Thermodynamics of the kaolinite-group minerals

The enthalpies of formation of kaolinite and dickite were determined by high-temperature melt solution calorimetry to be ΔfH°(298.15 K) = −4118 ± 10 and −4127 ±10 kJ/mol, respectively. These data represent the first calorimetric confirmation of the metastability of kaolinite with respect to dickite.     

Thermodynamics of feldspathoid solutions

We have developed models for the thermody-namic properties of nephelines, kalsilites, and leucites in the simple system NaAlSiO₄?KAlSiO₄?Ca_0.5AlSiO₄?SiO₂?H₂O that are consistent with all known constraints on subsolidus equilibria and thermodynamic properties, and have integrated them into the existing MELTS software package. The model for nepheline is formulated for the simplifying assumptions that (1) a molecular mixing-type approximation describes changes in the configurational entropy associated with the coupled exchange substitutions □Si?NaAl and □Ca? Na₂ and that (2) Na⁺ and K⁺ display long–range non-convergent ordering between a large cation and the three small cation sites in the Na₄Al₄Si₄O₁₆ formula unit. Notable features of the model include the prediction that the mineral tetrakalsilite (“panunzite”, sensu stricto) results from anti-ordering of Na and K between the large cation and the three small cation sites in the nepheline structure at high temperatures, an average dT/dP slope of about 55^°/kbar for the reaction over the temperature and pressure ranges 800–1050 ^°C and 500–5000 bars, roughly symmetric (i.e. quadratic) solution behavior of the K–Na substitution along joins between fully ordered components in nepheline, and large positive Gibbs energies for the nepheline reciprocal reactions and and for the leucite reciprocal reaction      

The oxygen isotopic composition of uranium minerals: A review

Uranium ore is an essential material in the preparation of nuclear fuel for civilian as well as military uses. Uranium is first extracted from uranium-bearing minerals using a variety of reagents, and is precipitated from solutions as yellow cake prior to isotope enrichment processes. The disintegration of the former Eastern Bloc in the 1990s and frequent unrest in the Middle East have underscored the need for better characterizing source uranium ores for forensic and attribution purposes.The world's major deposits of U occur in several distinctly different geological environments. Fourteen principal types of U deposits and rocks with elevated uranium contents are recognized with more than 40 subtypes. Combining our own analysis and literature data, we have amassed over 250 oxygen isotope data from 13 major U-producing countries, which vary widely from − 32 to + 11‰. However, interpreting the oxygen isotopic composition of uraninite in terms of the composition of the fluid from which it precipitated, or interacted with, requires knowledge of the fractionation factor and temperature of interactions, which are not always available. Since each deposit type occurs within a unique geologic setting and is generally formed from chemically distinct fluids, the chemical compositions of the uranium ores are also distinct: uranium deposits that form in igneous rocks have higher trace element compositions relative to sandstone-hosted deposits. Our data shows that one of the most useful techniques for distinguishing between uranium ore is to use a combination of δ¹⁸O values and rare-earth elements (e.g., La/Yb ratios). These methods may allow investigators to trace uranium ore back to the source.     

石笋矿物类型、成因及其对气候和环境的指示

洞穴石笋的矿物组成分为方解石、文石和文石-方解石三种类型。本文总结了国内外已有的研究成果,并结合野外观测现象和数据,讨论了影响石笋矿物形成和转变的因素,分析了利用石笋矿物类型特征研究古气候和古环境变化的可行性。洞内滴水饱和度和滴水中Mg/Ca比值是影响石笋矿物类型的主要因素:当滴水Mg/Ca 比值较低（Mg/Ca＜1或<<1）时,滴水饱和度较低易形成方解石,而文石沉积则需要更高的滴水饱和度;当滴水Mg/Ca 比值较高（Mg/Ca≥1）时,方解石相对文石沉积需要更高的滴水饱和度。洞穴围岩镁含量高且滴水多而稳定的洞内环境是我国南方大量文石笋发育的主要原因。长期处于滴水淋滤环境的文石笋容易向方解石转变,但若滴水中Mg2+浓度较大,此转变过程会受到抑制。在围岩镁含量较低的洞穴中,干旱时期渗流水滞留时间长、滴水速率变慢,会造成滴水中Mg/Ca比值升高并引起文石沉积。因此,石笋矿物类型及矿物相转变可指示气候和环境的变化。      

Silicate solid solutions and geothermometry

Principal component analysis, using eigenvalues and eigenvectors, of the encountered variation in the chemistry of 153 garnets indicates the following: (1) In low grade metamorphic rocks, spessertite and almandine are distinctly isomorphous. The variability of pyrope content does not influence the binary Fe-Mn relationship. However there may be some influence of the grossularite content. (2) In high grade metamorphic rocks, pyrope and almandine are distinctly isomorphous. Variability of grossularite content does not affect the binary Mg-Fe relationship. However, variability in spessertite content may influence the linearity particularly when there is little pyrope.Similar statistical analysis of the chemical data on 119 samples of clinopyroxenes indicates that only significant changes in the concentrations of Al in octahedral and/or of Al in tetrahedral sites and Ti could cause some change in the FeMg ratio in the mineral.Principal component analysis of the data on coexisting garnet and clinopyroxene could be used to classify rocks into their petrogenetic types.Distribution coefficient calculated by assuming ideal binary solution of Mg and Fe members in pyroxene and garnet is useful to indicate the P-T of the formation of the rocks.     

Silicate solid solutions and geothermometry

The properties of the regular solution are described. A solid solution is assigned certain theoretical values of the heat of mixing and the results of the distribution of a component between two coexisting solutions are shown graphically on Roozeboom diagrams. Such representations may be useful in explaining the distribution of elements observed in natural mineral assemblages.     

Oxygen isotopic composition of minerals in the Kenna ureilite

The δ¹⁸O and δ¹⁷O values of olivine from Kenna are 7.6 and 3.0%, respectively, relative to SMOW. These values are typical of ureilites which form a unique group on a δ¹⁷O -δ¹⁸O graph. The ureilites are related to, but not directly derived from, the anhydrous phases of C2 and C3 meteorites. The ¹⁸O/¹⁶O fractionation between pyroxene and olivine is 0.60, indicating a temperature of last equilibration of 1000 ± 100°C.     

Thermodynamic mixing behavior of synthetic Ca-Tschermak–diopside pyroxene solid solutions: II. Heat of mixing and activity–composition relationships

The heat of mixing for the binary solid solution diopside–Ca-Tschermak was investigated at T = 980 K by lead borate solution calorimetry. A new statistical technique was applied to overcome the problem of using experimental data of various precisions. A two-parameter Margules model was fitted to the calorimetric data leading to W _CaTs–Di^H = 31.3 ± 3.4 kJ mol⁻¹ and W ^H _Di–CaTs = 2.4 ± 4.3 kJ mol⁻¹. The results are in good agreement with calorimetric data given in the literature. They agree also with enthalpy data that were extracted from phase equilibrium experiments. With configurational entropy values taken from the literature, the volume and the vibrational entropy, presented in Part I of this work, and the enthalpy data of this study, the activity–composition relationships of the diopside–Ca-Tschermak binary were calculated.     

Hydrotalcite-like solid solutions with variable SO 4 2− and CO 3 2− contents at 50° C

Hydrotalcite-like solid solutions have been synthesized by coprecipitation in basic solutions with variable SO ₄ ^2? /CO ₃ ^2? ratios. Chemical determination of CO ₃ ^2? in the interlayer was impossible because of the presence of minor hydromagnesite. SO ₄ ^2? was determined both by chemical analysis and X-ray photoelectron spectroscopy (XPS), the two methods giving similar results. A Raman spectrometry gave additional data on the SO ₄ ^2? /CO ₃ ^2? ratio. Then, the stoichiometry of the anionic interlayers, X _s , X _c , and X _OH were determined, and the influence of X _s on the c′ parameter (increasing from c′=7.97 Å to c′=8.63 Å between X _s =0 and X _s =1) was characterized. In addition, a partitioning curve of SO ₄ ^2? and CO ₃ ^2? between aqueous solutions and hydrotalcite-like compounds was established. Its general shape strongly suggests a miscibility gap between a sulfate-rich end and a carbonate-rich solid solution (maximum SO ₄ ^2? /CO ₃ ^2? about 0.2). This result explains why most of the hydrotalcites synthesized during experimental alteration of basaltic glasses by sea-water (a sulfate-rich solution) are CO ₃ ^2? -rich solid solutions.     

Thermodynamics of NaOH(aq) in hydrothermal solutions

Apparent molar volumes and osmotic coefficients of NaOH solutions, calculated from critically evaluated literature data on volumes and vapor pressures, were used to fit the Pitzer equations to yield ion-interaction parameters as a function of temperature and pressure. These parameters allow the calculation of osmotic and activity coefficients from 0–350°C, saturation pressure to about 400 bars and 0–10 molal NaOH, and volumetric properties at saturation pressure over the same temperature and concentration range. Because the parameters for osmotic and activity coefficients above 300°C are based on less precise data, and because of possible ion-pairing above this temperature, calculated values above 300°C are considered only as best estimates available at this time. Partial molar volumes at infinite dilution calculated for NaOH are combined with literature data for NaCl, HCl, and H₂O to yield the pressure dependence of the ionization of water to 200°C, and are also combined with the potentiometric data of Sweeton et al. (1974) on the ionization of water to calculate the infinitely dilute partial molar volume of HCl to 300°C. Specific volumes of NaOH solutions at saturation pressure and up to 350°C are also calculated and tabulated.     

Platinum-group minerals and other solid inclusions in chromite of ophiolitic complexes: Occurrence and petrological significance

Summary Platinum-group mineral, silicate and other solid and fluid inclusions occur in disseminated and massive chromite in a variety of lithologies from ophiolitic and other mafic-ultramafic complex-types. The inclusions are small (<250 microns) and randomly distributed throughout their host. Silicate inclusions are modally more abundant than the other inclusion types. Platinum-group mineral phases are ruthenium-rich sulphides and PGE alloys are osmium-rich. Mafic silicates (olivine, pyroxenes, pargasitic-amphiboles, micas) are magnesium-, titanium-, and alkali-rich and felsic silicates are sodium-rich (albite, nepheline).The intimate association of these inclusions with chromite suggests that their origin must be considered within a chromite crystallization model. A hypothesis of origin is suggested wherein the platinum-group minerals and silicates are trapped as discrete, crystalline euhedral phases and silicate liquid during the precipitation of chromite. The similarity of physical characteristics, modal mineralogy and chemical compositions indicates that this model may be applicable to all mafic-ultramafic complex-types.

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Minerale der Platin-Gruppe und andere feste Einschlüsse in Chromiten aus Ophiolit-Komplexen: Vorkommen und petrologische Bedeutung

Zusammenfassung Minerale der Platin-Gruppe, Silikate und andere feste und flüssige Einschlüsse kommen in disseminierten und massiven Chromiten in einer Vielzahl von Gesteinen in ophiolitischen und anderen mafisch-ultramafischen Komplexen vor. Die Einschlüsse sind klein (<250 microns) und unregelmäßig im Chromit verteilt. Silikat-Einschlüsse sind modal weiter verbreitet als andere Arten von Einschlüssen. Minerale der Platin-Gruppe sind durch Ruthenium-reiche Sulfide und Osmium-reiche Legierungen vertreten. Mafische Silikate (Olivin, Pyroxen, pargasitische Amphibole, Glimmer) sind Magnesium-, Titan- und Alkali-reich; felsische Silikate sind Natrium-reich (Albit, Nephelin).Die ausgeprägte Assoziation dieser Einschlüsse mit Chromit weist darauf hin, daß ihre Herkunft im Zusammenhang mit einem Kristallisations-Modell für Chromit zu sehen ist. Ein genetisches Konzept wird vorgelegt, wobei die Platin-Gruppen-Minerale als gut ausgebildete, idiomorphe kristalline Phasen, und die Silikate als Silikatschmelze während des Ausfallens des Chromites eingeschlossen werden. Die Ähnlichkeit der physikalischen Eigenschaften, der modalen mineralogischen Zusammensetzung und der chemischen Zusammensetzung weisen darauf hin, daß dieses Modell auf alle mafisch-ultramafischen Komplexe anzuwenden ist.

     

Curtisite,idrialite and pendletonite,polycyclic aromatic hydrocarbon minerals: Their composition and origin

The rare polycyclic aromatic hydrocarbon minerals curtisite, pendletonite and idrialite have been analyzed by chromatography, and ultraviolet and mass spectrometry. Pendletonite is nearly pure coronene; the other minerals contain over 30 homologous series of CH, CHS and CHN compounds, with the total number of chemical components well above one hundred. The chemistry of the contributing compounds reflects the origin of the minerals in medium-temperature pyrolysis of organic matter. The components were further modified by extended equilibration at elevated temperatures in the subsurface and by recrystallization during migration. In this last step the high-melting pendletonite achieved its exceptional purity.     

Some features of minerals developing from gels of complex composition

Results of an investigation of the processes accompanying formation of pyrite, native arsenic, pitchblende, and coffinite are here reported. Differentiation of gel substance follows the pattern of processes inherent in colloids and grades into processes typical of crystalline substances. The colloidal origin of minerals determines the nature of paragenesie found in recrystallized ore. -- E.A. Alexandrov.     

固体矿产绿色勘查钻探技术方法探索与实践

西安矿产资源调查中心针对现有固体矿产地质调查（勘查）项目,积极探索和实践绿色地质勘查工作技术方法,因地制宜应用全液压履带钻机、便携式模块化钻机实施“一基多孔”,采用背包钻实施“以钻代槽”,通过优选环保型冲洗液,净化处理废弃冲洗液,控制临时占地规模等具体措施。与传统机场规格相比占地面积减少了80%~85%,临时便道修筑减少了60%~65%,工后复垦复绿达到了80%以上。通过绿色勘查成本费用分析,人员、临时用地（青苗）补偿、绿色环保材料及复垦复绿等费用成本总和降低了40%左右。最后探索实践了绿色勘查工作保障措施,对下一步绿色勘查工作提出了建议,为加强绿色勘查工作理念、完善相关的制度法规、激发绿色勘查工作活力提供了积极的导向。     

Computer simulation of mineral solid solutions

We discuss how two techniques, based on (1) lattice dynamics (lattice statics) simulations and (2) Monte Carlo methods may be used to calculate the thermodynamic properties of solid solutions and highly disordered systems. The lattice dynamics calculations involve a full free-energy structural optimisation of each of a number of configurations, followed by thermodynamic averaging. The Monte Carlo simulations include the explicit interchange of cations and use the semi-grand canonical ensemble for chemical potential differences. Both methods are readily applied to high pressures and elevated temperatures without the need for any new parameterisation. We discuss the application of the Monte Carlo technique to the study of surfaces. A range of examples, including binary oxides, spinels, carbonates and surface segregation, is used to illustrate the methods.     

End members,dominant valency,and identifying minerals of mixed composition

Two rules for identifying and naming minerals of mixed composition are compared. Olivine, monoclinic pyroxene, tourmaline, and mica are given as examples.