Mineralogical composition and ash geochemistry of raw and beneficiated high sulfur coals

Coal is one of the most available energy sources on earth. The mineralogical and geo-chemical aspects of coals are of prime importance for their utilization. The mineralogical composition, ash chemistry, and ash fusion temperature (AFT) ranges of raw and beneficiated coals are investigated in this paper. Further, the mineral matter transformation during the beneficiation processes viz. by oxidative desulfurization; alkali extraction and ultrasonication along with the relationship of the ash fusion temperature (AFT) ranges with the ash components in the coal are discussed. The major oxides present in the coal and beneficiated coal ashes include Fe₂O₃, Al₂O₃, SiO₂, CaO, and MgO, which significantly affect the ash fusion temperature ranges. Initial deformation temperature (IDT) changes with the ash components and, increases with the increase in the Fe₂O₃ content in coal ash. With increasing concentrations of both Al₂O₃ and SiO₂, the initial deformation temperature (IDT) also increases. The increasing and decreasing nature of the initial deformation temperature (IDT) observed is also dependent upon the CaO and MgO contents. XRD analysis of the coal samples revealed significant changes in mineral matter contents with the types of beneficiation processes adopted for coal. The minerals like chlorite, illite, montmorillonite, pyrite, calcite, aragonite, and alumina have been removed during the beneficiation processes. The FTIR spectra also indicate the presence of minerals like gypsum (G), calcite (C) aragonite (Ar), quartz (Q) and kaolinite (K) in the raw coal and their subsequent removal after the beneficiation processes.     

The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.     

Reactivity of sandstone and siltstone samples from the Ketzin pilot CO2 storage site-Laboratory experiments and reactive geochemical modeling

To evaluate mineralogical-geochemical changes within the reservoir of the Ketzin pilot CO₂ storage site in Brandenburg, Germany, two sets of laboratory experiments on sandstone and siltstone samples from the Stuttgart Formation have been performed. Samples were exposed to synthetic brine and pure CO₂ at experimental conditions and run durations of 5.5 MPa/40 °C/40 months for sandstone and 7.5 MPa/40 °C/6 months for siltstone samples, respectively. Mineralogical changes in both sets of experiments are generally minor making it difficult to differentiate natural variability of the whole rock samples from CO₂-induced alterations. Results of sandstone experiments suggest dissolution of the anorthite component of plagioclase, anhydrite, K-feldspar, analcime, hematite and chlorite + biotite. Dissolution of the anorthite component of plagioclase, anhydrite and K-feldspars is also observed in siltstone experiments. In an inverse modeling approach, an extensive set of equilibrium simulations was set up in order to reproduce the experimental observations of the sandstone experiments. Simulations generally show fairly good matches with the experimental observations. Best matches with measured brine data are obtained from mineral combinations of albite, analcime, anhydrite, dolomite, hematite, illite, and kaolinite. The major discrepancies during equilibrium modeling, however, are reactions involving Fe²⁺ and Al³⁺. The best matching subsets of the equilibrium models were finally run including kinetic rate laws. These simulations reveal that experimentally determined brine data was well matched, but reactions involving K⁺ and Fe²⁺ are not fully covered. The modeling results identified key primary minerals as well as key chemical processes, but also showed that the models are not capable of covering all possible contingencies.     

Characteristics of Coal Ashes in Yanzhou Mining District and Distribution of Trace Elements in Them

In the process of combustion of coal organic and inorganic materials in it will undergo a complex variation.Part of thew will become volatiles and,together with coal smoke,enter into atmosphere,some will remain in micro-particulates such as ash and dust and find their way into atmosphere in the form of solid particles,and the rest will be retained in ash and slag.Coal ashes are the residues of organic and inorganic substances in coal left after coal combustion and the compostition of coal ashes in dependent on that of minerals and organic matter in coal.This paper deals with the chemical composition of coal ashes,the distribution of trace elements in them and their petrological characteristics,and also studies the relationship between the yield of coal ashes and the distribution of trace elements.In addition,a preliminary study in also undertaken on the factors that affect the chemical composition of coal ashes.As viewed from the analyses of coal ash samples collected from the Yanzhou mining district,it can be seen clearly that coal ashes from the region studied are composed chiefly of crystalline materials,glassy materials and uncombusted organic matter and the major chemical compositions are SiO2,Al2O3,Fe2O3,and CaO,as well as minor amounts of SO3,PWO5,Na2O,K2O and TiO2.During the combustion of coal,its trace elements will be redistributed and most of them are enriched in coal ashes.At the same time,the concentrations of the trace elements in flying ash are much higher than those of bottom ash,i.e.,with decreasing particle-size of coal ashes their concentrations will become higher and higher.So the contents of trace elements are negatively proportional to the particle-size of coal ashes.There has been found a positive correlation between the trace elements Th.V.Zn,Cu and Pb and the yield of coal ashes while a negative correlation between Cl and the yield of coal ashes.     

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.     

A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism and degassing of Devonian evaporites in the Norilsk aureoles, Siberia

Devonian evaporites and associated sedimentary rocks in the Norilsk region were contact metamorphosed during emplacement of mafic sills that form part of the end-Permian (~252 Ma) Siberian Traps. We present mineralogical, geochemical and Sr–Nd isotopic data on sedimentary rocks unaffected by metamorphism, and meta-sedimentary rocks from selected contact aureoles at Norilsk, to examine the mechanisms responsible for magma-evaporite interaction and its relation to the end-Permian environmental crisis. The sedimentary rocks include massive anhydrite, rock salt, dolostone, calcareous siltstones and shale, and the meta-sedimentary rocks comprise calcareous hornfels, siliceous hornfels and minor meta-anhydrite and meta-sandstone. Contact metamorphism took place at low pressure and at maximum temperatures corresponding to the phlogopite-diopside stability field. Calcareous hornfels have high CaO, MgO, CΟ₂, SΟ₃, low SiO₂ and initial Sr isotopic ratios of 0.7079–0.7092, features indicative of calcareous siltstone protoliths. Siliceous hornfels, in contrast, have high SiO₂, Al₂O₃, Na₂O, low in other major element oxides and initial Sr isotopic ratios of 0.7083–0.7152, consistent with pelitic or shaley protoliths. Loss of CO₂ in a subset of calcareous hornfels can be explained by decarbonation reactions during metamorphism, but release of SO₂ from evaporites cannot be accounted for by a similar mechanism. Occurrences of wollastonite and a variety of hydrous minerals in the calcareous hornfels are consistent with equilibration with hydrous fluid, which was capable of leaching large quantities of anhydrite in the presence of dissolved NaCl. In this way, substantial sediment-derived sulfur could have been mobilized, incorporated into the magmatic system and released to the atmosphere. The release of CO₂ and SO₂ from Siberian evaporites added to the variety of toxic gases generated during metamorphism of organic matter, coal and rock salt, contributing to the end-Permian environmental crisis.     

An experimental study of the Fe oxidation states in garnet and clinopyroxene as a function of temperature in the system CaO–FeO–Fe2O3–MgO–Al2O3–SiO2: implications for garnet–clinopyroxene geothermometry

Samples with eclogitic composition in the system CaO–FeO–Fe₂O₃–MgO–Al₂O₃–SiO₂ were produced from various kinds of starting materials held in graphite-lined Pt capsules at a pressure of 2.5–3.0 GPa and temperatures of 800–1,300 °C using a piston-cylinder or Belt apparatus. Garnets and clinopyroxenes were characterized by analytical transmission electron microscopy and electron probe micro-analysis (EPMA). Fe³⁺/ΣFe ratios determined by electron energy-loss spectroscopy (EELS) decrease in clinopyroxene from 22.2 ± 3.4 % at 800 °C to 13.3 ± 5.4 % at 1,300 °C, while in garnet, they vary between 10.8 ± 1.5 and 15.4 ± 4.7 %, respectively. Temperature estimates according to Krogh (Contrib Mineral Petrol 99:44–48, 1988) reproduce the experimental temperature to ±60 °C without systematic deviations if total iron is used in the calculation. If only the Fe²⁺ content is used, which was obtained by combining EPMA and EELS results, the experimental temperature is underestimated by 33 °C on average at 800–1,200 °C and overestimated by 77 °C on average at 1,300 °C. These systematic deviations can be explained by the temperature-dependent ratio of Fe²⁺/ΣFe in garnet divided by that in clinopyroxene. Since the difference between the calculated and experimental temperature is relatively small, a Fe²⁺-based recalibration of the thermometer appears not to be necessary for the investigated system in the range of pressure, temperature and composition covered by the experiments of this study.     

Experiments on liquid immiscibility in silicate melts with H2O, P, S, F and Cl: implications for natural magmas

Isobaric (200 MPa) experiments have been performed to investigate the effects of H₂O alone or in combination with P, S, F or Cl on liquid-phase separation in melts in the systems Fe₂SiO₄–Fe₃O₄–KAlSi₂O₆–SiO₂, Fe₃O₄–KAlSi₂O₆–SiO₂ and Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ with or without plagioclase (An₅₀). Experiments were heated in a rapid-quench internally heated pressure vessel at 1,075, 1,150 or 1,200 °C for 2 h. Experimental fO₂ was maintained at QFM, NNO or MH oxygen buffers. H₂O alone or in combination with P, S or F increases the temperature and composition range of two-liquid fields at fO₂ = NNO and MH buffers. P, S, F and Cl partition preferentially into the Fe-rich immiscible liquid. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO₂-rich liquid and plot on similar but distinct power-law curves compared with equivalent anhydrous or basaltic melts. The addition of 2 wt% S to the system Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ stabilizes three immiscible melts with Fe-, FeS- and Si-rich compositions. H₂O-induced suppression of liquidus temperatures in the experimental systems, considered with the effects of pressure on the temperature and composition ranges of two-liquid fields in silicate melts, suggests that liquid-phase separation may be stable in some H₂O-rich silicate magmas at pressures in excess of 200 MPa.     

Chemical and petrographical characterization of feed coal, fly ash and bottom ash from the Figueira Power Plant, Paraná, Brazil

The aim of the present study is the petrographic and chemical characterization of the coal at the Figueira Power Plant, Paraná, Brazil, prior and after the beneficiation process and the chemical characterization of fly and bottom ashes generated in the combustion process.Petrographic characterization was carried out through maceral analysis and vitrinite reflectance measurements. Chemical characterization included proximate analysis, determination of calorific value and sulphur content, ultimate analysis, X-ray diffraction, X-ray fluorescence, Inductively Coupled Plasma — Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma — Atomic Emission Spectrometry (ICP-AES) analysis, and determination of Total Organic Carbon (TOC) content.Vitrinite reflectance analyses indicate a high volatile B/C bituminous coal (0.61 to 0.73% Rrandom). Maceral analyses show predominance of the vitrinite maceral group (51.6 to 70.9 vol.%, m.m.f). Except of the Run of mine (ROM) coal sample, the average calorific value of the coals is 5205 kcal/kg and ash yields range from 21.4 to 38.1 wt.%. The mineralogical composition (X-ray diffraction) of coals includes kaolinite, quartz, plagioclase and pyrite, whereas fly and bottom ashes are composed by mullite, ettringite, quartz, magnetite, and hematite. Analyses of major elements from coal, fly and bottom ashes indicate a high SiO₂, Al₂O₃, and Fe₂O₃ content. Trace elements analysis of in-situ and ROM coals by ICP-MS and ICP-AES show highest concentration in Zn and As. Most of the toxic elements such as As, Cd, Cr, Mo, Ni, Pb, and Zn are significantly reduced by coal beneficiation. Considering the spatial distribution of trace elements in the beneficiated coal samples, which were collected over a period of three months, there appears to be little variation in Cd and Zn concentrations, whereas trace elements such as As, Mo, and Pb show a larger variation.In the fly and bottom ashes, the highest concentrations of trace elements were determined for Zn and As. When compared with trace element concentrations in the feed coal, fly ashes show a significant enrichment in most trace elements (As, B, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Tl, and Zn), suggesting a predominantly volatile nature for these elements. In contrast, Sn is distributed evenly within the different ash types, whereas U shows depleted concentration in both bottom and fly ash samples.According to the International Classification of in-seam coals the Cambuí coals are of para/ortho bituminous rank of low grade (except for the ROM sample), and are characterized by the predominance of vitrinite macerals.     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.     

Humite- and scapolite-bearing assemblages in marbles and calcsilicates of Dronning Maud Land, Antarctica: new data for Gondwana reconstructions

This study investigates marbles and calcsilicates in Central Dronning Maud Land (CDML), East Antarctica. The paleogeographic positioning of CDML as part of Gondwana is still unclear; however, rock types, mineral assemblages, textures and P–T conditions observed in this study are remarkably similar to the Kerala Khondalite Belt in India. The CDML marbles and calcsilicates experienced a Pan-African granulite facies metamorphism at c. 570 Ma and an amphibolite facies retrogression at c. 520 Ma. The highest grade assemblage in marbles is forsterite+spinel+calcite+dolomite, in calcsilicates the assemblages are diopside+spinel, diopside+garnet, scapolite+wollastonite+clinopyroxene±quartz, scapolite±anorthite±calcite+clinopyroxene+wollastonite. These assemblages constrain the peak metamorphic conditions to 830±20 °C, 6.8±0.5 kbar and X _CO2>0.46. During retrogression, highly fluoric humite-group minerals (humite, clinohumite, chondrodite) replaced forsterite, and garnet rims formed at the expense of scapolite during reactions with wollastonite, calcite or clinopyroxene but without involvement of anorthite. Metamorphic conditions were about 650 °C, 4.5±0.7 kbar, 0.2< X _CO2^fluid<0.36, and the co-existence of garnet, clinopyroxene, wollastonite and quartz constrains f_O2 to FMQ-1.5 log units. Mineral textures indicate a very limited influx of H₂O-rich fluid during amphibolite facies retrogression and point to significant variations of fluid composition in mm-sized areas of the rock. Gypsum was observed in two samples; it probably replaced metamorphic anhydrite which appears to have formed under amphibolite facies conditions. The observed extensive anorogenic magmatism (anorthosites, A-type granitoids) and the character of metamorphism between 610 and 510 Ma suggest that the crustal thermal structure was characterized by a long-lived (50–100 Ma) rise of the crustal geotherm probably caused by magmatic underplating.     

Effect of chromium on phase relations in the join forsterite-anorthite-diopside in air at 1 Atm

The effect of Cr on the silicate system has been studied in air at 1 atm by adding a small amount of MgCr₂O₄ (0.2–0.5 wt.%) to the join Mg₂SiO₄ (forsterite) — CaAl₂Si₂O₈ (anorthite) — CaMgSi₂O₆ (diopside), which has been considered to form a thermal divide in the system CaO-MgO-Al₂O₃-SiO₂. The spinel primary field is enlarged compared with that in the Cr-free join at the expense of the anorthite primary field. The piercing points forsterite+anorthite+diopside+liquid and forsterite+anorthite+spinel+liquid approach each other with increasing MgCr₂O₄, meet at the join with 0.25 wt.% MgCr₂O₄ (0.20 wt.% Cr₂O₃) to form the ‘isobaric quaternary invariant point’ forsterite+anorthite+diopside+spinel+liquid, and then separate again as new ‘piercing points’ of diopside+spinel+anorthite+liquid and forsterite+diopside+ spinel+liquid. This process indicates that the join Mg₂SiO₄-CaAl₂Si₂O₈-CaMgSi₂O₆ containing more than 0.2 wt.% Cr₂O₃ cannot be a thermal divide in the basalt tetrahedron. The results of the present study show that the presence of a minor amount of Cr causes a significant effect on the phase relations and therefore, the role of Cr must be taken into account in the formulation of a petrologic model.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

Risk assessment of bottom ash from fuel oil power plant of Italy: mineralogical,chemical and leaching characterization

The main aim of the present study is to contribute to the field of environmental research by providing new data on bottom ash samples derived from an oil power plant located in Southern Italy. To achieve this purpose, the mineralogical and chemical properties of representative bottom ash samples were investigated through the integrated employment of different analytical techniques, i.e., X-ray powder diffraction, scanning electron microscopy, X-ray fluorescence and atomic absorption spectrometry. The obtained experimental results show that quartz, alunogen, rhomboclase and potassium hydrogen silicate are the major crystalline phases of all the analyzed samples. Furthermore, the revealed main ash constituents are SiO₂ and SO₃, with low contents of Fe₂O₃ and Al₂O₃, and little amounts of CaO, Na₂O, K₂O, MgO, P₂O₅ and TiO₂. Among the trace elements, very high amounts of heavy metals, i.e., V, Cr, Ni, La, Pb and Mo, were detected. The comparison of the obtained heavy metal abundance data with those reported in the literature highlights significant differences. Leaching test evidenced V, Ni and Cr values that make these ashes a potential contamination source for groundwater quality and for soil, nearby the ash disposal landfills area. All the obtained findings show that these materials are highly harmful for the human health, with a greater extent for the heavy metal concentrations.     

Geochemical characteristics of sediments from Lake El’gygytgyn,Chukotka Peninsula,as indicators of climatic variations for the past 350 ka

This paper presents data on the inorganic geochemical characteristics of the sediments from Hole LZ1024 (Lake El’gygytgyn, Chukotka, 67°30′ N 172°08′ E). It is demonstrated how these data are associated with climatic variations during isotope stages 1–9. The sediments of the warm stages are characterized by elevated contents of SiO₂, CaO, Na₂O, K₂O, and Sr and low concentrations of TiO₂, Al₂O₃, MgO, and Fe₂O₃. It has been established that the geochemical parameters correlate with global climatic variations.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The chemical composition of tertiary Indian coal ash and its combustion behaviour – a statistical approach: Part 2

In Part 1 of the present investigation, 37 representative Eocene coal samples of Meghalaya, India were analyzed and their physico-chemical characteristics and the major oxides and minerals present in ash samples were studied for assessing the genesis of these coals. Various statistical tools were also applied to study their genesis. The datasets from Part 1 used in this investigation (Part 2) show the contribution of major oxides towards ash fusion temperatures (AFTs). The regression analysis of high temperature ash (HTA) composition and initial deformation temperature (IDT) show a definite increasing or decreasing trend, which has been used to determine the predictive indices for slagging, fouling, and abrasion propensities during combustion practices. The increase or decrease of IDT is influenced by the increase of Fe₂O₃, Al₂O₃, SiO₂, and CaO, respectively. Detrital-authigenic index (DAI) calculated from the ash composition and its relation with AFT indicates Sialoferric nature of these coals. The correlation analysis, Principal Component Analysis (PCA), and Hierarchical Cluster Analysis (HCA) were used to study the possible fouling, slagging, and abrasion potentials in boilers during the coal combustion processes. A positive relationship between slagging and heating values of the coal has been found in this study.     

Unique Clinkers and Paralavas from a New Nyalga Combustion Metamorphic Complex in Central Mongolia: Mineralogy,Geochemistry, and Genesis

The paper presents mineralogical and geochemical data on clinkers and paralavas and on conditions under which they were formed at the Nyalga combustion metamorphic complex, which was recently discovered in Central Mongolia. Mineral and phase assemblages of the CM rocks do not have analogues in the world. The clinkers contain pyrogenically modified mudstone relics, acid silicate glass, partly molten quartz and feldspar grains, and newly formed indialite microlites (phenocrysts) with a ferroindialite marginal zone. In the paralava melts, spinel microlites with broadly varying Fe concentrations and anorthite–bytownite were the first to crystallize, and were followed by phenocrysts of Al-clinopyroxene ± melilite and Mg–Fe olivine. The next minerals to crystallize were Ca-fayalite, kirschsteinite, pyrrhotite, minerals of the rhönite–kuratite series, K–Ba feldspars (celsian, hyalophane, and Ba-orthoclase, Fe³⁺-hercynite ± (native iron, wüstite, Al-magnetite, and fresnoite), nepheline ± (kalsilite), and later calcite, siderite, barite, celestine, and gypsum. The paralavas contain rare minerals of the rhönite–kuratite series, a new end-member of the rhönite subgroup Ca₄Fe ₈ ²⁺ Fe ₄ ³⁺ O₄ [Si₈Al₄O₃₆], a tobermorite-like mineral Ca₅Si₅(Al,Fe)(OH)O₁₆ · 5H₂O, and high- Ba F-rich mica (K,Ba)(Mg,Fe)₃(Al,Si)₄O₁₀F₂. The paralavas host quenched relics of microemulsions of immiscible residual silicate melts with broadly varying Si, Al, Fe, Ca, K, Ba, and Sr concentrations, sulfide and calcitic melts, and water-rich silicate–iron ± (Mn) fluid media. The clinkers were formed less than 2 Ma ago in various parts of the Choir–Nyalga basin by melting Early Cretaceous mudstones with bulk composition varies from dacitic to andesitic. The pyrogenic transformations of the mudstones were nearly isochemical, except only for volatile components. The CM melt rocks of basaltic andesitic composition were formed via melting carbonate–silicate sediments at temperatures above 1450°C. The Ca- and Fe-enriched and silicaundersaturated paralavas crystallized near the surface at temperatures higher than 900–1100°C and oxygen fugacity \(f_{O_2 }\) between the IW and QFM buffers. In local melting domains of the carbonate–silicate sedimentary rocks and in isolations of the residual melts among the paralava matrix the fluid pressure was higher than the atmospheric one. The bulk composition, mineral and phase assemblages of CM rocks of the Nyalga complex are very diverse (dacitic, andesitic, basaltic andesitic, basaltic, and silica-undersaturated mafic) because the melts crystallized under unequilibrated conditions and were derived by the complete or partial melting of clayey and carbonate–silicate sediments during natural coal fires.     

Effectiveness of rice husk ash in stabilizing Kenyan red coffee soil for road subgrades construction

The high cost of traditional stabilizing agents such as lime and cement has led to the research on industrial and agricultural wastes as suitable alternatives. Rice growing areas of Kenya accumulate large quantities of rice husk which pose serious disposal problems. When burnt as a means of disposal, the rice husk ash formed is difficult to coagulate and thus contribute to air and water pollution, require a large space for disposal, and cause respiratory health problems when inhaled. Red coffee soil poses serious engineering problems such as swelling due to wetting, shrinkage due to drying, low bearing capacity, and differential settlement leading to cracks and needs improvement for strength and stability in service. Red coffee soil and rice husks samples were obtained from Gatundu and Mwea, respectively. The rice husk was burnt at temperatures between 500 and 700 °C to ensure maximal formation of siliceous component. Chemical analysis on the rice husk ash gave the sum of SiO₂, Fe₂O₃, and Al₂O₃ as 85.5 % indicating that it has pozzolanic activity. Rice husk ash was applied at 4, 6, 8, and 10 % by weight of dry soil. Plasticity index, liquid limit, and linear shrinkage decreased from 26.1, 67.1, and 13.0 % for lean sample to 18.5, 63.6, and 9.2 %, for 10 % rice husk ash stabilized samples, whereas plastic limit increased from 41.0 to 45.15 %. The soaked California bearing ratio value for rice husk ash stabilized samples increased from 5 to 22 % corresponding to soil subgrade class S4. However, lime-stabilized samples gave higher values.