Synthesis, crystal structure and crystal chemistry of ferri-clinoholmquistite, ?Li 2Mg 3Fe 3+ 2Si 8O 22(OH) 2

This work reports the synthesis of ferri-clinoholmquistite, nominally _Li2(Mg₃Fe³⁺₂)Si₈O₂₂(OH)₂, at varying f_O2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe₂O₃ ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is ^M2(Mg,Fe²⁺) ^M4(Mg,Fe²⁺) ^M2Fe³⁺_–1 ^M4Li_–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) ų. Mössbauer spectra show that Fe³⁺ is strongly ordered at M2 in all samples, whereas Fe²⁺ is disordered over the B and C sites. FTIR analysis shows that the amount of ^CFe²⁺ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.     

Calculation of the standard partial molal thermodynamic properties and dissociation constants of aqueous HCl0 and HBr0 at temperatures to 1000°C and pressures to 5 kbar

Dissociation constants of aqueous ion pairs HCl⁰ and HBr⁰ derived in the literature from vapor pressure and supercritical conductance measurements Quist and Marshall 1968b, Frantz and Marshall 1984 were used to calculate the standard partial molal thermodynamic properties of the species at 25°C and 1 bar. Regression of the data with the aid of revised Helgeson-Kirkham-Flowers equations of state Helgeson et al 1981, Tanger 1988, Shock et al 1989 resulted in a set of equations-of-state parameters that permits accurate calculation of the thermodynamic properties of the species at high temperatures and pressures. These properties and parameters reproduce generally within 0.1 log unit (with observed maximum deviation of 0.23 log unit) the log K values for HBr⁰ and HCl⁰ given by Quist and Marshall (1968b) and Frantz and Marshall (1984), respectively, at temperatures to 800°C and pressures to 5 kbar.     

The coprecipitation of Sr2+ with calcite at 25°C and 1 atm

The incorporation of Sr²⁺ into calcite at earth surface aqueous conditions is affected by the absolute concentration of Sr²⁺, the presence of Ba²⁺ and NaCl in the solution, and the rate of precipitation. At solution ratios (molar) of Sr²⁺ to Ca²⁺ in the low 10⁻³ range, which yield calcites with several hundred ppm Sr²⁺, K^sr_calcite typically assumes a value between 0.10 and 0.20. Above these concentrations the value of k^Sr_calcite drops to approximately 0.06. Furthermore, if minor amounts of Ba²⁺ or large amounts of Na⁺ (0.48 M) are added to a dilute Sr²⁺ solution, a value around 0.06 for k^Sr_calciteis found. This “strontium concentration effect” and the associated “competitive cation effect” suggest that small amounts of Sr²⁺ may be incorporated into a limited number of nonlattice sites in calcite. Incorporation of Sr²⁺ into these sites, presumably defects, noticeably affects k^Sr_calcite only at low Sr²⁺ concentrations and in the absence of competition from other large cations.An increase in k^Sr_calcite with rate of precipitation, qualitatively similar to that found in other studies, was observed only when precipitation times were decreased from days to hours.For many geologic settings a partition coefficient for Sr²⁺ into calcite of 0.06 appears appropriate, but there are situations—very low Sr²⁺ concentrations, the presence of Mg²⁺, and fast precipitation rates—in which a larger value might better approximate natural partitioning.     

Local relaxation around [6]Cr 3+ in synthetic pyrope–knorringite garnets, [8]Mg 3 [6](Al 1-X Cr X 3+) 2 [4]Si 3O 12, from electronic absorption spectra

Pyrope-knorringite garnets, Mg₃(Al_1-X Cr³⁺_X)₂Si₃O₁₂ with X=0.25, 0.50, and 1.00, were synthesized between 9 and 16 GPa and 1300 and 1600 °C, using multianvil high-pressure techniques. The garnets with X=0.25 and 0.50 are fine-grained, pink and violet in color. The end-member knorringites with X=1.00 are black when compact and gray when coarse-grained. The fine powder is greenish gray in natural light and pale pink under a tungsten lamp. Powder remission spectra in the wavenumber range 30 000–10 000 cm^–1 on finely powdered crystals were measured by two different methods: (I.) by the use of a small integrating sphere for small samples or (II.) microscope-spectrometric measurement using diffusely reflected radiation from a 45° illuminated microsample. Both methods yielded similar diffuse reflectance spectra. The following crystal-field parameters of ^[6]Cr³⁺ were determined for garnets with X=0.25, 0.50, 1.00: 10 Dq=17 856, 17 596, 17 286 cm^–1; and B=654, 677, 706 cm^–1; nephelauxetic ratio =(B_field/B_free)= 0.71, 0.74, 0.77. The -values indicate decreasing covalency of the Cr–O bond with increasing Cr content. The 10 Dq value for together with the mean Cr–O distance in end-member knorringite, 1.96 Å (Novak and Gibbs 1971), were used to calculate from the spectral data, local mean Cr–O distances (Langer 2001a) as a function of composition. The results indicate relatively strong local site relaxation with a value of =0.77.     

Crystal field and covalency of octahedral chromium in natural [8](Mg1?xCax) 3[6] (Al0.67Cr0.33)2Si3O12 garnets from upper mantle rocks

In the course of a thorough study of the influences of the second coordination sphere on the crystal field parameters of the 3d ^N -ions and the character of 3d ^N –O bonds in oxygen based minerals, 19 natural Cr³⁺-bearing (Mg,Ca)-garnets from upper mantle rocks were analysed and studied by electronic absorption spectroscopy, EAS. The garnets had compositions with populations of the ^[8] X-sites by 0.881 ± 0.053 (Ca + Mg) and changing Ca-fractions in the range 0.020 ≤ w _Ca[8] ≤ 0.745, while the ^[6] Y-site fraction was constant with x _Cr³⁺ _[6] = 0.335 ± 0.023. The garnets had colours from deeply violet-red for low Ca-contents (up to x _Ca = 0.28), grey with 0.28 ≤ x _Ca ≤ 0.4 and green with 0.4 ≤ x _Ca. The crystal field parameter of octahedral Cr³⁺ 10Dq decreases strongly on increasing Ca-fraction from 17,850 cm⁻¹ at x _Ca[8] = 0.020 to 16,580 cm⁻¹ at x _Ca[8] = 0.745. The data could be fit with two model which do statistically not differ: (1) two linear functions with a discontinuity close to x _Ca[8] ≈ 0.3,

Rates of aragonite conversion to calcite in dilute aqueous fluids at 50 to 100°C: experimental calibration using Ca-isotope attenuation

Aragonite was converted to calcite in dilute CaCl₂ fluid at temperatures ranging from 50 to 100°C. Surface areas of aragonite and calcite seed crystals were varied by over an order of magnitude to permit independent assessment of calcite nucleation and growth processes. Aragonite conversion rates were measured using isotopic attenuation of dissolved ⁴⁴Ca, which was added to the fluid at the beginning of each experiment. Measured conversion rates were found to be constant with respect to time and proportional to the initial surface area of aragonite. Rates were independent of the surface area of calcite seed crystals owing to heterogeneous nucleation of calcite on aragonite during experiments. The data imply that calcite nucleates on aragonite surfaces until the level of saturation with respect to calcite reaches a critical threshold value where further nucleation is precluded. Thereafter, conversion to calcite occurs at a steady state rate consistent with aragonite dissolution at a fixed level of saturation. Aragonite converts to calcite under these conditions and in dilute fluids at rates of approximately 10 and 100 microns/yr at 25 and 100°C, respectively.     

大气气溶胶中NO3- ,SO42-研究

根据对国内外有关文献资料的总结归纳，对气溶胶中ＮＯ＾－３，ＳＯ＾２－４的研究现状及其在不同类型样品中的浓度量值分别进行了阐述；对雪冰层中的ＮＯ＾－３和ＳＯ＾２－４进行了本底划分，并对这些本底的来源，组成及特征进行了分析。     

Calcite Dissolution in Deionized Water from 50°C to 250°C at 10 MPa: Rate Equation and Reaction Order

Carbonate minerals and water （or geofluids） reactions are important for modeling of geochemical processes and have received considerable attention over the past decades. The calcite dissolution rates from 50℃ to 250℃ at 10 MPa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor. The dissolution began near the equilibrium with c/ceq 〉 0.3 and finally reached the equilibrium at 100℃-250℃, so the corresponding solubility was also determined as 1.87, 2.02, 2.02 and 1.88×10^-4.mol/L at 100℃, 150℃, 200℃ and 250℃ respectively, which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃ and 200℃. The experimental dissolution rate not only increased with temperature, but also had a rapid increase between 150℃ and 200℃ at a constant flow rate of 4 mL/min. The measured dissolution rates can be described using rate equations of R = k（1-c/ceq）n or R = kc-n. In these equations the reaction order n changed with temperature, which indicates that n was a variable rather than a constant, and the activation energy was 13.4 kJ/mol calculated with R = k（1-c/ceq）n or 18.0 kJ/mol with R = kc^-n, which is a little lower than the surface controlled values. The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.     

鄂尔多斯盆地靖边气田北部马五41亚段储层特征

本文根据岩心和铸体薄片观察与储层物性分析,系统研究了鄂尔多斯盆地靖边气田北部马五₄¹亚段的储层特征。结果表明:马五₄¹亚段储集空间以晶间孔、溶蚀孔洞和微裂缝为主,为典型的低孔低渗型储层;溶蚀作用对储层的发育具有决定性作用。根据储层物性和产量等参数,将马五₄¹亚段划分为4类储层,其中Ⅰ、Ⅱ类为优质储层,主要分布在研究区西部和北部。     

Solubility of the buffer assemblage pyrite + pyrrhotite + magnetite in NaCl solutions from 200 to 350°C

In the design of hydrothermal solubility studies it is important that the system be completely defined chemically. If the solubilities of minerals containing m metallic elements are to be determined in hydrothermal NaCl solutions, the phase rule requires that a total of m + 6 independent intensive parameters be controlled or measured in order to determine completely the system.In this study the solubility of the univariant assemblage pyrite + pyrrhotite + magnetite has been determined in vapor saturated hydrothermal solutions from 200 to 350°C for NaCl concentrations ranging from 0.0 to 5.0 molal. At any temperature, oxygen and sulfur fugacities were buffered by the chosen assemblage. System pH was determined from excess CO₂ partial pressures and computed ionic equilibria. Equilibrium constants were calculated by regression analysis of solubility data. The results show that more than 10 ppm of each mineral can dissolve in typical hydrothermal solutions under geologically realistic conditions. Solubilities were best represented by the species Fe²⁺ and FeCl⁺ at 200 and 250°C; Fe²⁺, FeCl⁺ and FeCl₂⁰ at 300°C; and Fe²⁺ and FeCl₂⁰ at 350°C. Ore deposition would occur by lowering temperature, diluting chloride concentration, or by raising pH through wall rock alteration reactions.     

祁漫塔格成矿带磁铁矿Fe2+/Fe3+比值测定方法对比研究

为了厘清磁铁矿成分测试过程中Fe²⁺/Fe³⁺比值分析各种方法的准确性及适用范围;采用直接测氧法、Lβ/Lα强度比值法、电价差值法、剩余氧法和穆斯堡尔谱法,对祁漫塔格成矿带中典型矿床中磁铁矿的Fe²⁺/Fe³⁺比值进行了研究,结果表明电价差值法、剩余氧法和穆斯堡尔谱法是相对比较准确的测试方法,但穆斯堡尔谱法不是原位分析方法,存在适用范围的缺陷。     

三元体系K+,Mg2+∥B4O72--H2O 348K稳定相平衡研究

采用等温溶解平衡法开展了三元体系K+,Mg2+∥B4O72--H2O 348K的稳定相平衡研究,获得溶解度数据及平衡液相的密度,折光率,pH值。根据溶解度数据绘制了三元体系稳定相图。该三元体系在348K时的稳定相图含有一个共饱点E、两条单变量曲线AE,BE和两个结晶相区MgB4O7.9H2O(AECA)和K2B4O7·4H2O(BEDB)。共饱点的平衡固相组成为MgB4O7·9H2O和K2B4O7·4H2O,对应的平衡液相组成为w(K2B4O7)=42.28%、w(MgB4O7)=8.11%。研究结果表明,该三元体系属于简单共饱和型,无复盐和固溶体形成。K2B4O7·4H2O和MgB4O7·9H2O互相存在盐溶作用,使得这两种盐的溶解度明显增大。平衡液相的密度、折光率均随溶液中K2B4O7质量分数的增大而增大。     

Co-precipitation of Sr2+ and Ba2+ with aragonite by membrane diffusion of CO2 between 10 and 50 °C

Aragonite is precipitated by a new CO₂-diffusion technique from a Ca²⁺–Mg²⁺–Cl⁻ solution between 10 and 50 °C. Crystallisation of aragonite instead of calcite occurs by maintaining a [Mg²⁺]/[Ca²⁺] ratio of 2 in the fluid. The dissolved inorganic carbon (DIC) is received by diffusion of CO₂ through a polyethylene membrane (diffusion coefficient: D_CO2=10^−6.4 cm² s⁻¹ at 19 °C). It is suggested that significant amounts of DIC may be transferred by diffusion of CO₂ in natural systems if the CO₂ gradient is high. The CO₂-diffusion technique is used as a kind of simple mixed flow reactor for the co-precipitation of barium and strontium with aragonite. The distribution coefficients of Ba²⁺ and Sr²⁺ decrease from 10 to 50 °C according to D_Ba,a*=2.42−0.03595T (°C) and D_Sr,a*=1.32−0.005091T (°C). At 25 °C, the distribution coefficients are D_Ba,a*=1.5±0.1 and D_Sr,a*=1.19±0.03. The effect of temperature on D_Ba,a* is about one order of magnitude higher versus that on D_Sr,a*. Thus, Ba²⁺ may be a potential paleotemperature indicator if the composition of the solution is known.     

Experimental studies of Ta2O5 and columbite–tantalite solubility in fluoride solutions from 300 to 550°C and 50 to 100 MPa

It is well established that the fractionation of Li–F granitic magmas at depth leads to the accumulation of flux elements such as F and Li, and metal cations such as Ta and Nb in residual melts. However, it remains to be determined whether magmatic fractionation is sufficient to concentrate Nb and Ta into economically significant quantities, and what role hydrothermal–metasomatic processes play in the formation of such ore deposits. In the literature, reliable data about the solubility of Ta and Nb in hydrothermal solutions is missing or incomplete. This study provides a quantitative experimental estimation of the possible contribution from hydrothermal processes in Ta enrichment in cupolas of albitized and greisenized Li–F granite. Experimental studies of Ta₂O₅ and columbite–tantalite (Mn,Fe)(Nb,Ta)₂O₆ solubility were carried out in fluoride solutions consisting of HF, NaF, KF, and LiF. At low fluoride concentrations (0.01 and 0.1 m), Ta₂O₅ solubility at 550°C and 100 MPa under Co–CoO oxidizing conditions is low (near 10^?5–10^?4 m) in all fluoride solutions (HF, NaF, KF, LiF). At high fluoride concentrations (1 and 2 m) the highest Ta₂O₅ concentrations (10^?1 m) were detected in HF solutions. In KF, NaF, and LiF solutions, the Ta₂O₅ solubility is also high (10^?3–10^?2 m). The dependence of columbite–tantalite (Nb₂O₅-59 wt. %, Ta₂O₅-18 wt. %) solubility as a function of solution composition, T, and P has also been investigated. Tantalum and Nb concentrations have the highest values in HF solutions at reduced conditions (up to 10^?3 to 10^?2 m Ta in 1 m HF). In 1 m NaF solutions, the concentrations of Nb and Ta are, respectively, 2.5 and 3 orders of magnitude less than those in the 1 m HF solutions. Solubility of Ta and Nb in KF solutions has intermediate values. It is established that in NaF and KF solutions the dependence of solubility on pressure is distinctly negative. The Nb and Ta contents increase with increasing concentrations of HF and KF in solution, however, they do not change with increasing NaF concentration. In NaHCO₃, Na₂CO₃, and HCl solutions columbite–tantalite solubility is low. Even in 1 m chloride solutions the content is within the limits of 10^?5 m for Nb and 10^?6 to 10^?8 m for Ta. We conclude that hydrothermal transport of Ta and Nb is possible only in concentrated fluoride solutions.     

Surface acidity constants of α-Al2O3 between 25 and 70°c

The effect of temperature on the adsorption of H⁺ onto corundum was investigated experimentally by conducting potentiometric titrations at 25, 30, 40, 50, 60 and 70°C. These titrations were used to determine apparent acidity constants, given by the product of an intrinsic adsorption constant and a coulombic term (K_i^app = K_i^inte^{(−ΔZFΨ/RT)}) at the above temperatures.First and second intrinsic acidity constants were determined using a constant capacitance model (CCM). These constants and the point of zero charge change linearly with inverse temperature. These data were used to determine thermodynamic constants for the proton adsorption reactions.In the coulombic term, only the capacitance and the surface charge change with temperature and both were determined with the titration data at the various temperatures. Results show that the change in capacitance can be predicted with changes in the dielectric constant of water with increasing temperature. At a given pH, changes in the surface charge with temperature can, in turn, be predicted with a linear regression.With the above model, apparent acidity constants of corundum (including the chemical and electrostatic interactions) can be predicted for any temperatures between 25 and 70°C and possibly higher. These apparent constants change over several orders of magnitude in this temperature range (mainly due to a change in the coulombic term) and small temperature changes could have a strong influence on the stability of surface complexes.     

异质同构晶体的结构演变对Eu2+/Eu3+稳定性的影响

Eu具有2种价态,一般来说,还原条件的选择和控制是合成低价Eu材料的关键。而大量的实验结果也表明:基质晶体结构、取代离子半径和电荷以及电荷补偿剂等对Eu的价态改变和价态稳定性都有影响。Eu3+是Eu元素在化合物中的正常价     

齐齐哈尔碾子山麦饭石物化性能及其对Pb2+、Cd2+、Cr3+的吸附行为研究

以齐齐哈尔碾子山麦饭石为研究对象,通过比表面积及孔隙分析、阳离子交换容量(CEC)测试以及p H值缓冲能力测试等,对碾子山区麦饭石的结构和性能进行表征,并进一步研究麦饭石对Pb~(2+)、Cd~(2+)、Cr~(3+)的吸附行为。结果显示:碾子山区麦饭石具有海绵体大孔结构,阳离子交换容量(CEC)13~20 mmol/100 g。碾子山麦饭石对酸碱溶液都具有较好的调节能力,尤其对酸液的调节更高效。重金属吸附性能方面,对Pb~(2+)、Cd~(2+)、Cr~(3+)这3种离子吸附关系为:Pb~(2+)Cr~(3+)Cd~(2+)。     

Detection Statistics of Pulse Signals at Declinations from +42° to +52° at the Frequency 111 MHz

Astronomy Reports - A search for pulse signals was carried out in a new sky area included in the monitoring program for the search for pulsars and transients. Processing of several months data...     

Schüllerite, Ba2Na(Mn,Ca)(Fe3+,Mg,Fe2+)2Ti2(Si2O7)2(O,F)4, a new mineral species from the Eifel volcanic district, Germany

A new heterophyllosilicate mineral schüllerite was found in the L?hley basalt quarry in the Eifel volcanic region, Germany, as a member of the late mineral assemblage comprising nepheline, leucite, augite, phlogopite, magnetite, titanite, fresnoite, barytolamprophyllite, fluorapatite, perovskite, and pyrochlore. Flattened brown crystals of schüllerite up to 0.5 × 1 × 2 mm in size and their aggregates occur in miarolic cavities of alkali basalt. The mineral is brittle, with a Mohs hardness 3–4 and perfect cleavage parallel to (001). D _calc = 3.974 g/cm³. Its IR spectrum is individual and does not contain bands of OH⁻, CO₃²⁻ or H₂O. Schüllerite is biaxial (−), α = 1.756(3), β = 1.773(4), γ = 1.780(4), 2V _meas = 40(20)°. Dispersion is weak, r < ν. Pleochroism is medium X > Y > Z, brown to dark brown. Chemical composition (electron microprobe, mean of five-point analyses, Fe²⁺/Fe³⁺ ratio determined by the X-ray emission spectroscopic data, wt %): 3.55 Na₂O, 0.55 K₂O, 3.89 MgO, 2.62 CaO, 1.99 ArO, 28.09 BaO, 3.43 FeO, 8.89 Fe₂O₃, 1.33 Al₂O₃, 11.17 TiO₂, 2.45 Nb₂O₅, 26.12 SiO₂, 2.12 F, −0.89 -O=F₂, 98.98 in total. The empirical formula is (Ba_1.68Sr_0.18K_0.11Na_1.05Ca_0.43Mn_0.47Mg_0.88Fe_0.44²⁺Fe_1.02³⁺Ti_1.28Nb_0.17Al_0.24)_Σ7.95Si_3.98O_16.98F_1.02. The crystal structure was refined on a single crystal. Schüllerite is triclinic, space group P1, unit cell parameters: a = 5.4027(1), b = 7.066(4), c = 10.2178(1)?, α = 99.816(1), β = 99.624(1), γ = 90.084(1)°, V = 378.75(2) ?³, Z = 1. The strongest lines of the X-ray powder diffraction pattern [d, ?, (I, %)]: 9.96(29), 3.308(45), 3.203(29), 2.867(29), 2.791(100), 2.664(46), 2.609(36), 2.144(52). The mineral was named in honor of Willi Schüller (born 1953), an enthusiastic, prominent amateur mineral collector, and a specialist in the mineralogy of Eifel. Type specimens have been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, registration no. 3995/1,2.     

桂林潮田河Ca2+、Mg2+与HCO3-关系模型及岩溶碳汇影响因素分析

尽管大气中CO2浓度不断增加,但全球碳源与碳汇相抵后还存在遗失碳汇(missing sink).一般认为遗失碳汇主要为地质碳汇.而碳酸盐岩的溶蚀作用可在短时间内产生大量的地质碳汇,与此同时,该过程也伴随着HCO3-、Ca2+、Mg2+等离子进入水中.由于水中的Ca2+、Mg2+比HCO3-稳定,故探讨Ca2+、Mg2+与HCO3-的关系,可以间接得到影响碳汇的各种主要因素.本文通过对岩溶区3种岩性5个监测点的Ca2+、Mg2+与HCO3-数据建立关系模型发现:(1)灰岩地区Ca2+可以与HCO3-建立良好的关系模型,相关性较好,而白云岩区Ca2+、Mg2+与HCO3-的相关关系比Ca2+与HCO3-的相关关系好;总之,在岩溶动力系统下,Ca2+、Mg2+全面考虑可更好指示碳汇的去向;(2)Ca2+、Mg2+与HCO3-的关系模型可以间接说明碳汇主要影响因子;由Ca2+、Mg2+与HCO3-的关系模型可得岩溶区地表明流段,水生生物的光合作用是碳汇主要影响因子,而地下河或泉水出口处,地质作用、CO2分压可能是碳汇的主要影响因子.得出碳汇主要影响因素,为潮田河流域碳汇研究区域划分以及准确计算地质碳汇提供依据与基础.