Effect of Al2O3 and Cr2O3 on loquidus temperatures in the cristobalite and tridymite primary phase fields of the MgO-"FeO"-SiO2 ststem in equilibrium with metallic iron

The effects of alumina and chromite impurities on the liquidus temperatures in the cristobalite/tridymite (SiO2) primary phase fields in the MgO-FeO-SiO, system in equilibrium with metallic iron have been investigated experimentally. Using high temperature equilibration and quenching followed by electron probe X-ray microanalysis (EPMA), liquiclus isotherms have been determined in the temperatures range 1 673 to 1 898 K. The results are presented in the form of pseudo-ternary sections of the MgO-FeO-SiO, system at 2, 3 and 5 wt% Al2O3, 2 wt% Cr2O3, and 2 wt% Cr2O3+2 wt% Al2O3. The study enables the liquidus to be described for a range of SiO2/MgO and MgO/FeO ratios. It was found that liquiclus temperatures in the cristobalite and tridymite primary phase fields, decrease significantly with the addition of Al2O3 and Cr2O3.

Effects of Al2O3 on phase equilibria in the olivine primary phase field of the MgO-"FeO"-SiO2-Al2O3 system in equilibrium with metallic iron

Liquidus temperatures and phase equilibria have been determined in the olivine primary phase field of the MgO-FeO-SiO2-Al2O3 system. Liquidus isotherms have been determined in the temperature range from 1748 to 1873K. The results are presented in the form of pseudo-ternary sections of the MgO-FeO-SiO2 with 2 and 3wt% Al2O3 in the liquid. The study enables the liquidus to be described for a range of SiO2/MgO ratios. It was found that liquidus temperatures in the olivine primary phase field decrease with the addition of Al2O3.

A thermodynamic model for di-trioctahedral chlorite from experimental and natural data in the system MgO-FeO-Al2O3-SiO2-H2O. Applications to P-T sections and geothermometry

We present a new thermodynamic activity-composition model for di-trioctahedral chlorite in the system FeO–MgO–Al2O3–SiO2–H2O that is based on the Holland–Powell internally consistent thermodynamic data set. The model is formulated in terms of four linearly independent end-members, which are amesite, clinochlore, daphnite and sudoite. These account for the most important crystal-chemical substitutions in chlorite, the Fe–Mg, Tschermak and di-trioctahedral substitution. The ideal part of end-member activities is modeled with a mixing-on-site formalism, and non-ideality is described by a macroscopic symmetric (regular) formalism. The symmetric interaction parameters were calibrated using a set of 271 published chlorite analyses for which robust independent temperature estimates are available. In addition, adjustment of the standard state thermodynamic properties of sudoite was required to accurately reproduce experimental brackets involving sudoite. This new model was tested by calculating representative P–T sections for metasediments at low temperatures (<400 °C), in particular sudoite and chlorite bearing metapelites from Crete. Comparison between the calculated mineral assemblages and field data shows that the new model is able to predict the coexistence of chlorite and sudoite at low metamorphic temperatures. The predicted lower limit of the chloritoid stability field is also in better agreement with petrological observations. For practical applications to metamorphic and hydrothermal environments, two new semi-empirical chlorite geothermometers named Chl(1) and Chl(2) were calibrated based on the chlorite + quartz + water equilibrium (2 clinochlore + 3 sudoite = 4 amesite + 4 H2O + 7 quartz). The Chl(1) thermometer requires knowledge of the (Fe3+/ΣFe) ratio in chlorite and predicts correct temperatures for a range of redox conditions. The Chl(2) geothermometer which assumes that all iron in chlorite is ferrous has been applied to partially recrystallized detrital chlorite from the Zone houillère in the French Western Alps.

Predicting coal ash slag flow characteristics (viscosity model for the Al2O3-CaO-'FeO'-SiO2 system)

A model has been developed which enables the viscosities of coal ash slags to be predicted as a function of composition and temperature under reducing conditions. The model describes both completely liquid and heterogeneous, i.e. partly crystallised, slags in the Al2O3-CaO-'FeO'-SiO2 system in equilibrium with metallic iron. The Urbain formalism has been modified to describe the viscosities of the liquid slag phase over the complete range of compositions and a wide range of temperatures. The computer package F * A * C * T was used to predict the proportions of solids and the compositions of the remaining liquid phases. The Roscoe equation has been used to describe the effect of presence of solid suspension (slurry effect) on the viscosity of partly crystallised slag systems. The model provides a good description of the experimental data of fully liquid, and liquid + solids mixtures, over the complete range of compositions and a wide range of temperatures. This model can now be used for viscosity predictions in industrial slag systems. Examples of the application of the new model to coal ash fluxing and blending are given in the paper. (C) 2001 Elsevier Science Ltd. All rights reserved.

A quasi-chemical viscosity model for fully liquid slags in the Al2O3-CaO-'FeO'-SiO2 system

A structurally based viscosity model for fully liquid silicate slags has been proposed and applied to the Al2O3-CaO-'FeO'-SiO2 system at metallic iron saturation. The model links the slag viscosity to the internal structure of melts through the concentrations of various anion/cation structural units (SUs). The concentrations of structural units are equivalent to the second nearest neighbor bond concentrations calculated by the quasi-chemical thermodynamic model. This viscosity model describes experimental data over the entire temperature and composition range within the Al2O3-CaO-'FeO'-SiO2 system at metallic iron saturation and can be extended to other industrial slag systems.

Properties of glass-ceramics obtained from crystallization of the SiO2-Al2O3-MgO-Li2O system with addition of ZrO2

This paper presents the study results with glass-ceramics obtained from base glass (MgO-Al2O3- SiO2-Li2O system) with addition of ZrO2 as nucleating agent. The glass was melted at 1650 degrees C for 3 h and at a heating rate of 10 degrees C/min. The molten glass was poured into a graphite mold to obtain monolithic samples and also in water in order to obtain particulate material. Such material was grinded and then pressed by both uniaxial and isostatic pressing methods before being sintered. Both the monolithic and pressed samples were performed under two different conditions of heat treatment so that their nucleation and crystallization occurred. In the first one, the samples were heated to 1100 degrees C with a heating rate of 10 degrees C/min. In the second one, there was an initial heating rate of 10 degrees C/min up to 780 degrees C, which was kept for 5 minutes. After that, the samples were heated to 1100 degrees C at a heating rate of 1 degrees C/min. Microhardness analyses showed that base glass presented values around 7.0 GPa. The glass-ceramics obtained from the powder sintering showed microhardness values lower than those obtained from monolithic samples. The highest hardness values were observed in the samples which were treated with two heating rates, whose values were around 9.2 +/- 0.5 GPa. Moreover, the glass-ceramics which were produced with an only heating rate, presented values around 7.1 +/- 0.2 GPa, very close to those observed in the base glass.

Vitrocerâmicas de alta resistência mecânica obtidas a partir da cristalização do sistema SiO2-Al2O3-MgO-Li2O com adição de ZrO2 e B2O3

Pós-graduação em Engenharia Mecânica - FEG

Chemical composition of Ninetyeast Ridge basalts

On Leg 121 of the Ocean Drilling Program, we recovered basaltic rocks from a total of three basement sites in the southern, central, and northern regions of Ninetyeast Ridge. These new sites complement the previous four basement holes drilled during Legs 22 and 26 of the Deep Sea Drilling Project, and confirm the predominantly tholeiitic, light rare earth element-enriched character of the basalts that cap the ridge. The basalts show marked iron enrichment; ferrobasalts occur at Sites 214 and 216 and oceanic andesites at Site 253. All of the basalts recovered during Leg 121 are altered, and range from aphyric olivine tholeiites (Site 756), to strongly plagioclase-phyric basalts (Site 757). Basalts from Site 758, which were clearly erupted in a submarine environment (pillow basalts are present in the section), are sparsely to strongly plagioclase-phyric. The basalts recovered at any one hole are isotopically homogeneous (except for the basalts from Site 758, which show a range of Pb isotopes), and it is possible to relate the magmas at any one site by high-level fractionation processes. However, there are significant variations in isotope ratios and highly incompatible element ratios between sites, which suggest that the mantle source for the ridge basalts was compositionally variable. Such variation, in view of the large volume of magmatic products that form the ridge system, is not surprising. There is not, however, a systematic variation in basalt composition along the ridge. We agree with previous models that relate Ninetyeast Ridge to a mantle plume in the southern Indian Ocean. The tholeiitic, iron-enriched, and voluminous character of the ridge basalts is typical of oceanic islands associated with plumes on or near a mid-ocean ridge (e.g., Iceland, Galapagos Islands, and St. Paul/Amsterdam islands). The absence of recovered alkalic suites is inconsistent with an intraplate setting, such as the Hawaiian Islands or Kerguelen Island. Thus, the major element data, like the gravity data, strongly suggest that the ridge was erupted on or very close to an active spreading center. Isotopically, the most likely plume that created the excess magmatism on the Ridge is the Kerguelen-Heard plume system, but the Ninetyeast Ridge basalts do not represent a simple mixing of the Kerguelen plume and mid-ocean Ninetyeast Ridge basalt mantle.

Metamorphism on Chromite Ores from the Dobromirtsi ultramafic massif, Rhodope Mountains (SE Bulgaria)

Podiform chromitite bodies occur in highly serpentinized peridotites at Dobromirtsi Ultramafic Massif (Rhodope Mountains, southeastern Bulgaria). The ultramafic body is believed to represent a fragment of Palaeozoic ophiolite mantle. The ophiolite sequence is associated with greenschist - lower-temperature amphibolite facies metamorphosed rocks (biotitic gneisses hosting amphibolite). This association suggests that peridotites, chromitites and metamorphic rocks underwent a common metamorphic evolution. Chromitites at Dobromirtsi have been strongly altered. Their degree of alteration depends on the chromite/silicate ratio and to a lesser extent, on the size of chromitite bodies. Alteration is recorded in individual chromite grains in the form of optical and chemical zoning. Core to rim chemical trends are expressed by MgO- and Al2O3- impoverishment, mainly compensated by FeO and/or Fe2O3 increases. Such chemical variations correspond with three main alteration events. The first one was associated with ocean-floor metamorphism and was characterized by a lizardite replacement of olivine and the absence of chromite alteration. The second event took place during greenchist facies metamorphism. During this event, MgO- and SiO2-rich fluids (derived from low temperature serpentinization of olivine and pyroxenes) reacted with chromite to form chlorite; as a consequence, chromite became altered to a FeO- and Cr2O3-rich, Al2O3-poor chromite. The third event, mainly developed during lower temperature amphibolite facies metamorphism, caused the replacement of the primary and previously altered chromite by Fe2O3-rich chromite (ferritchromite).

Mineral chemistry of primary and secondary phases in basaltic rocks

Primary magmatic phases (spinel, olivine, plagioclase, clinopyroxene, amphibole, and biotite) and secondary phyllosilicates (smectite, chlorite-smectite, and celadonite) were analyzed by electron microprobe in alkalic and tholeiitic dolerites and basalts from Ocean Drilling Program Sites 800, 801, and 802. Aphyric alkalic dolerite sills (Hole 800A) and basalt flows (Holes 801B and 801C) share common mineralogical features: matrix feldspars are strongly zoned from labradorite cores to discrete sodic rims of alkali feldspar with a high Or component, which overlaps that of quench microlites in glassy mesostasis; little fractionated clinopyroxenes are Ti-rich diopsides and augites (with marked aegirine-augite rims at Site 801); rare, brown, Fe**3+-rich amphibole is winchite; and late biotites exhibit variable Ti contents. Alkalic rims to feldspars probably developed at the same time as quenched mesostasis feldspars and late-stage magmatic biotite, and represent the buildup of K-rich hydrous fluids during crystallization. Phenocryst phases in primitive mid-ocean ridge tholeiites from Hole 801C (Mg numbers about 70) have extreme compositions with chrome spinel (Cr/Cr + Al ratios about 0.2-0.4), Ni-rich olivine (Fo90), and highly calcic plagioclase (An90). Later glomerophyric clumps of plagioclase (An75-80) and clinopyroxene (diopside-augite) are strongly zoned and probably reflect rapidly changing melt conditions during upward transport, prior to seafloor quenching. In contrast, phenocryst phases (olivine, plagioclase, and clinopyroxene) in the Hole 802A tholeiites show limited variation and do not have such primitive compositions, reflecting the uniform and different chemical composition of all the bulk rocks. Replacive phyllosilicates in both alkalic and tholeiitic basalts include various colored smectites (Fe-, Mg-, and Al-saponites), chlorite-smectite and celadonite. Smectite compositions typically reflect the replaced host composition; glass is replaced by brown Fe-saponites (variable Fe/Mg ratios) and olivine by greenish Mg-saponites (or Al-rich chlorite-smectite).

Geochemistry of DSDP Leg 65 basalts

Leg 65 of the Deep Sea Drilling Project successfully recovered basalts from four sites in the mouth of the Gulf of California, thus completing a transect begun during Leg 64 from the continental margin of Baja California to the east side of the East Pacific Rise (EPR). Sixty-three whole-rock samples from Sites 482, 483, and 485 have been analyzed by X-ray fluorescence techniques, and a further eleven samples by instrumental neutron-activation techniques, in order to assess magma variability within and between sites. Although the major element compositions and absolute hygromagmatophile (HYG) element abundances are quite variable, all of the basalts are subalkaline tholeiites exhibiting strong more-HYG element (e.g., Rb, La, Nb, Ta) depletion (LaN/YbN ~ 0.4; Nb/Zr ~ 0.02; Ba/Zr ~ 0.23; Th/Hf ~ 0.05). These ratios, together with La/Ta ratios of 20 and Th/Ta ratios of 1.25, demonstrate that the Leg 65 basalts resemble the depleted "N-type" ocean ridge basalts recovered from the Mid-Atlantic Ridge (MAR) at 22 °N and other sections of the EPR. Zr/Ti, Zr/Y, and La/Yb ratios increase with increasing fractionation. It is clear that the basalts recovered from Sites 482, 483, and 485 were all derived from a compositionally similar source and that the compositional differences observed between lithological units can be explained by varying degrees of open system fractional crystallization (magma mixing) in subridge magma chambers. The basaltic rocks recovered from Site 474 near the margin of Baja California, and Sites 477, 478, and 481 in the Guaymas Basin, all drilled during Leg 64, have consistently higher Th/Hf, La/Sm, Zr/Ti, and Zr/Y ratios and higher absolute Sr contents than the Leg 65 basalts. While some of these variations may be explained by different conditions of partial melting, it is considered more likely that the mantle source underlying the Guaymas Basin is chemically distinct from that feeding the EPR at the mouth of the Gulf. These source variations probably reflect the complex tectonic setting of the Gulf of California, the magmas formed at the inception of spreading and in the central part of the Gulf containing a minor but significant component of sub-continental (calc-alkaline) material.