contributed from the parent black shales through weathering and pedogenesis. It is concluded that the soils were formed by at least two stages of geochemical processes: the early stage of chemical differentiation and the later stage of chemical homogenization. The chemical differentiation that was taken during black-shale weathering might have caused the depletion of CaO and Na₂O, and the enrichment of Al₂O₃ and Fe₂O₃; while the chemical homogenization that was taken during pedogenesis led to the depletion of SiO₂ and K₂O, and to the further enrichment of Al₂O₃ and Fe₂O₃. The heavy-metal enrichment (contamination) of the soils was then genetically related to the enrichment of Al₂O₃ and Fe₂O₃ in the soils.     

Geochemistry and zircon U–Pb chronology of charnockites in the Yinshan Block,North China Craton: tectonic evolution involving Neoarchaean ridge subduction

The Yinshan Block, part of the Neoarchaean basement of the Western Block of the North China Craton, is composed of granite–greenstone and granulite–charnockite complexes. We report research on a suite of charnockites from the granulite–charnockite complex and characterize their geochemistry, zircon U–Pb geochronology, and Hf isotopic composition. The charnockites can be divided into intermediate (SiO₂ = 59–63 wt.%) and silicic (SiO₂ = 69–71 wt.%) groups. U–Pb zircon data yield protolith formation ages of 2524 ± 4 Ma, 2533 ± 15 Ma, followed by metamorphism at 2498 ± 3 Ma, 2490 ± 11 Ma, respectively, for these groups. Although the intermediate charnockites are characterized by higher Al₂O₃, TiO₂, Fe₂O₃^T, MnO, MgO, CaO, P₂O₅, K₂O, Sr, and ΣREE content than the silicic charnockites, the ages and Hf isotopic composition of zircons and REE patterns of both intermediate and silicic charnockites are remarkably consistent, which indicates that they are genetically related. These charnockites are predominantly metaluminous to slightly peraluminous, calc-alkalic to calcic, and magnesian – characteristics generally related to a subduction setting. High-Sr + Ba granites with low K₂O/Na₂O characteristics, shown by these charnockites, imply a mixture of mafic and felsic magmas generated from an enriched mantle + lower crust. High MgO, Ni, Cr and Mg#, low K₂O/Na₂O, and metaluminous to slightly peraluminous natures imply that the source rocks most likely were amphibolites. Coeval calc-alkaline magmatism and high-T granulite-facies metamorphism under low-H₂O activity in the area lead us to propose a model involving mid-ocean ridge subduction within a Neoarchaean convergent margin. The arc-related rocks accreted along the continent margin, and became a barrier when the lithospheric mantle ascended through the slab window. Melt derived from the decompressing mantle mixed with melt derived from the overlying, juvenile lower crust melt, which was warmed and metamorphosed by the ascending lithospheric mantle.     

(Cr1−x Al x )N as a candidate for corrosion protection in high temperature segments of CCS plants

Three (Cr_1?x Al _x )N (x = 0.33, 0.5, 0.66) coatings were deposited on Ni-super alloy IN718 using reactive magnetron sputtering. The oxidation behavior of all coatings at 900 °C up to 500 h in air was studied. Furthermore, the corrosion behavior of the (Cr_0.33,Al_0.66)N coating at 900 °C (corrosion type I) by spraying a uniform salt scale of Na₂SO₄ on the sample surface (1 mg/cm²) was investigated. It was found that the coated samples indicate significantly higher oxidation and corrosion resistance compared to uncoated Ni super alloy. This is mainly due to the formation of protective Cr₂O₃ and Al₂O₃ layers on the coating surface. With the increase of Al content, the coatings exhibited improved oxidation resistance. The formation of thin and adherent Al₂O₃ scale on the surface of Al rich coating is the reason for its better oxidation behavior. The detailed structures of the oxide scales and the interdiffusion between coating and substrate were studied using energy dispersive X-ray spectroscopy-analysis.     

Investigation on mantle peridotites from Neyriz ophiolite, south of Iran: geodynamic signals

Neyriz ophiolite in Abadeh Tashk area appears as four major separated massifs in an area with 125 km², south of Iran. Peridotites including harzburgite, dunite, and lesser low-Cpx lherzolite are the major constituents of the ophiolite with very minor mafic rocks. Usual gabbros of ophiolite complexes are virtually absent from the study area. Mineral modality associated with bulk rock and mineral chemistry of the peridotites show a progression from fertile to ultra-refractory character, reflected by a progressive decrease in modal pyroxenes and in Al₂O₃, CaO, SiO₂, Sc, Ta, V, and Ga values of the studied rocks by approaching chromite deposits. The Neyriz peridotites vary from low-Cpx lherzolite (MgO, 41.97–43.1 wt.%; Al₂O₃, 0.8–1.3 wt.%) with low content of Cr# spinel (36.7–37.6) and Fo olivine (90.79–91.5) to harzburgite (MgO, 44.31–45.25 wt.%;Al₂O₃, 0.29–0.45 wt.%; Cr# spinel, 58.2–73.45; Fo olivine, 91.23–91.56), and then to dunite (MgO, 45.9–49.2 wt.%; Al₂O₃, 0.18–0.48 wt.%) with higher content of Cr# spinel (74.34–79.36) and Fo olivine (91.75–94.68). Compared to modern oceanic settings, mineral and rock composition of low-Cpx lherzolite plot within the field of mid-ocean-ridge environment, whereas those of harzburgite and dunite fall in the field of fore-arc peridotites. As a result of the studies on minerals and whole rock chemistry along with rock interrelationships, we contend that the peridotites were subsequently affected by percolating hydrous boninitic melt from which the high-Cr–Mg, low-Ti chromitites were formed within mantle wedge above the supra-subduction zone in a fore-arc setting.