Distribution of cations at two tetrahedral sites in Ca2MgSi2O7-Ca2Fe3+AlSiO7 series synthetic melilite and its relation to incommensurate structure

Synthetic melilites on the join Ca₂MgSi₂O₇ (åkermanite: Ak)-Ca₂Fe³⁺AlSiO₇ (ferrialuminium gehlenite: FAGeh) were studied using X-ray powder diffraction and ⁵⁷Fe Mössbauer spectroscopic methods to determine the distribution of Fe³⁺ between two different tetrahedral sites (T1 and T2), and the relationship between ionic substitution and incommensurate (IC) structure. Melilites were synthesized from starting materials with compositions of Ak₁₀₀, Ak₈₀FAGeh₂₀, Ak₇₀FAGeh₃₀ and Ak₅₀FAGeh₅₀ by sintering at 1,170–1,350 °C and 1 atm. The average chemical compositions and end-member components, Ak, FAGeh and Geh (Ca₂Al₂SiO₇), of the synthetic melilites were Ca_2.015Mg_1.023Si_1.981O₇ (Ak₁₀₀), Ca_2.017Mg_0.788Fe _0.187 ³⁺ Al_0.221Si_1.791O₇ (Ak₇₈FAGeh₁₉Geh₃), Ca_1.995Mg_0.695Fe _0.258 ³⁺ Al_0.318Si_1.723O₇ (Ak₆₉FAGeh₂₅Geh₆) and Ca_1.982Mg_0.495Fe _0.449 ³⁺ Al_0.519Si_1.535O₇ (Ak₄₉FAGeh₄₄Geh₇), respectively. Rietveld refinements using X-ray powder diffraction data measured using CuK _α -radiation at room temperature converged successfully with goodness-of-fits of 1.15–1.26. The refined Fe occupancies at the T1 and T2 sites and the Mg and Si contents determined by electron microprobe analysis gave the site populations of [0.788Mg + 0.082Fe³⁺ + 0.130Al]_T1[0.104Fe³⁺ + 0.104Al + 1.792Si]_T2 for Ak₇₈FAGeh₁₉Geh₃, [0.695Mg + 0.127Fe³⁺ + 0.178Al]_T1[0.132Fe³⁺ + 0.144Al + 1.724Si]_T2 for Ak₆₉FAGeh₂₅Geh₆ and [0.495Mg + 0.202Fe³⁺ + 0.303Al]_T1[0.248Fe³⁺ + 0.216Al + 1.536Si]_T2 for Ak₄₉FAGeh₄₄Geh₇ (apfu: atoms per formula unit), respectively. The results indicate that Fe³⁺ is distributed at both the T1 and the T2 sites. The mean T1–O distance decreases with the substitution of Fe³⁺ + Al³⁺ for Mg²⁺ at the T1 site, whereas the mean T2–O distance increases with substitution of Fe³⁺ + Al³⁺ for Si⁴⁺ at the T2 site, causing decrease in the a dimension and increase in the c dimension. However, in spite of the successful Rietveld refinements for the X-ray powder diffraction data measured using CuK _α-radiation at room temperature, each Bragg reflection measured using CuK _α1-radiation at room temperature showed weak shoulders, which were not observed in those measured at 200 °C. The Mössbauer spectra of the melilites measured at room temperature consist of two doublets assigned to Fe³⁺ at the T1 site and two or three doublets to Fe³⁺ at the T2 site, implying the existence of multiple T1 and T2 sites with different site distortions. These facts can be interpreted in terms of the IC structure in all synthetic melilites at room temperature, respectively. The results of Mössbauer analysis indicate that the IC structure in melilite is caused by not only known multiple T1 site, but also multiple T2 site at room temperature.     

Mg-Fe云母化学成分的解释和分类(Ⅰ)——基本置换和黑云母平面

 中国东部花岗岩类141个Mg-Fe云母的化学成分将近90%的变化属于八面体层内的类质同象置换,置换矢量Mg ₁Fe⁺²和Fe_-3⁺²(R_Ⅵ⁺³)_-2□_Ⅵ组成了天然黑云母平面,大约80%的变化应当解释为基本置换8Mg ₁Fe⁺²+Fe_-3⁺²(R_Ⅵ⁺³)₂□_Ⅵ.这些是Mg-Fe云母在广泛的自然条件下表现出来的最主要的晶体化学关系。文中还提出了置换矢量的长度、分量和以及电价和三个参数,用以识别矿物化学成分变化的类质同象置换特征。     

Minerals in the Triassic carbonaceous silicites of Sikhote Alin

Over 60 minerals, including native elements, intermetallic compounds, haloids, sulfides, sulfates, arsenides, oxides and hydroxides, silicates, borosilicates, wolframates, phosphates and REE phosphates, were established in Triassic siliceous rocks of Sikhote Alin. Allothigenic and authigenic minerals in the carbonaceous silicites were formed over a long period through several stages. Judging from morphology, chemical composition, and structural position, K-feldspar (K-Fsp), illite, kaolinite, metahalloysite, monazite, xenotime, zircon, rutile, or its polymorphs are the disintegration products of sialic rocks of continental crust. Authigenic sulfides are dominated by diagenetic pyrite (fine-crystalline, microglobular, framboidal, as well as those developed after biogenic siliceous and carbonate fragments), which has been formed prior to precipitation of siliceous cement and lithification of siliceous rocks. Most of other sulfides (sphalerite, galena, chalcopyrite, pyrrhotite, argentite, pentlandite, antimonite, ulmanite, and bravoite), arsenides and sulfoarsenides (arsenopyrite, nickeline, skutterudite, cobaltite, glaucodot, and gersdorffite), wolframates (scheelite and wolframite), intermetallides (Cu₂Zn, Cu₃Zn₂, Cu₃Zn, Cu₄Zn, CuSn, Cu₄Sn, Cu₈Sn, Cu₄Zn₂Ni, Ni₂Cu₂Zn, Ni₄Cd), and native elements (Au, Pd, Ag, Cu, Fe, W, Ni, Se) were crystallized later (during catagenesis after the lithification and brecciation of siliceous beds) from metals involved in the easily mobile fractions of bitumens. Supergene mineral formation was mainly expressed in the sulfide oxidation and replacement of diagenetic pyrite by jarosite and iron hydroxides.     

藏南查拉普金矿床载金矿物特征与金的赋存状态

黄铁矿和毒砂是卡林型和造山型金矿床重要的载金矿物。文章通过电子探针(EPMA)分析研究了藏南查拉普金矿床不同类型黄铁矿和毒砂中Au、As、S、Fe等元素的含量变化和分布规律,发现不同阶段的黄铁矿具有不同的结构特征和元素组成特点。沉积成岩期黄铁矿(Py1)主要呈草莓状、胶状,常构成环带状黄铁矿的核心,其中金的含量最高,显示了金在沉积成岩期的大量富集。热液期早阶段黄铁矿(Py2)主要呈自形-半自形的立方体,与Py1元素(S、Fe、As)组成相近,显示了一定的继承演化关系。热液期主阶段黄铁矿(Py3)与毒砂共生,多呈自形-半自形的五角十二面体、立方体,常包裹早期的黄铁矿形成环带结构。Py3中As的含量明显升高,其增加量近似等于S的减少量,说明As主要进入黄铁矿晶格替代了S的位置。各个阶段的黄铁矿和毒砂中Au的分布在EPMA微束的分辨率下均显示是不均匀的,Au在Py1和大部分Py2中主要以纳米级自然金(Au0)的形式存在;而在Py3中主要以(Au+)的形式存在,少部分以纳米级自然金(Au0)形式存在。Py1的结构及元素组成与典型卡林型金矿和造山型金矿沉积成岩期黄铁矿的特点相似,而Py3的大量发育则符合卡林型金矿的特征。     

On local structural changes in lizardite-1T: {Si4+/Al3+}, {Si4+/Fe3+}, [Mg2+/Al3+], [Mg2+/Fe3+] substitutions

Geometrical changes induced by cation substitutions {Si⁴⁺/Al³⁺}[Mg²⁺/Al³⁺], {2Si⁴⁺/2Al³⁺} [2Mg²⁺/2Al³⁺], {Si⁴⁺/Fe³⁺} [Mg²⁺/Al³⁺] or [Mg²⁺/Fe³⁺], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1T and 2H ₁, up to ~30% in the 2H ₂ polytype. Si⁴⁺ by Fe³⁺ substitution in the tetrahedral sheet with an Al³⁺ (Fe³⁺) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.     

Use of natural chabazite–phillipsite tuff in wastewater treatment from electroplating factories in Jordan

Chabazite-phillipsite tuff from Tell Rimah volcano was evaluated in industrial wastewater treatment. Samples of two different size fractions have suitable zeolite content and cation exchange capacity, and are characterized by good attrition resistance and high packed bed density. Such properties enable these fractions to be used as ion exchangers under column operation condition. In the presence of high concentration of competing ions, such as Na⁺, Ca⁺² and K⁺, and under conditions of high total ionic concentration of toxic metals, the chabazite-phillipsite tuff exhibits successful performance in removing Cu⁺², Cr⁺³, Ni⁺², Zn⁺² and Fe⁺² from electroplating effluents. The factors that influence selectivity and efficiency of the zeolitic tuff were evaluated. The experimental work indicates that both selectivity and efficiency of the zeolite shows similar trends. The selectivity sequence exhibited by the zeolitic tuff is Ni⁺²>>Zn⁺² and Cr⁺³>Cu⁺²>>Fe⁺².     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: I. Thermodynamic constants at ambient conditions

Understanding and deciphering processes proceeding near the surface are among the urgent tasks of contemporary mineralogy and geochemistry, which are especially important for resolving ecological challenges and developing principles of rational environmental management. The paper presents systematized data published on thermodynamics of minerals (arsenates, sulfates, selenites, and selenates), which are formed in the weathering zone of sulfide ores, and determines approaches to quantitative physicochemical modeling of their formation conditions. Diagrams of phase and chemical equilibria (Eh-pH, diagrams of solubility) of the subsystems of the model system Fe-Cu-Zn-Pb-Co-Ni-As-Se-S-H₂O (Fe²⁺, Fe³⁺, Cu²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Co²⁺, H⁺//SeO₃²⁻, SeO₄²⁻, AsO₄³⁻, SO₄²⁻, OH⁻-H₂O) are used as a thermodynamic basis for modeling mineral-forming processes in the weathering zone of ore deposits. Seventy-two arsenates, about 70 sulfates, and 7 selenites and selenates have been identified in the framework of this system. The available published values of standard thermodynamic functions of the formation of minerals and chemical compounds are given, as well as the Pitzer equation parameters to describe the sulfate systems, which are substantially specific due to the high solubility of their components.     

A study of phase transformation in hedenbergite to 40 GPa at ∼1200° C

Phase transformations in a natural sample of hedenbergite ((Ca_0.93Fe_0.61Mn_0.34Mg_0.08Na_0.01Zn_0.02Al_0.003)Si₂O₆) have been studied by X-ray diffraction up to 40 GPa at ∼ 1200°C in a diamond anvil cell interfaced with a laser heating system. The starting hedenbergite phase decomposed into a garnet plus γ-spinel and stishovite at ∼ 14 GPa; then into garnet plus stishovite and wüstite at ∼ 18 GPa; and finally into perovskite plus stishovite and wüstite at pressures higher than ∼ 24 GPa. On decompression to 0.1 MPa, all the high pressure phases are retained except for the cubic perovskite, which reverts back into the ɛ-CaSiO₃ phase, in accordance with previous reports. Energy-dispersive SEM analyses show that the garnet is present as a calcium-rich ABO ₃-type phase. As no garnet phase has been previously observed either in pure CaSiO₃ or in pure CaMgSi₂O₆, it appears that the observed calcium-rich garnet phase has been stabilized by the presence of other cations such as the Na⁺, Zn²⁺, Mn²⁺, Fe²⁺, Mn³⁺, Fe³⁺ and Al³⁺.     

O and S isotopic composition of dissolved and attached oxidation products of pyrite by Acidithiobacillus ferrooxidans: Comparison with abiotic oxidations

The acidophilic iron-oxidizing bacterium, Acidithiobacillus ferrooxidans, plays a part in the pyrite oxidation process and has been widely studied in order to determine the kinetics of the reactions and the isotopic composition of dissolved product sulphates, but the details of the oxidation processes at the surface of pyrite are still poorly known. In this study, oxygen and sulphur isotopic compositions (δ¹⁸O and δ³⁴S) were analyzed for dissolved sulphates and water from experimental aerobic acidic (pH < 2) pyrite oxidation by A. ferrooxidans. The oxidation products attached to the pyrite surfaces were studied for their morphology (SEM), their chemistry (Raman spectroscopy) and for their δ¹⁸O (ion microprobe). They were compared to abiotically (Fe³⁺, H₂O₂, O₂) oxidized pyrite surface compounds in order to constrain the oxidation pathways and to look for the existence of potential biosignatures for this system.The pyrite dissolution evolved from non-stoichiometric (during the first days) to stoichiometric (with increasing time) resulting in dissolved sulphates having distinct δ¹⁸O (e.g. +11.0‰ and −2.0‰, respectively) and δ³⁴S (+4.5‰ and +2.8‰, respectively) values. The “oxidation layer” at the surface of pyrite is complex and made of iron oxides, sulphate, polysulphide, elemental sulphur and polythionates. Bio- and Fe³⁺-oxidation favour the development of monophased micrometric bumps made of hematite or sulphate while other abiotic oxidation processes result in more variable oxidation products. The δ¹⁸O of these oxidation products at the surface of oxidized pyrites are strongly variable (from ≈−40‰ to ≈+30‰) for all experiments.Isotopic fractionation between sulphates and pyrite, Δ³⁴S_SO4-pyrite, is equal to −1.3‰ and +0.4‰ for sulphates formed by stoichiometric and non-stoichiometric processes, respectively. These two values likely reflect either a S-S or a Fe-S bond breaking process. The Δ¹⁸O_SO4-H2O and Δ¹⁸O_SO4-O2 are estimated to be ≈+16‰ and ≈−25‰, respectively. These values are higher than previously published data and may reflect biological effects. The large δ¹⁸O heterogeneity measured at the surfaces of oxidized pyrites, whatever the oxidant, may be related (i) to the existence of local surface environments isolated from the solution in which the oxidation processes are different and (ii) to the stabilization at the pyrite surface of reaction intermediates that are not in isotopic equilibrium with the solution. Though the oxygen isotopic composition of surface oxidation products cannot be taken as a direct biosignature, the combined morphological, chemical and isotopic characterization of the surfaces of oxidized pyrites may furnish clues about a biological activity on a mineral surface.     

Comprehensive physicochemical study of dioctahedral palygorskite-rich clay from Marrakech High Atlas (Morocco)

This study is devoted to the physicochemical and mineralogical characterizations of palygorskite from Marrakech High Atlas, Morocco. The raw clay and its Na⁺-saturated <2 μm fraction were characterized using chemical, structural, and thermal analytical techniques. Measurements of specific surface area and porous volume are reported. The clay fraction was found to be made up of 95 % of palygorskite and 5 % of sepiolite. An original feature of this palygorskite is its deficiency in zeolitic H₂O. The half-cell structural formula of its dehydrated form was determined on the basis of 21 oxygens to be (Si_7.92Al_0.08)(Mg_2.15Al_1.4Fe_0.4Ti_0.05 $ \square_{1} $ )(Ca_0.03Na_0.08K_0.04)O₂₁, while the hydrated form could be formulated as (Si_7.97Al_0.03)(Mg_2.17Al_1.46Fe_0.40Ti_0.05)(Ca_0.03Na_0.07K_0,03)O_20.18(OH)_1.94(OH₂)_3.88·2.43 H₂O. These formulas show that the (Al³⁺+Fe³⁺)/Mg²⁺ ratio is around 0.84, revealing a pronounced dioctahedral character. Further, inside its octahedral sheet, it was determined that the inner M₁ sites are occupied by vacancies, whereas the M₂ sites are shared between 90 % of trivalent cations (78 % for Al³⁺ and 22 % for Fe³⁺), 7.5 % of Mg²⁺, and 2.5 % of Ti⁴⁺, all of them linked to 1.94 of structural hydroxyls. The two remaining Mg²⁺ by half-cell occupy edge M₃ sites and are coordinated to 3.88 molecules of OH₂. Channels of this palygorskite are deficient in zeolitic H₂O since they contain only 2.43 H₂O molecules. A correlation was found between these results and the observation of very intense and well-resolved FTIR bands arising from dioctahedral domains (mainly Al₂OH, Fe₂OH, and AlFeOH) along with very small responses from a trioctahedral domain (Mg₃OH). Accordingly, a schematic representation of the composition of the octahedral sheet was proposed. The cation exchange capacity, specific surface area, and total pore volume were also assessed to be ca. 21.2 meq/100 g, 116 m²/g, and 0.458 cm³/g, respectively.     

The kinetics of the dissolution of chlorite as a function of pH and at 25°C

Far from equilibrium, quasi-steady state dissolution rates of an iron rich chlorite (Mg_2.76Fe²⁺_1.90Fe³⁺_0.07Al_0.97)[Si_2.48Al_1.52O₁₀](OH)₈, have been measured as a function of H⁺ concentration for the pH range 3 to 10.5 and at 25°C. The rates were determined using a single pass flow through cell and with a time frame for observing the steady state condition of between 10 to 50 days. Rates are independent of the buffers used to control the pH, sample preparation, experimental methodology and chlorite composition. The results were collated with literature values allowing the rate to be expressed as a function of H⁺ as;

     

Fe-Li云母化学成分的解释和分类

用置换矢量概念解释了115个天然 Fe-Li 云母化学成分的变化。Fe-Li 云母是三八面体 Li-Fe-Al 云母,其基本置换是四锂云母置换。由于 Al-Li 白云母置换和白云母置换的影响,其化学组成变化的基本趋势呈明显的非线性,因而 Fe-Li 云母不是真正的二元系。作为 Fe-Li 云母,富铁黑云母和铁叶云母都是最富铁的成员,因而建议称 Fe-Li 云母为黑云母-锂云母系列。根据化学成分,晶胞参数和折光率的异常变化还提出了该系列自然分类的方案。     

Geobarometers involving clinopyroxene,garnet, plagioclase,ilmenite, rutile,sphene and quartz: estimation of pressure in quartz-absent assemblages

Enthalpy of formation and third law entropy for andradite (Ca₃Fe₂Si₃O₁₂) and hedenbergite (CaFeSi₂O₆) at standard state have been retrieved from experimental P-T-f(O₂) data on the stability relations of these phases. The data for hedenbergite were combined with the thermodynamic data for related phases (Berman 1988) to formulate the geobarometers based on the reactions CaFeSi₂O₆+2CaAl₂Si₂O₈+2FeTiO₃= Ca₃Al₂Si₃O₁₂+Fe₃Al₂Si₃O₁₂+2TiO₂ (CPG-IR), 3CaFeSi₂O₆+3CaAl₂Si₂O₈+3FeTiO₃=Ca₃Al₂Si₃O₁₂ +2Fe₃Al₂Si₃O₁₂+3CaTiSiO₅ (CPG-IS) and 3CaFeSi₂O₆+3CaAl₂Si₂O₈=2Ca₃Al₂Si₃O₁₂+ Fe₃Al₂Si₃O₁₂+3SiO₂ (CPG-O). The geobarometers involving rutile and sphene are proposed for the first time. In several granulite terranes, pressures have been estimated from the three geobarometers for basic granulites and charnockitic suite of rocks containing the above assemblages. In clinopyroxene-garnet-plagioclase-quartz-ilmenite-rutile assemblages, pressures obtained from CPG-IR are within ±500 bars of pressures calculated from the CPG-Q barometer. However, if rutile is absent, the pressures computed from the CPG-IR barometer are 300 to 1,200 bars higher than those calculated from the CPG-Q barometer. For maximum differences in pressures obtained from the two equilibria TiO₂ activity [a(TiO₂)] in the rocks is calculated to be 0.8. The sphene-bearing geobarometer (CPG-IS) also registers pressures comparable (<±500 bars) to those obtained from the CPG-Q barometer. The close agreement in pressure values obtained from the CPG-IR and the CPG-IS equilibria with those registered by the CPG-Q geobarometer in assemblages containing quartz implies that the rutile- and sphene-bearing geobarometers which do not involve quartz, can also be applied to estimate pressures from quartz-absent assemblages-assemblages which are not amenable to quantitative geobarometry using existing formulations.     

Fe-rich Li-bearing magnesionigerite-6N6S from Xianghualing tin-polymetallic orefield, Hunan Province, P.R. China

The Fe-rich Li-bearing magnesionigerite-6N6S occurs in the Xianghualing tin-polymetallic ore field, Linwu County, Hunan Province, Peoples Republic of China. It was found near the outer contact zone of the Laizhiling granite body and in the Middle-Upper Devonian carbonate rocks of Qiziqiao Formation. The mineral formed during the skarn stage. Its empirical formula is Sn_1.81Li_0.67(Fe_1.43Zn_1.19 Mn_0.41)_Σ3.03(Al_14.89Mg_1.46 Ti_0.11Si_0.01)_Σ16.47O₃₀(OH)₂. The structure for magnesionigerite-6N6S was solved and refined in space group R-3?m, with a?=?5.7144(8), c?=?55.446(11) Å, V?=?1568.0(4) ų, to R1?=?0.0528. Based on the structural refinement of single crystal diffraction data the formula of magnesionigerite-6N6S is Sn_1.80Li_0.97(Fe_1.89Zn_0.91) _Σ2.80 (Al_14.60Mg_1.63 Ti_0.20)_Σ16.43O₃₀(OH)₂ with Z?=?3. Fe-rich Li-bearing magnesionigerite-6N6S contains 0.74 wt.% Li₂O. The idealized charge-balanced composition of magnesionigerite-6N6S may be expressed by bivalent and trivalent cations: (Mg²⁺)₄(Al³⁺)₁₈O₃₀(OH)₂. The simplified general formula for the 6N6S polysomes in the nigerite and högbomite groups can be given as A _x B_18-x O₃₀(OH)₂, x?=?~4, where A?=?Mg²⁺, Fe²⁺, Zn²⁺; B?=?Al³⁺, Sn⁴⁺, Ti⁴⁺, Li⁺, □.     

Calculation of multicomponent chemical equilibria and reaction processes in systems involving minerals,gases and an aqueous phase

The compositional characteristics of many geochemical systems which involve the interaction of natural aqueous solutions with minerals and gases are conveniently described using the following thermodynamic components: Cl^?, SO₄⁼, HS^?, CO₃⁼, H⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Fe⁺⁺, Zn⁺⁺, Cu⁺, Al⁺⁺⁺, SiO₂ and H₂O. A set of mass balance and mass action equations equal in number to the number of components plus the number of saturated minerals (and gases) is defined for a specified temperature, pressure and bulk composition. The mass balance equations include terms for minerals, gases and the molalities of aqueous complexes and dissociated species. This set of non-linear equations can be solved with the aid of a computer using'a Newton-Raphson technique. The calculation takes account of aqueous ion complexing, oxidation-reduction equilibria, activity coefficients, non-unit water activity and solid solutions. The use of H⁺, SO₄⁼, HS^? and H₂O as components allows straightforward treatment of processes involving oxidation-reduction, evaporation, boiling and changes of total aqueous H⁺ due to hydrolysis, mineral reaction or temperature change. One product of this approach is a technique for calculating pH at high temperature from measurement of pH at room temperature.By linking a series of discrete overall heterogeneous equilibrium calculations in which incremental changes of bulk composition, temperature or pressure are made, dynamic geochemical processes can be modeled. Example calculations for two such processes are given. These are the heating of seawater from 25° to 300°C and the isothermal irreversible reaction of rhyolite with an aqueous solution at 250°C.     

A new Cu-rich variety of lyonsite from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia) and its crystal structure

A new Cu-rich variety of lyonsite has been found from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia). The empirical formula is Cu_4.33Fe _2.37 ³⁺ Ti_0.26Al_0.26Zn_0.07(V_5.85As_0.07Mo_0.07P_0.01S_0.01)O₂₄. The crystal structure was studied on single crystal using synchrotron radiation, R = 0.0514. The mineral is orthorhombic, Pnma, a = 5.1736(7), b =10.8929(12), c = 18.220(2) Å, V = 1026.8(2) ų, and Z = 2. The structural formula is (Cu_0.6Ti_0.3Al_0.3Fe _0.2 ³⁺ □_0.6)_Σ2Cu₂(Fe _2.2 ³⁺ Cu_1.8)_Σ4(V_5.8As_0.1Mo_0.1)_Σ6O₂₄. It is proposed to recast the simplified formula of lyonsite as Cu_3+x (Fe _4?2x ³⁺ Cu_2x )(VO₄)₆, where 0 ≤ x ≤ 1.     

Auriacusite, Fe3+Cu2+AsO4O, the first M 3+ member of the olivenite group, from the Black Pine mine, Montana, USA

Auriacusite, ideally Fe³⁺Cu²⁺AsO₄O, is a new arsenate mineral (IMA2009–037) and the Fe³⁺ analogue of olivenite, from the Black Pine mine, 14.5 km NW of Philipsburg, Granite Co., Montana, USA. It occurs lining quartz vughs and coating quartz crystals and is associated with segnitite, brochantite, malachite, tetrahedrite and pyrite. Auriacusite forms fibrous crystals up to about 5?µm in width and up to about 100?µm in length, which are intergrown to form fibrous mats. Individual crystals are a brownish golden yellow, whilst the fibrous mats are ochreous yellow. The crystals have a silky lustre and a brownish yellow streak. Mohs hardness is about 3 (estimated). The fracture is irregular and the tenacity is brittle. Auriacusite crystals are biaxial (+), with α?=?1.830(5), β?=?1.865(5) and γ?=?1.910(5), measured using white light, and with 2V _meas.?=?83(3)º and 2V _calc. = 84.6º. Orientation: X?=?a, Y?=?c, Z?=?b. Crystals are nonpleochroic or too weakly so to be observed. The empirical formula (based on 5 O atoms) is (Fe _1.33 ³⁺ Cu_0.85Zn_0.03)_Σ2.21(As_0.51Sb_0.27Si_0.04?S_0.02Te_0.01)_Σ0.85O₅. Auriacusite is orthorhombic, space group Pnnm, a?=?8.6235(7), b?=?8.2757(7), c?=?5.9501(5) Å, V?=?424.63(6) ų, Z?=?4. The five strongest lines in the powder X-ray diffraction pattern are [d _obs in Å / (I) / hkl]: 4.884 / (100) / 101, 001; 2.991 / (92) / 220; 2.476 / (85) / 311; 2.416 / (83) / 022; 2.669 / (74) / 221. The crystal structure was solved from single-crystal X-ray diffraction data utilising synchrotron radiation and refined to R ₁?=?0.1010 on the basis of 951 unique reflections with F _o?>?4σF. Auriacusite is identified as a member of the olivenite group with Fe³⁺ replacing Zn²⁺ or Cu²⁺ in trigonal bipyramidal coordination. Evidence suggests that auriacusite is an intermediate member between olivenite and an as yet undescribed Fe³⁺Fe³⁺-dominant member. The name is derived from the Latin auri (golden yellow) and acus (needle), in reference to its colour and crystal morphology.     

Iron sulfide oxidation and the chemistry of acid generation

Acid mine drainage, produced from the oxidation of iron sulfides, often contains elevated levels of dissolved aluminum (AI), iron (Fe), and sulfate (SO₄) and low pH. Understanding the interactions of these elements associated with acid mine drainage is necessary for proper solid waste management planning. Two eastern oil shales were leached using humidity cell methods. This study used a New Albany Shale (4.6 percent pyrite) and a Chattanooga Shale (1.5 percent pyrite). The leachates from the humidity cells were filtered, and the filtrates were analyzed for total concentrations of cations and anions. After correcting for significant solution species and complexes, ion activities were calculated from total concentrations. The results show that the activities of Fe³⁺, Fe²⁺, Al³⁺, and SO₄ ²⁻ increased due to the oxidation of pyrite. Furthermore, the oxidation of pyrite resulted in a decreased pH and an increased pe+pH (redox-potential). The Fe³⁺ and Fe²⁺ activities appeared to be controlled by amorphous Fe(OH)₃ solid phase above a pH of 6.0 and below pe+pH 11.0. The Fe³⁺, Fe²⁺, and SO₄ ²⁻ activities reached saturation with respect to FeOHSO₄ solid phase between pH 3.0 and 6.0 and below pe+pH 11.0 Below a pH of 3.0 and above a pe+pH of 11.0, Fe²⁺, Fe³⁺, and SO₄ ²⁻ activities are supported by FeSO₄·7H₂O solid phase. Above a pH of 6.0, the Al³⁺ activity showed an equilibrium with amorphous Al(OH)₃ solid phase. Below pH 6.0, Al³⁺ and SO₄ ²⁻ activities are regulated by the AlOHSO₄ solid phase, irrespective of pe+pH. The results of this study suggest that under oxidizing conditions with low to high leaching potential, activities of Al and Fe can be predicted on the basis of secondary mineral formation over a wide range of pH and redox. As a result, the long-term chemistry associated with disposal environments can be largely predicted (including trace elements).     

Cation substitution in synthetic meridianiite (MgSO4·11H2O) II: variation in unit-cell parameters determined from X-ray powder diffraction data

We have prepared aqueous MgSO₄ solutions doped with various divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. In a companion paper (Fortes et al., in Phys Chem Min 39) we reported the identification of various phases using X-ray powder diffraction, including meridianiite-structured undecahydrates, melanterite- and epsomite-structured heptahydrates, novel enneahydrates and a new octahydrate. In this work we report the changes in unit-cell parameters of these crystalline products where they exist over sufficient dopant concentrations. We find that there is a linear relationship between the rate of change in unit-cell volume as a function of dopant concentration and the ionic radius of the dopant cation; large ions such as Mn²⁺ produce a substantial inflation of the hydrates’ unit-cell volume, whereas smaller ions such as Ni²⁺ produce a modest reduction in unit-cell volume. Indeed, when the data for all hydrates are normalised (i.e., divided by the number of formula units per unit-cell, Z, and the hydration number, n), we find a quantitatively similar relationship for different values of n. Conversely, there is no relationship between the degree of unit-cell inflation or deflation and the limit to which a given cation will substitute into a certain hydrate structure; for example, Co²⁺ and Zn²⁺ affect the unit-cell volume of MgSO₄·11H₂O to a very similar degree, yet the solubility limits inferred in our companion paper are >60 mol. % Co²⁺ and <30 mol. % Zn²⁺.     

Laser-induced time-resolved luminescence of tugtupite,sodalite and hackmanite

We have interpreted a number of luminescence centers in natural tugtupite Na₈Al₂Be₂Si₈O₂₄Cl₂, sodalite Na₈Al₆Si₆O₂₄C₂ and hackmanite Na₈Al₆Si₆O₂₄(Cl₂,S) by use of laser-induced time-resolved luminescence spectroscopy. The main new results are the following: Fe³⁺, Mn²⁺, Eu²⁺, Ce³⁺, mercury type (potentially Pb²⁺, Tl⁺, Sn²⁺ and/or Sb³⁺), radiation induced luminescence centers; several types of S₂ ⁻ centers. Spectral shift connected with the presence of luminescence centers, which are detected together with S₂ ⁻ centers and impossible to resolve with continuous wave luminescence spectroscopy, is the possible reason for spectral diversity of S₂ ⁻ luminescence centers presented in different publications.