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1.
 General equations to correlate and predict the thermodynamic properties of hydrated borates were developed based on the experimental results according to their structural types. The thermodynamic properties (ΔH f 0 and ΔG f 0) of a hydrated borate phase are the sum of the contributions of the cations in aqueous solution, the borate polyanions, and the structural water to the corresponding thermodynamic properties. This method is called the group contribution method, and it is extensively used to calculate the thermodynamic properties of many kinds of inorganic compounds, such as silicates and clay minerals. Received: 23 November 1998 / Accepted: 11 October 1999  相似文献   

2.
Borates consisting of diverse fundamental building blocks (FBB) formed from complex polymerization of planar triangular [Bϕ3] groups and tetrahedral [Bϕ4] groups, where ϕ = O and OH, provide an excellent opportunity for investigation of correlations between the NMR parameters and local structures. However, previous studies suggested that the 11B NMR parameters in borates are insensitive to local structural environments other than the B coordination number, in contrast to those documented for 29Si, 23Na and 27Al in silicates, and no correlation between 11B chemical shifts and the sum of bond valences has been established for borate minerals with hydroxyl groups or molecular water in the structures. In this study, high-resolution NMR spectra have been acquired at the ultra high field of 21 T as well as at 14 T for selected borate and borosilicate minerals, and have been used to extract high-precision NMR parameters by using combined ab initio theoretical calculations and spectral simulations. These new NMR parameters reveal subtle correlations with various structural characters, especially the effects of the 11B chemical shifts from the bridging oxygen atom(s), site symmetry, symmetry of FBB, the sum of bond valences, as well as the next-nearest-neighbor cations and hydrogen bonding. Also, these results provide new insights into the shielding mechanism for 11B in borate and borosilicate minerals. In particular, this study demonstrates that the small variation in 11B chemical shifts can still be used to probe the local structural environments and that the established correlations can be used to investigate the structural details in borates and amorphous materials.  相似文献   

3.
Chloropinnoite, 2MgO·2B2O3·MgCl2·14H2O, was a new borate, obtained from the natural concentrated salt lake brine in Qinghai–Xizang Plateau, P. R. China. The phase transitions from chloropinnoite dissolved in water and boric acid solution would strongly consist of magnesium borate minerals deposited in a salt lake of China. The obtained results from phase relations and kinetic mechanism of chloropinnoite–water/boric acid system would further propose a new geochemical hypothesis for hydrated magnesium borate deposition. The chloropinnoite was diluted by rich boric acid or solution, and it would accelerate the phase transition of chloropinnoite into other borates, which would explain well the geochemical formation of hydrated borate minerals deposited in Qinghai–Xizang Plateau, China.  相似文献   

4.
Orthorhombic magnesium-iron ludwigite-vonsenite forms a continuous isomorphic series Mg2Fe3+[BO3]O2-Fe 2 2+ Fe[BO3]O2; its composition at the magnesioskarn and other deposits varies from magnesian to ferriferous members. In addition, they demonstrate isovalent substitution of Mn for Mg (in pinakiolite, blatterite, and others) and practically complete substitution of Ni for Mg (in bonaccordite). Ferric iron in the borates is substituted by isovalent Al and Cr. The incorporation of Ti, Sn, Sb, and V via heterovalent substitution has been studied in less detail. Our research revealed new manifestations of Ti-and Sn-bearing borates. They are magnesioludwigite and azoproite with variable Ti content, as well as by Sn-bearing aluminian borates formed via the 2Fe3+ → (Ti4+ + Mg)6+ and/or (Sn4+ + Mg)6+ substitution. The incorporation of pentavalent elements according to the scheme 3Fe3+ → (Sb5+ + 2Mg)9+ or (V5+ + 2Mg)9+ is not excluded. The highest Ti borates were found in the marbles and calciphyres of the Tazheran deposit in the Baikal region and Nalednoe, Dokuchan, and Titovskoe deposits in Yakutia, where azoproites contain more than 50 and even higher 75 mol % of the Mg2(TiMg)0.5[BO3]O2 end member. Aluminum magnesioludwigites from Yakutia and Chukotka simultaneously contain tin and titanium. Mount Brooks, Alaska, contains tin-bearing azoproite or its tin-bearing varieties. New data are reported on Sb-and V-bearing orthoborates. Calciphyres of Alaska contain monoclinic magnesiohulsite (Mg,Fe)2(SnMg) 0.5 6+ [BO3]O2, which is replaced by schoenfliesite MgSn(OH)6. The studied borate occurrences belong to hypabyssal magnesian skarns of the periclase and monticellite metasomatic PT facies at contacts of dolomites with granitoid intrusions of increasing alkalinity or leucocratic granites. Their formation was related to interaction between disequilibrium kotoite and early oxides and spinellides of various compositions, on the one hand, and, on the other hand, to the influx of Ti-and Sn-bearing hydrothermal solutions.  相似文献   

5.
The B K-edge X-ray absorption near-edge structure (XANES) spectra of two borates with tetrahedrally-coordinated B [[4]B; natural danburite (CaB2Si2O8) and synthetic boron phosphate (BPO4)] have been recorded in total electron yield (TEY) and fluorescence yield (FY) modes to investigate the surface and bulk structure of these materials. The TEY XANES measurement shows that danburite is susceptible to surface damage involving conversion of [4]B sites to [3]B sites by reaction with moisture and/or mechanical abrasion (grinding, polishing, etc.). The bulk of the mineral is essentially unaffected. Commercial boron phosphate powder exhibits more extensive surface and bulk damage, which increases with air exposure but is recovered on heating at 650°C. In contrast to ELNES, the XANES technique is not affected by beam damage and when collected in the FY mode is capable of yielding meaningful information on the coordination and intermediate-range structure of B in borate and borosilicate materials. Received: 7 April 1997 / Accepted: 30 July 1997  相似文献   

6.
A large number of Paleoproterozoic borate deposits are hosted by the lower units of a volcanic-sedimentary sequence in Liaoning Province, northeastern China, and are a major source of boron in China. The ore-bearing wall rocks in the deposits are serpentinized ultrabasic rocks and carbonates, with layered leptynites, leptites, amphibolites, and migmatites adjacent to the ore. Both the borate ores and country rocks contain tourmaline, although the country rocks have much lower abundances of the mineral. Based on in situ boron isotope measurements using laser ablation–multi-collector–inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS), boron isotope data show that: (1) δ11B values of borate ores range from + 6.8‰ to + 13.9‰ (mean + 10.8‰); (2) tourmalines from the borate ores have δ11B values from + 9.5‰ to + 12.7‰; and (3) the wall rocks within the borate ores yield slightly lower δ11B values ranging from + 5.7‰ to + 7.6‰, and those outside the deposits from − 9.9‰ to − 5.9‰. Positive δ11B values in borates as well as in tourmalines inside the mining area indicate that boron in these Paleoproterozoic borate deposits was derived from marine evaporites. δ34SV-CDT (where V-CDT is Vienna Canyon Diablo Troilite) values of borate ores, serpentinized marbles, and anhydrites range from + 16.1‰ to + 24.7‰, whereas δ13CV-PDB (where V-PDB is Vienna Pee Dee Belemnite) values of marbles range from + 3.2‰ to + 5.9‰. These isotopic characteristics are interpreted to reflect formation in a marine evaporative environment. LA–MC–ICP–MS zircon weighted207Pb/206Pb ages of leptite and serpentinized olivine basalt from the hanging wall of the borate deposits are 2139 ± 13 Ma and 2130 ± 19 Ma, respectively. Therefore, the (~ 2.2 Ga) borate deposits may have originated from marine evaporative boron-bearing sediments, which were interbedded within bimodal volcanic rocks during the early stages of development of the Liaoji rift.  相似文献   

7.
The hydration of kotoite, suanite, and szaibelyite with ultimate brucitization was considered by the example of skarn deposits of endogenous magnesium borates. This process involves isomorphic substitution of hydroxyl groups for equivalent amounts of boron radicals. The degree of kotoite hydration varies from 2 to 40%. The hydration products reach Mg2[BO3](OH) and Mg3{[BO3]1.5(3OH)0.5}2, are isostructural with orthoborate, approach Mg3[BO3](OH)3, and do not contain szaibelyite. Kotoite in association with humites is replaced by Si-bearing pertsevite with variable F content. In contrast, suanite is directly replaced by szaibelyite, with preservation of its relics or inheritance of crystal shapes. The composition of szaibelyite also changes owing to the partial substitution of hydroxyl for boric radical (in hydroxylszaibelyite) or an increase in H2O content (in hydroszaibelyite), which does not rule out its brucitization. The hydration of borates is caused by a decrease in boron content in hydrothermal solutions with decreasing temperature. The borate assemblages studied are characterized by low F content, the increase of which leads to the appearance of F-bearing low-and moderate-Si pertsevites in humite-kotoite calciphyres. The investigation of hydration became possible owing to the direct determination of boron content in borates. The obtained data were compared with experimental studies on the hydrothermal synthesis of kotoite, suanite, szaibelyite, and fluoborates. The established geochemical tendencies in the hydration of boron minerals, which is accompanied by partial migration and loss of boron into the adjacent rocks, are important for estimating the quality of borate ores in magnesian-skarn deposits.  相似文献   

8.
The Miocene borate deposits of western Turkey are associated with extensive medium- to high-K calc-alkali ignimbritic volcanism and a differentiated comagmatic alkaline trachybasalt–trachydacite lava suite. Ignimbritic air-fall and reworked pumiceous clastic materials are intimately associated with lake sediments that host the borate deposits. Local ignimbritic volcanism is considered the primary source of the B for the Kirka borate deposit in this area. Comparison of the geochemical composition of Turkish ignimbrites associated with borates (`fertile' ignimbrites) with those that do not (`barren' ignimbrites), exhibit a number of features that might prove useful in the exploration for borates in similar volcanic domains. In particular, `fertile' ignimbrites are (a) generally a high-K calc-alkali suite, well-evolved and fractionated (K/Rb is low, <200) with a high-silica rhyolitic bulk composition, (b) exhibit a combined high content of B, As, F, Li and Pb, with high B/La (>1) and B/K (>0.001) ratios, and (c) a mildly fractionated REE pattern (LaN/YbN∼2) and large positive Eu anomaly (Eu/Eu*∼0.1). Other apparent discriminants involving both compatible and incompatible elements (relative to major silicate phases) are largely a function of different degrees of partial melting and fractionation. It is suggested that the initial source of the B (and other associated elements) was from LIL-rich fluids released by the progressive dehydration of altered oceanic crust and pelagic sediments in a subduction zone. The absence or presence of sediments in a segmented subduction zone may influence the variable lateral distribution of borates in active margins on a global scale. Once the crust has become enriched in B via previous or contemporary subduction-related calc-alkali magmatism, the effect of tectonic environment, climate and hydrothermal activity influence the local development of the deposits.  相似文献   

9.
The boron isotope-pH technique is founded on a theoretical model of carbonate δ11B variation with pH that assumes that the boron isotopic composition of carbonates mirrors the boron isotopic composition of borate in solution (δ11Bcarb = δ11Bborate). Knowledge of the fractionation factor for isotope exchange between boric acid and borate in solution (α4-3), the equilibrium constant for the dissociation of boric acid (pKB*), as well as the isotopic composition of boron in seawater (δ11Bsw) are required parameters of the model.The available data suggests that both the value of α4-3 and the history of δ11Bsw are poorly constrained. However, if one assumes that δ11Bcarb = δ11Bborate, an empirical value for α4-3 can be estimated from the results of inorganic carbonate precipitation experiments. This exercise yields an α4-3 value of ∼0.974 in accordance with recent theoretical estimates, but substantially deviates from the theoretical value of 0.981 often used to estimate paleo-ocean pH. Re-evaluation of ocean pH using an α4-3 value of 0.974 and published foraminiferal δ11B values for the Cenozoic yield pH estimates that are relatively invariant, but unrealistically high (∼8.4-8.6). Uncertainty increases as foraminiferal ‘vital effects’ are considered and different models for secular changes in seawater δ11B are applied.The inability to capture realistic ocean pH possibly reflects on our understanding of the isotopic relationship between carbonate and borate, as well as the mechanism of boron incorporation in carbonates. Given the current understanding of boron systematics, pH values estimated using this technique have considerable uncertainty, particularly when reconstructions exceed the residence time of boron in the ocean.  相似文献   

10.
A new statistical model is proposed for the molecular mass distributions (MMD) of polymerized anions in silicate melts. The model is based on the known distribution of Q n species in the MeO-Me2O-SiO2 system. In this model, chain and ring complexes are regarded as a random series of Q n structons with various concentrations of bridging bonds (1 ≤ n ≤ 4, Q 0 corresponds to SiO 4 4? ). This approach makes it possible to estimate the probability of formation of various ensembles of polymer species corresponding to the general formula (Si i O3i+1?j )2(i+1?j)?, where i is the size of the ion, and j is the cyclization number of intrachain bonds. The statistical model is utilized in the STRUCTON computer model, which makes use of the Monte Carlo method and is intended for the calculation of the composition and proportions of polyanions at a specified degree of polymerization of silicate melts (STRUCTON, version 1.2; 2007). Using this program, we simulated 1200 MMD for polyanions in the range of 0.52 ≤ p ≤98, where p is the fraction of nonbridging bonds in the silicon-oxygen matrix. The average number of types of anions in this range was determined to increase from three (SiO 4 4? , Si2O 7 6? , and Si3O 10 8? ) to 153, and their average size increases from 1 to 7.2. A special option of the STRUCTON program combines MMD reconstructions in silicate melts with the formalism of the Toop-Samis model, which enables the calculation of the mole fraction of the O2? ion relative to all anions in melts of specified composition. It is demonstrated that, with regard for the distribution and average size of anion complexes, the concentration of the O2? ion in the MeO-SiO2 system is characterized by two extrema: a minimum at 40–45 mol % SiO2, which corresponds to the initial stages of the gelenization of the polycondensated silicate matrix, and a maximum, which is predicted for the range of 60–80 mol % SiO2.  相似文献   

11.
1H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -(CH2)n - CH3 (n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.  相似文献   

12.
The crystal structure of ilinskite, NaCu5O2(SeO3)2Cl3, a rare copper selenite chloride from volcanic fumaroles of the Great fissure Tolbachik eruption (Kamchatka peninsula, Russia), has been solved by direct methods and refined to R 1?=?0.044 on the basis of 2720 unique observed reflections. The mineral is orthorhombic, Pnma, a?=?17.769(7), b?=?6.448(3), c?=?10.522(4) Å, V?=?1205.6(8) Å3, Z?=?4. The The CuOmCln coordination polyhedra share edges to form tetramers that have 'additional' O1 and O2 atoms as centers. The O1Cu4 and O2Cu4 tetrahedra share common Cu atoms to form [O2Cu5]6+ sheets. The SeO3 groups and Cl atoms are adjacent to the [O2Cu5]6+ sheets to form complex layers parallel to (100). The Na+ cations are located in between the layers. A review of mixed-ligand CuOmCln coordination polyhedra in minerals and inorganic compounds is given. There are in total 26 stereochemically different mixed-ligand Cu-O-Cl coordinations.  相似文献   

13.
The borate polyhedra BO 3 3? , B(OH)3, BO 4 5? , and B(OH) 4 ? are studied using the ab initio and multiple scattering Xα quantum mechanical methods. The ab initio self-consistent-field (SCF) molecular orbital (MO) method, at the minimum basis set level, predicts equilibrium B-O distances within 0.04 Å of their average values in solids so long as the polyhedron charge is small. Orbital energies from double zeta basis set ab initio calculations and analogies with isoelectric compounds are used to assign the X-ray spectra of BO 3 3? and to predict the valence region spectra of BO 4 5? . Contour maps of the difference between molecular and superimposed free atom electron densities show charge buildup along the B-O bond which is only slightly smaller than that observed in CO 3 2? .  相似文献   

14.
An analysis of a five-parameter family of cosmological models in a spatially flat Friedmann Universe with a zero Λ term is presented. The five parameters are (1) σ8, the dispersion of the mass fluctuations in a sphere with radius 8h ?1 Mpc, where h=H 0/100 km s?1 Mpc?1 and H 0 is the Hubble constant; (2) n, the slope of the density-perturbation spectrum; (3) Ωv, the normalized energy density of hot dark matter; (4) Ωb, the baryon density; and (5) h, the normalized Hubble constant. The density of cold dark matter is determined from the condition Ω cdm >1?Ωv?Ω b . Analysis of the models is based on comparison of computational results with observational data for: (1) the number density and mass function of galaxy clusters (a so-called Press-Schechter formalism) and (2) the cosmic microwave background anisotropy. The first method enabled us to determine the value σ8=0.52±0.01 with high accuracy. Using the resulting normalization of the density-perturbation spectrum, we calculated a model for the anisotropy of the cosmic microwave background radiation on large scales (l?10, where l is the harmonic number) and the required contribution of cosmological gravitational waves, characterized by the parameter T/S. The restrictions on T/S become weaker as Ωv increases. Nevertheless, even when Ωv≤0.4, models with h+n≥1.5 require a considerable contribution from gravitational waves: T/S?0.3. On the other hand, in models with Ωv≤0.4 and a scale-invariant density-perturbation spectrum (n=1), we find T/S ?10(h?0.47). The minimization of T/S is possible only for the family of models with red spectra (n<1) and small h (<0.6). The value of Ωv is determined most accurately by the data onΔT/T near the first acoustic peak (l?200). By imposing a general restriction on the amplitude of gravitational waves T/S∈[0, 3] and taking into account the available observational data on the amplitude of the acoustic peak of Sakharov oscillations, ranges of possible values n and Ωv are derived. If the baryon number is constrained by nucleosynthesis data, the models under consideration can have both moderately red and blue power spectra n∈[0.9, 1.2] with a rather high concentration of hot particles Ωv∈[0.2,0.4]. The conditions that n<0.9 and/or Ωv<0.2 decrease the relative amplitude of the acoustic peak by over 30% compared to its value in the standard cold-dark-matter (CDM) model normalized using COBE data.  相似文献   

15.
Plumboselite, ideally Pb3O2(SeO3), is a new selenite (IMA2010?C028) from the Tsumeb mine, Namibia. It occurs as fibres on clausthalite and is also associated with smithsonite, mimetite and vaterite. Plumboselite occurs in subparallel to divergent clusters of thin, flattened, colourless fibres up to 0.3?mm in length, but not exceeding 5???m in width and 2???m in thickness. The fibres are elongated parallel to [001] and flattened on {010}, with {010} the only form observed. The crystals have a dull to adamantine lustre and a white streak. The tenacity is brittle and the Mohs hardness is estimated to be between 2 and 3. Plumboselite crystals are optically biaxial with parallel extinction and are length fast in all orientations. The Gladstone-Dale relationship predicts n av?=?2.115. The high indices of refraction and small crystal size prevented the determination of other optical properties. The calculated density is 7.814?g/cm3. The empirical formula (based on 5 O atoms) is Pb2.92Ca0.01Se1.03O5. Plumboselite is orthorhombic, space group Cmc21, a?=?10.5384(11), b?=?10.7452(13), c?=?5.7577(7) ?, V?=?651.98(12) ?3 and Z?=?4. The five strongest lines in the powder X-ray diffraction pattern are [d obs in ?/(I)/hkl]: 3.155/(100)/221; 1.956/(26)/042,402; 2.886/(22)/311,002; 1.713/(21)/223; 2.691/(17)/040. The crystal structure was solved from single-crystal X-ray diffraction data and refined to R 1?=?0.0371 on the basis of 200 unique reflections with F o?>?4??F. The structure is based on double [O2Pb3] chains of edge-sharing oxo-centered [OPb4] tetrahedra along c, between which are sited SeO3 triangles. The two independent Pb2+ atoms and the Se4+ atom have sterochemically active lone electron pairs.  相似文献   

16.
The evaporites on the Khorat Plateau comprise one of the largest potash deposits in the world, and their origin has long been a controversial problem. Based on boron isotope measurements from borate as a good indicator to distinguish marine and nonmarine evaporites, the borates of potash layers were identified and the results were used to indicate the source of evaporites in the study area as representative of the whole Khorat Plateau. The results show that the main borates include boracite and hilgardite. The boracites occur as crystals and ooids with minor amounts of hilgardite aggregates. The range of δ11B values is from +21.30‰ to +32.94‰ (averaging +29.74‰) and falls in the range of marine borates. The δ11B values in the potash layer are seemingly variable because of the influence of fluvial influx when salts were precipitating. Although the composition of seawater has possibly been modified, the evidence from boron isotopic composition implies that the evaporites in the study area or in the whole Khorat Plateau are marine deposits.  相似文献   

17.
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18.
Here, I describe a theoretical approach to the structure and chemical composition of minerals based on their bond topology. This approach allows consideration of many aspects of minerals and mineral behaviour that cannot be addressed by current theoretical methods. It consists of combining the bond topology of the structure with aspects of graph theory and bond-valence theory (both long range and short range), and using the moments approach to the electronic energy density-of-states to interpret topological aspects of crystal structures. The structure hierarchy hypothesis states that higher bond-valence polyhedra polymerize to form the (usually anionic) structural unit, the excess charge of which is balanced by the interstitial complex (usually consisting of large low-valence cations and (H2O) groups). This hypothesis may be justified within the framework of bond topology and bond-valence theory, and may be used to hierarchically classify oxysalt minerals. It is the weak interaction between the structural unit and the interstitial complex that controls the stability of the structural arrangement. The principle of correspondence of Lewis acidity–basicity states that stable structures will form when the Lewis-acid strength of the interstitial complex closely matches the Lewis-base strength of the structural unit, and allows us to examine the factors that control the chemical composition and aspects of the structural arrangements of minerals. It also provides a connection between a structure, the speciation of its constituents in aqueous solution and its mechanism of crystallization. The moments approach to the electronic energy density-of-states provides a link between the bond topology of a structure and its thermodynamic properties, as indicated by correlations between average anion coordination number and reduced enthalpy of formation from the oxides for [6]Mg m [4] Si n O(m+2n) and MgSO4(H2O) n .  相似文献   

19.
Ore mineralization is formed by postsedimentary (concentrated by evaporation to stage SW2) chloride brines metamorphosed in hydrogeochemical systems that are closed with respect to CO2, evolve according to “calcic” trend, and have high 2mCa2+ > mHCO 3 ? + 2mCO 3 2? ratios. In these situations at high R/W ratios (10–100) and temperatures (100–200°C), these brines concentrate ore elements (Zn, Pb, Fe, and Mn) that are geochemical analogues of Ca. The sulfide precipitation of these elements occurs under the effect of carbonate rocks at the abiogenic sulfate reduction of S(VI) of the original brines at low Eh values, which are created in carbonate rocks at higher (>100°C) temperatures. This origin of sulfide mineralization is intensified at decreasing R/W ratios during the dilution of the original brines by elision waters and an increase in the temperature. The hydrodynamics of these ore-forming brines is controlled by the elision hydrogeological regime, which is defined in hydrogeological structures by the geostatic pressure. The brines migrate into the zones of geochemical barriers during the relaxation of hydrogeological structures toward their equilibrium hydrostatic state. Hydrogeological structures, optimal for the precipitation of ore mineralization, are hydrodynamically active and able to maintain a steady (during 105-106 years) inflow of ore-forming brines into the zones of geochemical barriers and the maximum number of water-exchange cycles at these barriers. Modern analogues of these structures are miogeosyncline foredeeps with Cl-Na-Ca chloride brines with high concentrations of ore elements and overall flow rates ranging from 0.n to n m3/year. Stagnate hydrogeological platform structures in hydrostatic equilibrium cannot ensure water exchange needed for ore formation, and, hence, the brines of these structures are not able to deposit the ore elements contained in them, in spite of the high concentrations of these elements.  相似文献   

20.
The composition and structure of aktashite from the Aktash deposit, Gorny Altai, Russia, have been studied by electron microprobe and X-ray structural analysis. On the basis of close compositions and crystal structures, the identity of aktashite from the Gal-Khaya and Aktash deposits has been demonstrated. Crystals of aktashite are of trigonal symmetry; the unit-cell dimensions are: a = 13.7500(4), c = 9.3600(3) Å, V = 532.54(8) Å3, space group R3, Z = 3 for the composition of Cu6Hg3As4S12, R = 0.043. The structure of aktashite as a framework of vertex-shared HgS4? and CuS4? tetrahedrons of the same orientation is intimately related to the sphalerite-type structure. The earlier identified uncommon cluster group [As4] has been verified and its parameters have been refined. It is shown that the structure may be represented as construction blocks (As4S12)12? packed according to the law of the distorted cubic I-cell.  相似文献   

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