SYNTHESIS OF THE CLINOPYROXENES JOIN CAMGSI2O6-NAALSI2O6 FOR JEWELRY

Clinopyroxenes of the join CaMgSi2O6(diopside)-NaAlSi2O6 (jadeite) were synthesized in the temperature range 800-1900 degrees C and under varying pressure, 10-55 kbar. The stability regions of various compositions of diopside-jadeite have been established experimentally using different compositions of glass materials: stoichiometric composition NaAlSi2O6, 0.1CaMgSi(2)O(6)-0.9NaAlSi(2)O(6), 0.2CaMgSi(2)O(6)0.8NaAlSi(2)O(6), 0.3CaMgSi(2)O(6)-0.7NaAlSi(2)O(6), and 0.4CaMgSi(2)O(6)-0.6NaAlSi(2)O(6). Unit cell parameters of synthetic clinopyroxenes with the above compositions were determined. The physical properties, such as hardness, toughness, density, and refractive index, etc., were also measured. The results show that synthetic clinopyroxenes have the same properties as the natural one. The gem quality of diopside-jadeite clinopyroxenes was achieved by synthesised on the basis of the above experiments. Various colouring agents, such as Cr2O3, Co2O3, NiO2, Fe2O3, TiO2, MnO, CuO, and their combinations, FeO-Cr2O3, etc., were added to obtain the different colours of gem. In addition, small amounts of the rare-earth oxides, such as CeO2, Nd2O3, Sm2O3, Dy2O3, Eu2O3, Er2O3, Pr6O11, Lu2O3 and CuO-Eu2O3, Co2O3Nd2O3, etc., were also added to produce fluorescent clinopyroxenes for jewellery.

绿辉石固溶体NaAlSi_2O_6-CaMgSi_2O_6的合成和高压下熔化过程研究

在2×10~9～5×10~9Pa,1 000～2 300℃下合成了由二元组分NaAlSi_2O_6(Jadeit)-CaMgSi_2O_6(Diopside)构成的绿辉石,通过XRD分析数据计算了绿辉石Jd_xDi_(1-x)的晶胞参数随组成变化的规律。采用高温高压淬火法和XRD研究了Jd_xDi_(1-x)(x=0～1.0)高压下(2×10~9～5×10~9 Pa)的固溶关系,并根据Jd_xDi(1-x)的固溶相图计算了不同压力下的熔化热。

东海榴辉岩向斜长角闪岩的转化过程

The Ultrahigh Pressure Metamorphic (UHPM) eclogite, which was resulted from deep subduction of crustal continent, is very significant due to its continental dynamic implications. Further more, this kind of rocks experienced great P-T, fluid and stresses changes during its forming and exhumation, causing mineral reactions occur intensively, which resulted in a lot of fantastic micro-texture. The micro-texture was preserved duo to a rapid exhumation of the eclogite. This PhD dissertation takes such micro-textures in 10 Donghai eclogite samples South Sulu UHPM terrene, as research object to reveal the transformation of the eclogite to amphibolite. Microscope and Scanning Electron Microscope were employed to observe the micro-texture. Basing on microprobe analysis of minerals, the ACF projections and iso-con analysis were used to uncover the mineral reactions during the transformation. Micro-texture observation (both of Microcopy and Electron Scanning Microscope), demonstrated: l.The peak mineral assemblage of the researched Donghai eclogites is garnet + omphacite + rutile (+ kyanite + aptite +coesite). 2.The transformation of the Donghai eclogite to amphibolite can be divided into two stages: The earlier one is Symplectization, resulting in the forming of diopside + albite (+magnetite) symplectite that occurred only along the boundary between two adjacent omphacite grains. Other minerals were not involved in such reaction. The latter stage is Fluid-Infiltration of the eclogite, which was caused by fluid-intrusion. The infiltration is demonstrated by amphibolization of the symplectite, decomposition of garnet and the forming of some hydrous minerals such as phengite and epidote, and resulted in an amphibole + plagioclase + phengite + epidote or ziosite assemblage. Basing on microprobe analysis of the minerals, ACF projections indicated: In the ACF diagrams, the two joint lines of peak Grt + Omp and Dio + Ab crossed at Omp projection-point, indicating that the garnet had not taken part in the forming reaction of the Dio + Ab symplectite, just like that had been pointed out by micro-texture observation. In the ACF diagrams, the hornblende + plagioclase + epidote + phengite quadrilateral intersected with Dio + Ab + Grt triangle, demonstrating that the hydrous mineral assemblage was formed by fluid infiltration through garnet, diopside and albite. Iso-con (mass-balance) analysis of the symplectization and infiltration reveals: 1.The symplectization of the omphacite has a very complex mass exchange: Some symplectite gained only silicon from its surroundings; and some one requires Ca, but provides Na to its surroundings; while other symplectite provides Ca, Mg and Fe to its surroundings. 2.The infiltration cause variable mass exchanges occurring among the garnet, diopside and albite: In some eclogite sample, no mass, except H2O, exchange occurred during the infiltration. Meanwhile, there was not any hydrous mineral except hornblende formed in the sample accordingly. In some samples, the mass exchange among the three minerals is complex: amphibolization of the diopside in a symplectite gained Al from garnet, and provided Si and Ca to its surrounding, resulting in a Si, Ca and Al-rich fluid. Correspondingly, there was a lot of phengite and ziosite occurred in the sample. In other samples, the amphibolization of a symplectite provided Fe and Mg besides Si and Ca to its surrounding while gained Al. In such kind of sample, epidote occurred within the hydrous mineral assemblage. Synthesizing the micro-texture observation, ACF analysis and iso-con analysis, we deduced the transformation procedure as following: 1. A symplectite after an omphacite was resulted by one, or two, or all of following mineral reactions together: Jd (Ca-Tsch) +SiO2=Ab (An) (1) 4NaA IS i.A+CaO=2NaAlS i308+Na20+CaAl2S 1208 (2) 2NaAlSi2OB (Jd in Omp)+CaMgSi;,0B(Dio in Omp)-2NaAlSi:,O"(Ab)+Ca0+Mg0 (3) 2(CaAl2Si0fi) (Ca-tsch in Omp)+CaFeSi2O6(Hed in 0mp)-H>2CaAl2Si208(An)+Ca0 + FeO (4) A CO2-rich fluid is suggested as cataclysm for the above reactions, which largely increased the mobility of Ca, Mg and Na resulted from reaction (2), (3) and (4). The immobile product Fe2* combined with rutile to form ilmenite, resulting in rutile + ilmenite symplectite. Or, the Fe was precipitated as hematite locally. A procedure of the fluid infiltration as following is suggested: I .A hydrous fluid intruded into the eclogite, and reacted first with garnet to form hornblende and extra Al, resulting in a hornblende film around the garnet grain and an Al-rich fluid. 2.The Al-rich fluid infiltrated through the symplectite, OH" and part of the Al in the fluid combined with Dio while some Si and Ca in the Dio were dissolved made the Dio transferred to amphibole. Meanwhile, plagioclase-type cation exchange occurred between the fluid and plagioclase in the symplectite, making the plagioclase have a higher An-content. 3.Above infiltration and cation exchange resulted in an Al, Si, Ca (and K, providing the primary hydrous fluid contain K)-rich fluid. 4.Under suitable conditions, the solute in the fluid precipitated to form phengite firstly. After the K element in the fluid was consumed up, ziosite or epidote was formed. If the fluid did not contain any K. element, only ziosite or epidote was precipitated. For those eclogites, where all omphacite had been replaced by symplectite before infiltration, neither element exchange occurred, nor did phengite or epidote form during the infiltration. At the last stage, the garnet was oxidized and breakdown: garnet + H2O = epidote + hornblende + hematite, due to more and more fluid intruding into the eclogite. At this time, all the peak minerals were replaced by amphibolite-phase ones, and the eclogite transformed to an amphibolite completely. Tentative pressure calculation indicates that the infiltration occurred at 3-6kbar (about 10-20km depth), where the deformation mechanics transformed from brittle to ductile yield. At such depth, the surface water can permeate the rocks through fault system, causing a rapid cooling.

NCMAS系统熔体结构和动力学性质压力效应的分子动力学研究

Molecular dynamics simulations were used to study the pressure dependence of the structure and the dynamic properties of forsterite melt (Mg_2SiO_4), diopside melt (CaMgSi_2O_6), anorthite melt (CaAl_2Si_2O_8), jadite melt (NaAlSi_2O_6) and albite melt (NaAlSi3O8) from 0 GPa to 25 GPa at about 2000 K and the following conclusions have been reached. Firstly, the ratio of NBO to T (NBO and T denote the content of non-bridging oxygen and the total content of Si~(4+) and Al~(3+) respectively) is closely related to the pressure and the composition of the melts. It decreases monotonously in forsterite, diopside and anorthite melts while increases at the initial stage and then decreases in jadite and albite melts with increasing pressure. At a fixed pressure, the shear viscosity of the melts decreases with increasing NBO/T and the variation rate is almost 150 times higher in fully polymerized melts than that in de-polymerized melts in comparison with anorthite melts. Secondly, it is generally accepted that the formation of the Si and A1 will promote the diffusion of the network-forming ions. The hypothesis is frequently employed to explain the emergence of the maximum self-diffusion coefficient of the network-forming ions in fully polymerized melts. However, I detected that the pressure corresponding to the peak of the self-diffusion coefficient of the network-forming ions is lower than that corresponding to the maximum content of Si and A1, and that there exists an approximately linear relationship between the self-diffusion coefficient of the ions and the breaking frequency of the bonds under a given pressure, which is different from the present understanding about the mechanism of self-diffusion. Thirdly, the relationship between the self-diffusion coefficient of Si~(4+), Al~(3+) and O~(2-) and the shear viscosity of the melts evolves from the Stokes-Einstein equation and Sutherland-Einstein equation to the Eyring equation with increasing pressure. And the key to obtain self-diffusion coefficient from shear viscosity under difference pressures is to determine A. in the Eyring equation. For Si~(4+) and O~(2-), this could be done using the linear relationship between A, and NBO% in anorthite melts. However, this method is inapplicable in other kinds of melts.

Clinopyroxene based glasses and glass-ceramics for functional applications

As piroxenas são um vasto grupo de silicatos minerais encontrados em muitas rochas ígneas e metamórficas. Na sua forma mais simples, estes silicatos são constituídas por cadeias de SiO3 ligando grupos tetrahédricos de SiO4. A fórmula química geral das piroxenas é M2M1T2O6, onde M2 se refere a catiões geralmente em uma coordenação octaédrica distorcida (Mg2+, Fe2+, Mn2+, Li+, Ca2+, Na+), M1 refere-se a catiões numa coordenação octaédrica regular (Al3+, Fe3+, Ti4+, Cr3+, V3+, Ti3+, Zr4+, Sc3+, Zn2+, Mg2+, Fe2+, Mn2+), e T a catiões em coordenação tetrahédrica (Si4+, Al3+, Fe3+). As piroxenas com estrutura monoclínica são designadas de clinopiroxenes. A estabilidade das clinopyroxenes num espectro de composições químicas amplo, em conjugação com a possibilidade de ajustar as suas propriedades físicas e químicas e a durabilidade química, têm gerado um interesse mundial devido a suas aplicações em ciência e tecnologia de materiais. Este trabalho trata do desenvolvimento de vidros e de vitro-cerâmicos baseadas de clinopiroxenas para aplicações funcionais. O estudo teve objectivos científicos e tecnológicos; nomeadamente, adquirir conhecimentos fundamentais sobre a formação de fases cristalinas e soluções sólidas em determinados sistemas vitro-cerâmicos, e avaliar a viabilidade de aplicação dos novos materiais em diferentes áreas tecnológicas, com especial ênfase sobre a selagem em células de combustível de óxido sólido (SOFC). Com este intuito, prepararam-se vários vidros e materiais vitro-cerâmicos ao longo das juntas Enstatite (MgSiO3) - diopsídio (CaMgSi2O6) e diopsídio (CaMgSi2O6) - Ca - Tschermak (CaAlSi2O6), os quais foram caracterizados através de um vasto leque de técnicas. Todos os vidros foram preparados por fusão-arrefecimento enquanto os vitro-cerâmicos foram obtidos quer por sinterização e cristalização de fritas, quer por nucleação e cristalização de vidros monolíticos. Estudaram-se ainda os efeitos de várias substituições iónicas em composições de diopsídio contendo Al na estrutura, sinterização e no comportamento durante a cristalização de vidros e nas propriedades dos materiais vitro-cerâmicos, com relevância para a sua aplicação como selantes em SOFC. Verificou-se que Foi observado que os vidros/vitro-cerâmicos à base de enstatite não apresentavam as características necessárias para serem usados como materiais selantes em SOFC, enquanto as melhores propriedades apresentadas pelos vitro-cerâmicos à base de diopsídio qualificaram-nos para futuros estudos neste tipo de aplicações. Para além de investigar a adequação dos vitro-cerâmicos à base de clinopyroxene como selantes, esta tese tem também como objetivo estudar a influência dos agentes de nucleação na nucleação em volume dos vitro-cerâmicos resultantes á base de diopsídio, de modo a qualificá-los como potenciais materiais hopedeiros de resíduos nucleares radioactivos.

Avaliação do desempenho in vivo do biovidro FastOs™

O conceito de bioatividade surgiu com a descoberta, no início década de 70, de que algumas composições vítreas (ex.: 45S5 Bioglass®), tinham a capacidade de estabelecer uma ligação direta e estável com os tecidos vivos. Desde então, este grupo de biomateriais tem vindo a receber uma atenção cada vez maior por parte dos investigadores, tendo como motivação principal a busca de novas composições com propriedades mais adequadas para a regeneração óssea do que as composições comercialmente disponíveis. Na presente tese, avaliou-se o desempenho in vivo de duas composições de biovidro do sistema diopsite (CaMgSi2O6) - fluorapatite (Ca5(PO4)3F) - fosfato tricálcico (3CaO•P2O5) aplicados em defeitos ósseos de tamanho não crítico em carneiros, tendo também sido avaliada a biocompatibilidade dos biomateriais através da aplicação subcutânea de placas dos mesmos vidros. O trabalho realizado também incluiu a avaliação dos materiais in vitro, através de estudos de biomineralização em fluido corporal simulado e estudos de degradação. Os biomateriais foram comparados com o biovidro 45S5 Bioglass®, sendo que em termos de bioatividade in vitro, as duas composições investigadas apresentaram um maior potencial bioativo, levando à formação de uma camada superficial de hidroxiapatite carbonatada, em contraste com a formação de calcite na composição comercial, sob condições idênticas. Os testes de degradação in vitro também apresentaram resultados melhores para as duas novas composições, traduzidos por variações de pH e taxas de degradação menores do que os observados no caso do 45S5 Bioglass®. A avaliação in vivo dos implantes subcutâneos permitiu apurar a biocompatibilidade dos biovidros testados, tendo sido considerados ligeiramente irritantes. Os resultados relativos à aplicação dos pós de vidro bioativo nos defeitos ósseos não foram obtidos em tempo útil de modo a poderem ser incluídos na presente tese. Considerando o desempenho in vitro e a biocompatibilidade dos materiais estudados, estes podem apontar-se como materiais promissores para aplicações em engenharia de tecidos, particularmente na regeneração do tecido ósseo.

A actividade sintética de hMSCs em contacto com vidros bioativos

Os vidros bioativos constituem um material apropriado para o preenchimento de defeitos ósseos, como alternativa a enxertos autólogos, uma vez que, quando expostos a fluidos fisiológicos promovem a formação de uma ligação com o tecido ósseo sob a forma de uma camada de hidroxiapatite carbonatada. No presente trabalho caracterizaram-se vidros bioativos sem conteúdo alcalino, cuja composição incide no sistema binário de diópsido (CaMgSi2O6) e fosfato de tricálcio (3CaO·P2O5), em função da sua molhabilidade, carga superficial, perfil de degradação, carácter bioativo em fluido fisiológico simulado e do seu comportamento in vitro em contacto com células estaminais mesenquimais humanas (hMSCs). A medição do ângulo de contacto inicial de água sobre os vidros demonstrou o carácter hidrofílico dos vidros investigados. A determinação do potencial zeta mostrou que a carga superficial dos vidros é negativa, sendo mais negativa na composição Di-70. O estudo da biodegradação dos vidros, efetuado através da sua imersão em Tris-HCl, permitiu concluir que a perda de peso dos vidros foi reduzida. A caraterização in vitro em meio acelular foi efetuada através da imersão dos vidros numa solução de fluido fisiológico simulado (SBF) e verificou-se que estes possuem capacidade de formar uma camada de hidroxiapatite carbonatada à sua superfície após 7 dias, detetável por XRD, FTIR e SEM/EDS, sugerindo que este conjunto de vidros é potencialmente bioativo, e poderá estimular a proliferação e diferenciação celular. A resposta das hMSCs em cultura aos vidros bioativos foi avaliada em termos de atividade metabólica, morfologia, viabilidade, proliferação e diferenciação osteogénica e conclui-se que os biovidros Di-60 e Di-70 poderão constituir um suporte viável para a proliferação e diferenciação de hMSCs.

Alkali-free bioactive glasses for bone regeneration

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tissue engineering. Another aim was to understand the structure-property relationships in the investigated bioactive glasses. In this quest, various glass compositions within the Diopside (CaMgSi2O6) – Fluorapatite (Ca5(PO4)3F) – Tricalcium phosphate (3CaO•P2O5) system have been investigated. All the glasses were prepared by melt-quenching technique and characterized by a wide array of complementary characterization techniques. The glass-ceramics were produced by sintering of glass powders compacts followed by a suitable heat treatment to promote the nucleation and crystallization phenomena. Furthermore, selected parent glass compositions were doped with several functional ions and an attempt to understand their effects on the glass structure, sintering ability and on the in vitro bio-degradation and biomineralization behaviours of the glasses was made. The effects of the same variables on the devitrification (nucleation and crystallization) behaviour of glasses to form bioactive glass-ceramics were also investigated. Some of the glasses exhibited high bio-mineralization rates, expressed by the formation of a surface hydroxyapatite layer within 1–12 h of immersion in a simulated body fluid (SBF) solution. All the glasses showed relatively lower degradation rates in comparison to that of 45S5 Bioglass®. Some of the glasses showed very good in vitro behaviour and the glasses co-doped with zinc and strontium showed an in vitro dose dependent behaviour. The as-designed bioactive glasses and glass–ceramic materials are excellent candidates for applications in bone regeneration and for the fabrication of scaffolds for tissue engineering.

Alkaline-earth aluminosilicate-based glass and glass-ceramic sealants for functional applications

The planar design of solid oxide fuel cell (SOFC) is the most promising one due to its easier fabrication, improved performance and relatively high power density. In planar SOFCs and other solid-electrolyte devices, gas-tight seals must be formed along the edges of each cell and between the stack and gas manifolds. Glass and glass-ceramic (GC), in particular alkaline-earth alumino silicate based glasses and GCs, are becoming the most promising materials for gas-tight sealing applications in SOFCs. Besides the development of new glass-based materials, new additional concepts are required to overcome the challenges being faced by the currently existing sealant technology. The present work deals with the development of glasses- and GCs-based materials to be used as a sealants for SOFCs and other electrochemical functional applications. In this pursuit, various glasses and GCs in the field of diopside crystalline materials have been synthesized and characterized by a wide array of techniques. All the glasses were prepared by melt-quenching technique while GCs were produced by sintering of glass powder compacts at the temperature ranges from 800−900 ºC for 1−1000 h. Furthermore, the influence of various ionic substitutions, especially SrO for CaO, and Ln2O3 (Ln=La, Nd, Gd, and Yb), for MgO + SiO2 in Al-containing diopside on the structure, sintering and crystallization behaviour of glasses and properties of resultant GCs has been investigated, in relevance with final application as sealants in SOFC. From the results obtained in the study of diopside-based glasses, a bilayered concept of GC sealant is proposed to overcome the challenges being faced by (SOFCs). The systems designated as Gd−0.3 (in mol%: 20.62MgO−18.05CaO−7.74SrO−46.40SiO2−1.29Al2O3 − 2.04 B2O3−3.87Gd2O3) and Sr−0.3 (in mol%: 24.54 MgO−14.73 CaO−7.36 SrO−0.55 BaO−47.73 SiO2−1.23 Al2O3−1.23 La2O3−1.79 B2O3−0.84 NiO) have been utilized to realize the bi-layer concept. Both GCs exhibit similar thermal properties, while differing in their amorphous fractions, revealed excellent thermal stability along a period of 1,000 h. They also bonded well to the metallic interconnect (Crofer22APU) and 8 mol% yttrium stabilized zirconium (8YSZ) ceramic electrolyte without forming undesirable interfacial layers at the joints of SOFC components and GC. Two separated layers composed of glasses (Gd−0.3 and Sr−0.3) were prepared and deposited onto interconnect materials using a tape casting approach. The bi-layered GC showed good wetting and bonding ability to Crofer22APU plate, suitable thermal expansion coefficient (9.7–11.1 × 10–6 K−1), mechanical reliability, high electrical resistivity, and strong adhesion to the SOFC componets. All these features confirm the good suitability of the investigated bi-layered sealant system for SOFC applications.

Spectral Reflectance Characteristics of Kimberlite Indicator Minerals and Other Selected Mineral Grains

High chromium content in kimberlite indicator minerals such as pyrope garnet and diopside is often correlated with the presence of diamonds. In this study, kimberlite indicator minerals were examined using visible light reflectance spectroscopy to determine if chromium content can be correlated with spectral absorption features. The depth of absorption features in the visible spectral region were correlated with the molecular percentage of chromium and other first series transition metal elements obtained by electron microprobe data. In the visible part of the spectrum, chromium is evident by 3 absorption features in the pyrope reflectance spectrum; one isolated and narrow feature at the wavelength 689 nm was used to correlate with the chromium mol %. The isolation of this feature in the pyrope spectra is advantageous since it is not directly affected by other proximal absorption bands that could be caused by other transition metals. Analysis of the feature indicates that as grain volume increases the depth of the absorption feature will also increase. Clustering grain volumes into fractions yields better correlation between absorption depth and mol % chromium. Other types of garnet (almandine, grossular, spessartine) and kimberlite indicator minerals (olivine, diopside, chromite, ilmenite) were analyzed to determine if other absorption features could be used to predict the proportion of specific transition metal elements. Diopside in particular illustrates the same isolated chromium absorption feature as pyrope and may indicate mol percent but needs further study with larger sample sets.

Alkaline magmatism in the Amambay area, NE Paraguay: The Cerro Sarambi complex

The Early Cretaceous alkaline magmatism in the northeastern region of Paraguay (Amambay Province) is represented by stocks, plugs, dikes, and dike swarms emplaced into Carboniferous to Triassic-Jurassic sediments and Precambrian rocks. This magmatism is tectonically related to the Ponta Pora Arch, a NE-trending structural feature, and has the Cerro Sarambi and Cerro Chiriguelo carbonatite complexes as its most significant expressions. Other alkaline occurrences found in the area are the Cerro Guazu and the small bodies of Cerro Apua, Arroyo Gasory, Cerro Jhu, Cerro Tayay, and Cerro Teyu. The alkaline rocks comprise ultramafic-mafic, syenitic, and carbonatitic petrographic associations in addition to lithologies of variable composition and texture occurring as dikes; fenites are described in both carbonatite complexes. Alkali feldspar and clinopyroxene, ranging from diopside to aegirine, are the most abundant minerals, with feldspathoids (nepheline, analcime), biotite, and subordinate Ti-rich garnet; minor constituents are Fe-Ti oxides and cancrinite as the main alteration product from nepheline. Chemically, the Amambay silicate rocks are potassic to highly potassic and have miaskitic affinity, with the non-cumulate intrusive types concentrated mainly in the saturated to undersaturated areas in silica syenitic fields. Fine-grained rocks are also of syenitic affiliation or represent more mafic varieties. The carbonatitic rocks consist dominantly of calciocarbonatites. Variation diagrams plotting major and trace elements vs. SiO(2) concentration for the Cerro Sarambi rocks show positive correlations for Al(2)O(3), K(2)O, and Rb, and negative ones for TiO(2), MgO, Fe(2)O(3), CaO, P(2)O(5), and Sr, indicating that fractional crystallization played an important role in the formation of the complex. Incompatible elements normalized to primitive mantle display positive spikes for Rb, La, Pb, Sr, and Sm, and negative for Nb-Ta, P, and Ti, as these negative anomalies are considerably more pronounced in the carbonatites. Chondrite-normalized REE patterns point to the high concentration of these elements and to the strong LRE/HRE fractionation. The Amambay rocks are highly enriched in radiogenic Sr and have T(DM) model ages that vary from 1.6 to 1.1 Ga. suggesting a mantle source enriched in incompatible elements by metasomatic events in Paleo-Mesoproterozoic times. Data are consistent with the derivation of the Cerro Sarambi rocks from a parental magma of lamprophyric (minette) composition and suggest an origin by liquid immiscibility processes for the carbonatites. (C) 2011 Elsevier Ltd. All rights reserved.

Geochemistry of natural chromium occurrence in a sandstone aquifer in Bauru Basin, Sao Paulo State, Brazil

Anomalous concentrations of Cr(VI) occur in groundwaters of the Adamantina Aquifer, in a large region in the western state of Sao Paulo, sometimes exceeding the potability limit (0.05 mg L(-1)). To identify the possible geochemical reactions responsible for the occurrence of Cr in groundwater in Urania, borehole rock samples were collected in order to carry out mineralogical and chemical analyses. In addition, multilevel monitoring wells were installed and groundwater samples were analyzed. Analyses of the borehole rock samples show the occurrence of a geochemical anomaly of Cr in the quartzose sandstones (average concentrations of 221 ppm). Chrome-diopside is one of the main minerals contributing to this anomaly, having an average Cr content of 1505 ppm. Sequential extraction experiments indicated weakly adsorbed Cr in the order of 0.54 ppm, and this quantity is enough to provide the Cr concentrations observed in groundwater. Groundwaters from the monitoring wells proved to be stratified, with the highest concentrations of Cr(VI) (0.13 mg L(-1)) being associated with high redox and pH values (over 10) and high concentrations of Na. Geochemical reactions that may explain the release of Cr from the solid phase to groundwater involve the release of Cr(III) from minerals (like chrome-diopside and Cr-Fe hydroxide), followed by oxidation of Cr(III) to Cr(VI), probably related to the reduction of Mn oxides present in the aquifer. Then cation exchange occurs and dissolution of carbonates which increases the pH of groundwater, resulting in the desorption and mobilization of Cr(VI) into groundwater. (C) 2011 Elsevier Ltd. All rights reserved.

Anomalous content of chromium in a Cretaceous sandstone aquifer of the Bauru Basin, state of Sao Paulo, Brazil

Anomalous and natural concentrations of Cr(6+), occasionally exceeding the permitted limit for human consumption (0.05 mg/L), have been detected in groundwater in the northwestern region of the state of Sao Paulo. As part of a water-rock interaction investigation, this article describes the chemical and mineralogical characterization of rock samples taken from boreholes in the municipality of Urania, with the objective of identifying Cr-bearing minerals and determining how chromium is associated with these minerals. Rock sample analysis were performed using X-ray Fluorescence, X-ray Diffraction, Scanning Electron Microscopy, electron microprobe and sequential extraction techniques. Chemical analyses indicated that the quartzose sandstones show a geochemical anomaly of chromium, with an average content of 221 ppm, which is higher than the reported chromium content of generic sandstones (35 ppm). Diopside was identified as the primary Cr-bearing mineral potentially subject to weathering processes, with a chromium content of up to 1.2% as Cr(2)O(3). Many of the diopside grains showed dissolution features, confirming the occurrence of weathering. Sequential extraction experiments indicated that 99.3% of the chromium in samples is tightly bonded to minerals, whereas 0.24% is weakly bonded via adsorption. Assuming hypothetically that all adsorbed chromium is released via desorption, the theoretical Cr concentration in water would be one order of magnitude higher than the concentrations of Cr(6+) detected in groundwater. (C) 2010 Elsevier Ltd. All rights reserved.

Estudo de Matérias-Primas do Rio Grande do Norte para Uso em Revestimento Poroso: Influência do teor de dolomita e temperatura de calcinação nas propriedades físico-mecânicas

The state of Rio Grande do Norte presents a great potentiality for the production of ceramic tiles because of having natural raw material in quantity and quality making its economical exploration possible, beyond the great energetic differential of the state, the natural gás. This works aims to study the influence of the dolomite and granulometry concentration and calcinations temperature in the obtaining of formulations for porous coverings which have to be coherent to the project,s specifications. The experiments have involved the physical-chemical and mineralogical characterizations of raw materials and mechanical tests in the dry and burnt proof bodies preceding a mixture experiment planning with the use of the response surface methodology, in order to get the best raw materials combinations to produce a ceramic mass with specific properties. The twelve ceramic masses studied in this work were prepared by the via dry process, characterized, shaped by uniaxial pressing and sinterized in the temperatures of 940ºC, 1000ºC, 1060ºC, 1120ºC and 1180ºC, using a fast burning cycle. The crystalline phases formed during the sintering in the temperatures in study have revealed the presence of anorthite and diopside beyond quartz with a remaining phase. These phases were the main responsible ones by the physical- mechanical properties of the sinterized proof bodies. The proof bodies after the sintering stage have presented water absorption higher than 10% and a good dimensional stability in all studied temperatures. However, the flexural breaking strength results in the temperatures of 940ºC, 1000ºC and 1060ºC, under the temperature zone of the vitrification of ceramic whiteware do not reach the flexural breaking strength specific for the porous wall tile (15 MPa), but in the temperature of 1120ºC next to the vitrification temperature zone, some whiteware ceramic (formulations) has reached the specified value for the porous wall tile. The results of this work have showed that the studied raw materials have great importance for used in the production of porous wall tiles (BIII)

Estudo geoquímico e geocronológico Rb-Sr e Sm-Nd em zonas de cisalhamento mineralizadas em ouro e suas relações com as rochas encaixantes e geocronológico Sm-Nd em mineralizações de scheelita na faixa Seridó

Great part of the gold mineralizations are associated with shearing zones through which circulate a great volume of fluids, that interact with the host rocks, originating leaching or precipitation of chemical elements, including gold. The studied mineralizations are inserted in the Seridó Belt. The tungsten mineralization in Brejuí Mine is hosted in calcsilicate rocks from Jucurutu Formation. The São Francisco auriferous mineralization has as host rocks mica-schists from Seridó Formation, while the Ponta da Serra and Fazenda Simpático mineralizations are hosted in orthogneisses of this fold belt basement. The research conducted on these mineralizations had the purpose of integrate the data of chemical elements behavior during the shearing/mineralizing event, and its influence on the isotopic systems Rb-Sr and Sm-Nd. The studies of chemical mobility in the auriferous mineralizations showed that elements that during the shearing displayed in general an immobile behavior were Al, Ti and Zr. Among the elements that were mobilized during the event, K and Rb showed mass gain in ali belts of transformed rocks, while the elements Ca, Na and Sr normally lost mass. Petrographic studies showed that the minerais biotite and plagioclase, in all investigated mineralizations, played an important role in the chemical reactions occurred in the transformed rocks to the generation of muscovite, cordierite and sillimanite, justifying the input of K to the formation of muscovite, and the release of Na and Ca from plagioclase to the fluid phase. In the São Francisco auriferous mineralization, the results of the Rb-Sr isotopic analysis yielded ages of 645 ± 19 Ma and 596 ± 17 Ma, with both samples, from original and transformed rocks. Two ages, 569 ± 20 Ma. and 554 ± 19 Ma., were obtained with samples frem the transformed rocks domain. These ages suggest that there were two metamorphic pulses during the emplacement of the mineralized shearing zone. The Sm-Nd data yielded TDM ages of 1,31 Ga and 1,26 Ga with 3Nd (0,6 Ga) of -0,26 e -0,40 for the original and final transformed rocks, respectively. In case of the orthogneisses of Caicó Complex, e.g. the Ponta da Serra and Fazenda Simpático mineralizations, the Rb-Sr data did not yield ages with geological significance. In the Ponta da Serra mineralization, the Sm-Nd isotopic data yielded T DM ages of 2,56 Ga and 2,63 Ga to the original rocks and of 2,71 Ga to the mineralized sheared rock, and values of 3Nd (2,0 Ga) between -3,70 e -5,42 to the original and sheared rock, respectively. In the Fazenda Simpático, Sm-Nd data yielded TDM between 2,65 and 2,69 Ga with values of 3Nd (2,0 Ga) between -5,25 e -5,52. Considering the Sm-Nd data, the TDM ages may be admitted as the age of the parental magma extraction, producer of the protoliths of the orthogneisses from Ponta da Serra and Fazenda Simpático mineralizations. The chemical mobility studies showed that in the basement hosted mineralizations, Rb achieved mass while Sr lost mass, as Sm as well as Nd were strongly mobilized. The Sm/Nd ratio remained constant, however, confirming the isochemical character of those elements. In the basement mineralizations, Rb-Sr ages are destituted of geological significance, because of the partial opening of the isotopic system during the tectono-metamorphic transformations. In the tungsten mineralization, the diagram Sm-Nd constructed with the whole-rock data of calcsilicatic and the high-temperature paragenesis (garnet, diopside and iron-pargasitic hornblende) indicated an 631 ± 24 Ma age, while with the whole-rock data and low-temperature paragenesis (vesuvianite, epidote and calcite), a 537 ± 107 Ma age was obtained. These ages, associated with the petrographic observations, suggest that there was a time gap among the hydrothernal events responsible by the formation of the high and low temperature paragenesis in the calcsilicatic rocks mineralized in scheelite