Direct calculation of thermodynamic properties of the barite/celestite solid solution from molecular principles

 Thermodynamic properties of the barite–celestite solid solution were calculated using molecular principles. Cation–cation (Ba–Ba, Sr–Sr, and Ba–Sr) interaction energies were derived from a number of random and ordered cation distributions which were energy-optimized using force potentials as incorporated in the program package GULP. With these interaction energies, diagrams for the enthalpy and free energy of mixing could be computed for the entire range of the solid solution between the barite and celestite end members and for a number of annealing temperatures. These thermodynamic data show that the solid solution is nonideal. The system has a tendency for Ba²⁺ and Sr²⁺ cations to order onto alternating layers ||(100). However, this ordering scheme is thermodynamically only relevant for annealing temperatures below approximately 500 K and systems that are kinetically inhibited during crystal growth. For sufficiently long annealing times at room temperature, the solid solution tends to exsolve with barite–celestite interfaces ||(100). The cell parameters a and c were calculated to have almost linear behavior for the whole solid solution, suggesting close to ideal behavior according to Vegard's law. In contrast, b tends to deviate positively from linearity, in agreement with experimental values. Received: 6 April 1999 / Revised, accepted: 29 September 1999     

Luminescence centers in anhydrite,barite, celestite and their synthesized analogs

The intrinsic luminescence center (LC) of SO ₄ ^2? appears at 360 nm in all types of sulfates, but is absent in sulfates with large quantities of impurities. Three nonequivalent Gd³⁺ LC have been observed in luminescence spectra of anhydrite. Gd³⁺, Ce³⁺ O ₂ ^? LC were established in celestite. Photoluminescence (PL) bands in the sulfates were assigned as follows: the band at 460 nm is related to Eu²⁺ (a connection with Al³⁺ or donor-acceptor pair is possible also) in sulfates of Ca and Ba; bands at 520 nm and 590 nm are related to VO₄, MoO₄ and TiO₄ substituting SO₄; the band at 660 nm is assigned to Ti³⁺ X-ray luminescence (XL) band at 620 nm is assigned to Ag⁺.     

EPR and ENDOR of the PO 4 2− radical in anhydrite,celestite and barite

Electron paramagnetic resonance (EPR) and eletron nuclear double resonance (ENDOR) low temperature measurements of natural anhydrite CaSO₄, celestite SrSO₄ and barite BaSO₄ have revealed the presence of PO ₄ ^2– radical. The principal values of the g tensor and the A tensor [MHz] of hyperfine interaction (HFI) are found to be g _xx =2.0124, g _yy =2.0159, g _zz =2.0098, A _xx =82.1, A _yy =81.4, A _zz =77.2 in CaSO4, g _xx =2.0250, g _yy =2.0070, g _zz =2.0131, A _xx =84.8, A _yy =82.7, A _zz = 90.5 in SrSO₄, g _xx =2.0302, g _yy =2.0079, g _zz =2.0135, A _xx =85.2, A _yy =82.3, A _zz =90.0 in BaSO₄. The principal axes A _xx , A _yy and A _zz are parallel to the crystallographic axes a, b, c in all three matrices. In anhydrite the principal g axes coincide with the A axes. In celestite and barite such coincidence is found to be only along the b axis (a low symmetry effect). The coherence effect of splitting of ENDOR lines by a strong microwave field has been detected. From the analysis of the relative intensities of the ENDOR lines of the PO ₄ ^2– radical in CaSO₄ the relation of probabilities of cross-relaxation processes W _x/W _xx =3.5 are evaluated.     

Electron paramagnetic resonance of the SO 4 3- radical in barite and celestite

The electron paramagnetic resonance (EPR) study of gammaor x-ray-irradiated natural barite and celestite has revealed the presence of a radiation center with principal values of the g tensor and the A tensor [MHz] of hyperfine interaction (from the ³³S isotope): g_xx=1.9963, g_yy=2.0073, g_zz=2.0025, A_xx=434, A_yy=447, A_zz=528 in BaSO₄, g_xx=1.9990, g_yy=2.0075, g_zz=2.0027, A_xx=426, A_yy=439, A_zz=520 in SrSO₄. The center has been identified as SO _3- ⁴ radical. The electron centers SO ₄ ^3- in barite have been found to be produced along with the hole centers SO ₄ ^3- , and maximum concentration of both centers is reached at a gamma-ray-radiation dose of about 5·10⁵ Gy. UV or thermal treatment causes both centers to disappear. The SO ₄ ^3- radicals proved to be more thermally stable than the SO ₄ ^3- radicals: within about 0.5 h the latter disappear at 125° C, whereas the former do so at 180° C.     

Electron paramagnetic resonance of PO 3 2− and SO 3 − radicals in anhydrite,celestite and barite: the hyperfine structure and dynamics

Electron paramagnetic resonance (EPR) measurements of natural anhydrite CaSO₄, celestite SrSO₄ and barite BaSO₄ have revealed the presence of PO ₃ ^2? and SO ₃ ^? radicals. Hyperfine structure from³³S has been detected and measured for the first time. Low-symmetry effects, which are manifested in noncoincidence of g and hyperfine axes, were observed for SO ₃ ^? . The dynamics of one of the two SO ₃ ^? types in anhydrite has been investigated. Variations of spin Hamiltonian parameters with temperature have been attributed to thermally induced jumps between the two magnetically inequivalent sites of this center.     

Xenon in Archean barite: Weak decay of Ba, mass-dependent isotopic fractionation and implication for barite formation

In order to investigate radioactive decay of ¹³⁰Ba and ¹³²Ba which have half-lives on the order 10²⁰-10²¹ a, the isotopic composition of xenon has been measured in 3.5 Ga barite of the Dresser Formation, Pilbara, Western Australia. The analyzed samples were collected at about 86 m depth from a diamond drill core (Pilbara Drilling Project). The fact that the sample has been shielded from modern cosmic ray exposure reduces the number of potentially interfering production pathways, simplifying interpretation of the Xe isotope spectrum. This spectrum is clearly distinct from that of either modern or ancient atmospheric Xe. A strong excess of ¹³⁰Xe is identified, as well as other isotopic excursions which are attributed to mass-dependent isotopic fractionation and contributions from products of uranium fission. The mass-dependent fractionation, estimated at 2.1 ± 0.3% amu⁻¹, can be accounted for by mutual diffusion and Rayleigh distillation during barite formation that is consistent with geological constraints. After correction for mass-dependent fractionation, the concentrations of fissiogenic Xe isotopes demonstrate that the U-Xe isotope system has remained closed over 3.5 Ga. From the excess of ¹³⁰Xe, the two successive electron capture half life of this isotope is estimated at 6.0 ± 1.1 × 10²⁰ a, which is 3.4 times faster than previously estimated (Meshik et al., 2001). We could not find evidence of ¹³²Ba decay within our Xe isotope spectra.     

甲烷和固态硫酸钙的热化学还原反应模拟实验初步研究

碳酸盐岩地层中常伴有硫酸盐岩的沉积，在一定的温度和压力条件下，干酪根热降解生成的气态烃与硫酸盐岩接触后发生热化学还原反应(简称为TSR反应)，使气态烃消失，这可能是造成生气死亡线的主要原因之一。本文对CH4-CaSO4热化学还原反应的热力学问题进行了探讨，发现该反应能够自发进行，而且升高温度对反应有利。利用高温高压模拟装置对CH4-CaSO4反应体系进行了初步的模拟实验研究，通过微库仑、气相色谱和傅里叶变换红外光谱(FT-IR)等分析手段对实验结果进行了进一步验证。结果表明，甲烷和固态硫酸钙能够发生热化学还原反应，生成硫化氢、碳酸钙和水。最后，将CH4-CaSO4反应体系同国内外的研究工作进行了对比，认为本实验研究能够更好地补充和完善TSR反应体系，解释地质条件下工业气藏的死亡线问题。     

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

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

Dual-thermodynamic estimation of stoichiometry and stability of solid solution end members in aqueous–solid solution systems

The dual-thermodynamic (DualTh) approach is shown to provide a useful alternative to other methods in: (i) forward modelling of equilibrium speciation, activities, and element partitioning in a heterogeneous system involving several variable-composition phases, such as the aqueous–solid solution system; (ii) estimation of interaction parameters of a non-ideal mixing model from known bulk compositions of coexisting aqueous and solid-solution phases; and (iii) retrieval of unknown stoichiometries and apparent standard chemical potentials of trace solid-solution end-members. Inverse-modelling tasks (ii) and (iii) can be performed when the solid solution of interest is shown experimentally to co-exist with the aqueous phase either in the equilibrium or at the minimum stoichiometric saturation state.DualTh calculations exploit the ability of Gibbs energy minimisation (GEM) algorithms to find simultaneously two numerical solutions of the isobaric–isothermal chemical equilibrium speciation problem: (1) primal solution x — a vector of amounts of components (species) in phases; and (2) dual solution u — a vector of chemical potentials of stoichiometry units (usually chemical elements and charge). Conversely, the chemical potential of a phase component can be found in two complementary ways: (i) primal via its standard-state potential, concentration and activity coefficient (the latter two are functions of the x vector); and (ii) dual through its formula stoichiometry multiplied by the u vector. The DualTh methods compare primal and dual values of the chemical potential in simple and straightforward equations that can be easily computed in a spreadsheet, or implemented in GEM geochemical modelling codes.     

重晶石成矿地质特征、成矿作用及成矿机制

重晶石全球范围内广泛分布,重晶石矿床具有形成时代多、元素来源复杂、成矿作用多样等特点,目前有关重晶石矿床的成因仍存在争议。文章系统分析前人的研究成果,厘定了不同类型的典型矿床、成矿时代规律,探讨了不同类型矿床中成矿元素来源、成矿作用及成矿机制。矿床类型方面,重晶石矿可分为沉积型、岩浆热液型、层控型、火山-沉积型和风化（残积）型,主要分布在特提斯成矿域和劳亚成矿域,其他地区主要是冈瓦纳成矿域和环太平洋成矿域,其中沉积型是最主要的成矿类型,占重晶石矿床的60%以上。成矿时代方面,重晶石的成矿时代主要为古生代和中生代,赋矿岩系以沉积岩为主,其次为岩浆岩。成矿物质来源方面,全球典型重晶石矿床中的S同位素和Sr同位素显示,成矿物质来源具有多源性、多样性、差异复合性等特点。成矿机制方面,重晶石的成矿机理复杂,具有多阶段性、多因素等特点。     

The solid solution chemistry of vesuvianite

Solid solution in vesuvianite is elucidated by examining chemical trends and cation abundances in 22 microprobe analyses of samples from the Big Maria Mountains, southeastern California. Two recent structure refinements indicate 50 filled cation sites per formula, providing the basis for data normalization. Previous optical absorption and Mössbauer studies help clarify site occupancies. Stoichiometric abundances of Si and Ca + Na indicate 18 and 19 per formula, filling all 4- and 8-fold sites respectively. The four 6-fold A-sites are filled with Al. The solid solution occurs mainly within the eight 6-fold AlFe-sites (Al, Mg, Fe²⁺, Fe³⁺, Ti) and one 5-fold B-site (Mg, Fe²⁺, Fe³⁺). Chemical trends and crystal chemical constraints delineate eight independent substitutions.An extensive solid solution in the elements Mg, Fe, Al, and Ti suggests considerable potential as a petrogenetic indicator. In order to treat equilibria involving vesuvianite thermodynamically, a reference composition must be chosen and activity-composition relations modeled. For a reference composition, Mg-vesuvianite (Fe, Ti, Na-free) was chosen because of its chemical simplicity, but problems in ascertaining its stoichiometry have led previous workers to propose at least six different formulas. In this study, its formula is determined from the microprobe analyses by applying exchange vectors to substitute components of pure Mg-vesuvianite for Fe and Ti. This yields Ca₁₉Mg₂Al₁₁-Si₁₈ O₆₉(OH)₉, with AlFe-sites=MgAl₇, and B-sites=Mg. Subdivision of the AlFe-sites into at least two distinct sites is suggested by observed chemical trends which are explanable only when different substitutions are considered to operate within different AlFe-sites.A thermodynamic mole fraction is formulated for Mg-vesuvianite based on an ideal mixing-on-sites solution model. A method is provided for estimating the distribution of Fe between the AlFe- and B-sites. Thermodynamic mole fractions calculated using Fe site distributions estimated from microprobe data yield results similar to those calulated using Fe site distributions determined from Mössbauer analysis.     

青海大风山锶矿床中天青石的成分特征

青海大风山是中国典型的陆相碳酸盐-硫酸盐沉积组合锶矿床,也是中国目前储量最大的锶矿床.文章对大风山矿床中不同产状的天青石进行了系统的电子探针测试,分析归纳了不同类型矿石中天青石的成分变化规律,发现同心圆状天青石中的SrO含量最高,其次是细纤维状、花朵状、钟乳状、假层纹状、粗纤维状天青石,隐晶质天青石含量最低.通过与江西省萍乡包公庙、宜春慈化、湖南浏阳永和海相碳酸盐沉积组合锶矿床、重庆大足、玉峡及干沟等海相碳酸盐-硫酸盐沉积组合锶矿床、云南金顶硫化物-天青石层控伴生锶矿床天青石的对比,总结了不同类型矿床中天青石的特征,指出青海大风山天青石矿床成分简单,除SrSO4较高外,其余均相对较低,有利于碳酸锶的提取和回收,具有很高的工业价值.     

Petrogenesis of a Senonian barite deposit,Judean Desert,Israel

A small productive barite deposit in chalks and cherts of the Senonian Mishash Fm, Judean Desert, Israel, exhibits both syngenetic and epigenetic features. A sedimentary origin is proposed on the basis of the coarse bedding within the granular barite ore, intimate interbedding on both the macro and micro scales with chalk, chert and clay, the fine crystallinity of the barite, and the trace element composition. Barite and calcite were redeposited from solutions at a later stage resulting in the epigenetic features. A marine or marine organic origin for the barium is considered.     

沉积岩容矿天青石矿床的发育特征与成因综述

沉积岩容矿的天青石矿床是锶最主要的来源.文章对全球该类矿床的资料进行了系统梳理,对矿床的发育特征和成因进行了综述和探讨.研究显示:①该类矿床的产出与含石膏或硬石膏的蒸发盐密切相关,或赋存在碳酸盐岩-蒸发岩沉积建造中,或出现在蒸发岩底辟环境;②多数为后生成因,表现为富锶流体交代石膏或硬石膏,或富锶流体与富硫酸盐流体混合、充填开放空间;少数矿床为同生成因,天青石直接从蒸发环境的水体中沉淀出;③后生天青石矿床中的锶可以来自不同途径,包括盆地流体与富钙矿物相互作用萃取的锶、碳酸盐岩重结晶过程文石转变为方解石或硬石膏转变为石膏释放的锶;同生天青石矿床中的锶来自沉积水体本身,沉积源区岩石提供了锶;④天青石中的硫来源于围岩地层中的石膏或硬石膏,有些矿床中的硫来自发生过硫酸盐还原作用后的(溶解的)石膏/硬石膏,而在个别矿床中,还原硫氧化成硫酸盐提供了部分硫;⑤一些天青石矿床中出现有铅锌硫化物,两者可以有成因关系,也可以无成因关系;⑥少数天青石矿床中重晶石含量较高,与高Ba/Sr流体与富硫酸盐流体混合有关.天青石从低钡流体中结晶时,钡在流体中含量的震荡变化会导致SrSO4-BaSO4固溶体的形成,从而使天青石出现环带或出溶结构.     

The energetics of natural garnet solid solution

Approximate mixing properties of the dominant calcium silicate end-member components of natural garnets, namely grossularite, andradite and uvarovite, have been derived through theoretical thermodynamic and crystal chemical analysis, and appropriate reduction of the available experimental data. The stability of the solid solution with respect to phase separation in the ternary system has been analyzed. Finally, a general model is presented as to the approximate mixing properties of multicomponent natural garnet solid solution involving substitutions in both eight and six coordinated sites.     

The energetics of natural garnet solid solution

Approximate mixing properties of the end-member components of the quarternary garnet solid solution, (Fe,Mg,Ca,Mn)₃Al₂Si₃O₁₂, have been derived through theoretical analysis of observational data, combined with certain experimental results and crystal chemical considerations. The results suggest that the mixing of pyrope with grossularite, spessartite, and almandine would involve significant positive excess free energies of mixing leading to the critical mixing temperatures of 694±55, 535±140, and 479±63 °C respectively. Spessartite would mix with almandine nearly ideally, and with grossularite with small positive deviation from ideality. The quarternary solution reduces essentially to a ternary mixture of pyrope, grossularite, and almandine + spessartite. The solid solubility relation, and tie line coordinates in this ternary system has been calculated as a function of temperature; the solid solution is found to be intrinsically stable for practically all ternary compositions at 600 °C.     

Structure and lattice vibrations of Mg-Al spinel solid solution

X-ray structure refinements have been made for nonstoichiometric (MgO · 3Al₂O₃) and stoichiometric Mg-Al spinels. Several structure variations with chemical composition have been observed and are discussed in relation to Al substitution in tetrahedral sites. Infrared reflection and Raman spectra of the single crystal of the nonstoichiometric spinel (MgO · 3Al₂O₃) have been measured and analyzed. The results obtained are compared with those reported for the stoichiometric sample. From the infrared and Raman frequencies reported for the stoichiometric Mg-Al spinel, which are partly complemented with our results, the effective ionic charges of the ions in MgAl₂O₄ have been estimated on the basis of the rigid ion model.