我国产出的曼纳德石(Mannardite)Ba(Ti6V2)O(16)

一九八○年,四川省地矿局中心实验室在研究四川甘孜白玉麻邛呷村多金属矿床的物质成分及银的赋存状态时,发现了一个新矿物,后命名为甘孜矿。经过较长时间反复研究,直到最近才决定报国际矿物协会(IMA)。但我国新矿物及矿物命名委员会告知,加拿大J.D.Scott等在一九八三年就以曼纳德石     

我国产出的板硼石晶体

前言板硼石(Inyoite——Ca2B6O11·13H2O)是由 W.T.沙勒（Schaller）在美国加利福尼亚州死谷发现的一种含水的钙硼酸盐矿物,以后在加拿大新不伦瑞克（New Brunswick）、苏联的印迭尔和秘鲁的一干盐湖沉积物中均有发现。近几年来,在我国个别表生硼酸盐矿床中也发现有板硼石产出,其中有一矿床所产的板硼石晶形十分完美,因而使我们有可能对这些晶体进行较全面的分析和研究,本文即主要报导我们工作的初步结果。     

Equilibrium experiments in the system MgO–SiO2–H2O (MSH): stability fields of clinohumite-OH [Mg9Si4O16(OH)2], chondrodite-OH [Mg5Si2O8(OH)2] and phase A (Mg7Si2O8(OH)6)

The water-pressure and temperature stability fields of clinohumite-OH, chondrodite-OH and phase A were determined in reversed equilibrium experiments up to 100 kbar within the system MgO–SiO₂–H₂O. Their PT-fields differ from results from former synthesis experiments. Bracketing experiments on the reaction phase A + low P-clinoenstatite ⇆ forsterite + water resulted in a slightly steeper dP/dT-slope compared to earlier experiments for this equilibrium. Clinohumite-OH and chondrodite-OH both have large stability fields which extend over pressure ranges of more than 80 kbar. However, they are hardly relevant as hydrous minerals within the subducted oceanic lithosphere. Both are too Mg-rich for a typical mantle bulk composition. In addition, the dehydration of subducted oceanic lithosphere – due to (forsterite + water)-forming reactions – will occur before the two humite-group phases even become stable. Restricted to the cool region of cold subducting slabs, phase A, however, might be formed via the reactions phase A + low P-/high P-clinoenstatite ⇆ forsterite + water or antigorite + brucite ⇆ phase A + water, before dehydration of the oceanic lithosphere occurs. Received: 22 July 1997 / Accepted: 12 March 1998     

透视石晶体中[CuO_4(H_2O)_2]~(6-)络离子的晶场谱项和磁性质

透视石的化学式是Cu_6[Si_6O_(18)]·6H_2O。其晶体结构包括六个水分子的折叠三角环,此环分布在由六个硅氧四面体形成的折叠三角环的层中,Cu~(2 )离子纵向和横向连接三角环。Cu~(2 )离子由四个O~(2-)和二个H_2O构成的畸变八面体所围绕,四个O~(3-)位于平面正方形的四个顶点,H_2O位子沿z轴伸长的八面体的二个顶点上。Cu-O的键长为1.95—1.98,Cu-H_2O的键长为2.50—2.68。据多数文献报     

High-pressure behaviour of Ca-rich C 2 /c clinopyroxenes along the join diopside-enstatite (CaMgSi2O6-Mg2Si2O6)

 An in situ high-pressure (HP) X-ray diffraction investigation of synthetic diopside and of the Ca_0.8Mg_1.2Si₂O₆ clinopyroxene (Di₈₀En₂₀) was performed up to respectively P=40.8 and 15.1 GPa, using high brilliance synchrotron radiation. The compression of the cell parameters is markedly anisotropic, with β_b ⋙ β_c > β_a > β_asinβ for any pressure range and for both diopside and Di₈₀En₂₀. The compressibility along the crystallographic axes decreases significantly with pressure and is higher in Di₈₀En₂₀ than in diopside. The β cell parameter decreases as well with pressure, at a higher rate in Di₈₀En₂₀. The cell volume decreases at almost the same rate for the two compositions, since in diopside a higher compression along a* occurs. A change in the mechanism of deformation at P higher than about 5–10 GPa is suggested for both compositions from the analysis of the strain induced by compression. In diopside at lower pressures, the deformation mainly occurs, at a similar rate, along the b axis and at a direction 145° from the c axis on the (0 1 0) plane. At higher pressures, instead, the deformation occurs mostly along the b axis. In Di₈₀En₂₀ the orientation of the strain axes is the same as in diopside. The substitution of Ca with Mg in the M2 site induces at a given pressure a higher deformation on (0 1 0) with respect to diopside, but a similar change in the compressional behaviour is found. Changes in the M2 polyhedron with pressure can explain the above compressional behaviour. A third-order Birch-Murnaghan equation of state was fit to the retrieved volumes, with K=105.1(9) GPa, K′=6.8(1) for diopside and K=107.3(1.4) GPa, K′=5.7(3) for Di₈₀En₂₀; the same equation can be applied for any pressure range. The elasticity of diopside is therefore not significantly affected by Mg substitution into the M2 site, in contrast to the significant stiffening occurring for Ca substitution into Mg-rich orthopyroxenes. Received: 3 January 2000 / Accepted: 21 May 2000     

Vibrational analysis of dioptase Cu6Si6O18 · 6(H2O) and its puckered six-membered ring

The normal modes of vibration and their frequencies are calculated for dioptase, a mineral whose crystal structure (space group R or C _3i ² ) consists of puckered six-membered silicate rings (Si₆O₁₈) linked by Cu²⁺ ions and H₂O groups. The calculation employs a valence force potential consisting of central interactions between nearest neighbors and bond-bending interactions centered at the Si⁴⁺ and Cu²⁺ ions. The force constants are determined by fitting the calculated frequencies to values obtained by measuring the single-crystal Raman spectra. The calculated frequencies are in reasonable agreement with experiment, permitting assignment of normal modes to the observed spectral frequencies. Considerable mixing of Cu and H₂O motions with those of the ring is found for the Raman-active modes below 430 cm^-1. The normal modes and frequencies of the hypothetical isolated ring with C _3i symmetry are determined by neglecting all interactions between the rings and the surrounding Cu and H₂O. The identification of normal modes characteristic of the puckered six-membered silicate rings and the effect of the environment on these modes may prove useful in the interpretation of the Raman spectra of amorphous silicates.     

Kasatkinite, Ba2Ca8B5Si8O32(OH)3 · 6H2O6, a new mineral from the Bazhenovskoe deposit, the Central Urals, Russia

A new mineral, kasatkinite, Ba₂Ca₈B₅Si₈O₃₂(OH)₃ · 6H₂O, has been found at the Bazhenovskoe chrysotile asbestos deposit, the Central Urals, Russia in the cavities in rhodingite as a member of two assemblages: (l) on prehnite, with pectolite, calcite, and clinochlore; and (2) on grossular, with diopside and pectolite. Kasatkinite occurs as spherulites or bunches up to 3 mm in size, occasionally combined into crusts. Its individuals are acicular to hair-like, typically split, with a polygonal cross section, up to 0.5 mm (rarely, to 6 mm) in length and to 20 μm in thickness. They consist of numerous misoriented needle-shaped subindividuals up to several dozen μm long and no more than 1 μm thick. Kasatkinite individuals are transparent and colorless; its aggregates are snow white. The luster is vitreous or silky. No cleavage was observed; the fracture is uneven or splintery for aggregates. Individuals are flexible and elastic. The Mohs’ hardness is 4–4.5. D _meas = 2.95(5), D _calc = 2.89 g/cm³. Kasatkinite is optically biaxial (+), α = 1.600(5), β = 1.603(2), γ = 1.626(2), 2V _meas = 30(20)°, 2V _calc = 40°. The IR spectrum is given. The ¹¹B MAS NMR spectrum shows the presence of BO₄ in the absence of BO₃ groups. The chemical composition of kasatkinite (wt %; electron microprobe, H₂O by gas chromatography) is as follows: 0.23 Na₂O, 0.57 K₂O, 28.94 CaO, 16.79 BaO, 11.57 B₂O₃, 0.28 Al₂O₃, 31.63 SiO₂, 0.05 F, 9.05 H₂O, ?0.02 ?O=F₂; the total is 99.09. The empirical formula (calculated on the basis of O + F = 41 apfu, taking into account the TGA data) is: Na_0.11K_0.18Ba_1.66Ca_7.84B_5.05Al_0.08Si_8.00O_31.80(OH)_3.06F_0.04 · 6.10H₂O. Kasatkinite is monoclinic, space group P2₁/c, P2/c, or Pc; the unit-cell dimensions are a = 5.745(3), b = 7.238(2), c = 20.79 (1) Å, β = 90.82(5)°, V = 864(1) ų, Z = 1. The strongest reflections (d Å–I[hkl]) in the X-ray powder diffractions pattern are: 5.89–24[012], 3.48–2.1[006], 3.36–24[114]; 3.009–100[ $12\bar 1$ , 121, $10\bar 6$ ], 2.925–65[106, $12\bar 2$ , 122], 2.633–33[211, 124], 2.116–29[ $13\bar 3$ , 133, 028]. Kasatkinite is named in honor of A.V. Kasatkin (b. 1970), a Russian amateur mineralogist and mineral collector who has found this mineral. Type specimen is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

A study on the effects of drying conditions on the stability of NaNd(CO3)2·6H2O and NaEu(CO3)2·6H2O

The effect of different drying conditions on the stability of NaNd(CO₃)·6H₂O and NaEu(CO₃)·6H₂O and the identity of the decomposition product have been investigated. The rate of decomposition and the nature of the altered phases are dependant on the drying conditions used. When the phases are oven dried at 120 °C, the decomposition is immediate and the phase completely alters to Nd₂(CO₃)₃ or Eu₂(CO₃)₃ respectively. Under less severe drying conditions, the Na rare earth carbonate phases alter to Nd₂(CO₃)₃·8H₂O and Eu₂(CO₃)₃·8H₂O over a period of 24–48 h, but they can be kept indefinitely in a water saturated environment. The implications for using Nd and Eu as actinide analogues are discussed.     

Solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) at 5–75°C

The solubility of ettringite (Ca₆[Al(OH)₆]₂(SO₄)₃ · 26H₂O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log K_SP for the reaction Ca₆[Al(OH)₆]₂(SO₄)₃ · 26H₂O ⇌ 6Ca²⁺ + 2Al(OH)₄⁻ + 3SO₄²⁻ + 4OH⁻ + 26H₂O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log K_SP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log K_SP with pH and the mean log K_SP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH^°_r and ΔS^°_r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol⁻¹ and 170 ± 38 J mol⁻¹ K⁻¹. Using our values for log K_SP, ΔH^°_r, and ΔS^°_r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG^°_f,298, the enthalpy of formation ΔH^°_f,298, and the entropy of formation ΔS^°_f,298 to be −15211 ± 20, −17550 ± 16 kJ mol⁻¹, and 1867 ± 59 J mol⁻¹ K⁻¹. Assuming ΔC_P,r is zero, the heat capacity of ettringite is 590 ± 140 J mol⁻¹ K⁻¹.     

河西石NiMg(CO_3)_2

作者在1960年6月于我国某地铜镍硫化物矿床露头中找到一种翠绿色的矿物,经研究后证明为前所未知的镍碳酸盐的新矿物,并定名为河西石。由于矿物结晶太细小,因恐标本中混有其他镍的矿物,研究工作虽在当年间即已基本完成,但没有发表。1963年9     

Solid solubility in the system NaLREETi2O6– ThTi2O6 (LREE, light rare-earth elements): experimental and analytical data

The existence of an incomplete solid solution series between loparite (NaLREETi₂O₆), a member of the perovskite mineral group, and thorutite (ThTi₂O₆) is established on the basis of experimental and mineralogical data. The products of low- and high-pressure synthesis in the system NaLaTi₂O₆– ThTi₂O₆ were studied by energy-dispersive spectrometry, X-ray diffractometry and Rietveld analysis. At atmospheric pressure, Th is incorporated in loparite as both ThTi₂O₆ and Na₂ThTi₃O₉. In synthetic systems, the maximum determined ThTi₂O₆ content of loparite is 18 mol%, with a corresponding A-site cation deficiency of 9%. The structure of such loparite is tetragonal and presumably derived from the cubic aristotype by octahedral rotation [I4/mcm, a=5.4652(1) Å, c=7.7476(2) Å]. At a pressure of 6 GPa, no solubility between loparite and ThTi₂O₆ is observed, and Th is accommodated in the loparite structure entirely as Na₂ThTi₃O₉ (up to 30 mol%). Naturally occurring loparite contains up to 29 mol% ThTi₂O₆, based on the conventional method of analysis recalculation, or 23.5 mol% ThTi₂O₆, assuming the presence of protons at the vacant A-sites. ThTi₂O₆ synthesized by the solid-state reaction, crystallizes with monoclinic symmetry [C2/m, a=9.8140(2) Å, b=3.8228(1) Å, c=7.0313(2) Å,β=118.82(1)°]. Atomic coordinates for ThTi₂O₆ obtained in this study from X-ray powder data, as well as structural parameters derived from the new data, are in a good agreement with those known from single-crystal refinement. ThTi₂O₆ does not crystallize at high pressure, and Th is accommodated in perovskite-type compounds and cubic ThO₂ that provide a twelve- and eight-fold coordination site for Th, respectively.     

Experimental study of the K2ZrSi3O9 (wadeite)–K2TiSi3O9 and K2(Zr,Ti)Si3O9–phlogopite systems at 2–3 GPa

Experiments ranging from 2 to 3 GPa and 800 to 1300 °C and at 0.15 GPa and 770 °C were performed to investigate the stability and mutual solubility of the K₂ZrSi₃O₉ (wadeite) and K₂TiSi₃O₉ cyclosilicates under upper mantle conditions. The K₂ZrSi₃O₉–K₂TiSi₃O₉ join exhibits complete miscibility in the P–T interval investigated. With increasing degree of melting the solid solution becomes progressively enriched in Zr, indicating that K₂ZrSi₃O₉ is the more refractory end member. At 2 GPa, in the more complex K₂ZrSi₃O₉–K₂TiSi₃O₉–K₂Mg₆Al₂Si₆O₂₀(OH)₄ system, the presence of phlogopite clearly limits the extent of solid solution of the cyclosilicate to more Zr-rich compositions [Zr/(Zr + Ti) > 0.85], comparable to wadeite found in nature, with TiO₂ partitioning strongly into the coexisting mica and/or liquid. However, at 1200 °C, with increasing pressure from 2 to 3 GPa, the partitioning behaviour of TiO₂ changes in favour of the cyclosilicate, with Zr/(Zr + Ti) of the K₂(Zr,Ti)Si₃O₉ phase decreasing from ∼0.9 to ∼0.6. The variation in the Ti content of the coexisting phlogopite is related to its degree of melting to forsterite and liquid, following the major substitution ^VITi+^VI□=2^VIMg. Received: 26 January 1999 / Accepted: 10 January 2000     

锑钙石(Romeite)在我国的发现

锑钙石(Romeife)是极其少见的锑的氧化物类矿物,是由辉锑矿经长期风化作用而形成,常见于锑矿床的氧化带。该矿物属烧绿石型结构。据文献,锑钙石首次于1841年由Dufréney在黎巴嫩的Damour发现,后来在意大利的Pidmont地区的Sant Marcel矿山、巴西的Mines Geraes、瑞典的Langban和奥地利的Schneeb-     

钙贝塔石(Calciobetafite)在我国的发现

钙贝塔石发现于四川西昌的霓辉石-钠铁闪石脉中，与之共生的矿物是霓辉石，钠铁闪石，钠长石，铈磷灰石，硅钛铈矿，沥青铀矿，重晶石，方解石和彩钼铅矿等。钙贝塔石呈黑色，黑褐色，具八面体晶形，大小为2mm～8mm，条痕为黑色或黄褐色，油脂到沥青光泽，贝壳状断口。摩氏硬度为6．05～6．44(Hv=570．08kg／mm^2～689．06kg／mm^2)；无解理，比重4．51(扭力天平法测定)，反射率从406nm(13．53％)到659nm(11．87％)。经计算钙贝塔石的化学式为：(Ca，Na，U)2(Nb，Ti)2(0，OH)，。钙贝塔石的强X射线：2．975(10．222)，2．570(5．400)，1．816(9．440)，1．549(8．622)，1．050(6．844)，等轴晶系，α=1．029nm。     

Arsenic(V) adsorption onto α-Al2O3 between 25 and 70°C

The adsorption of As(V) onto α-Al₂O₃ was investigated at 25, 50 and 70°C using batch adsorption experiments. Results indicate that As is strongly adsorbed at low pH and gets progressively released to the fluid with increasing pH above 7. At any pH, increasing temperature favors aqueous species of As over surface species. Surface complexation constants were determined at the experimental temperatures by fitting the adsorption data. Adsorption reactions were then converted to semi-isocolumbic reactions, i.e. reactions with balanced like-charged aqueous species. Intrinsic adsorption constants of semi-isocolumbic reactions change linearly when plotted against inverse temperature, suggesting that the heat capacity of these reactions remains constant over the temperature range considered. This permitted thermodynamic parameters of intrinsic surface complexation constants to be determined. Changes in surface complexation constants result in a change in the surface speciation with increasing temperature. This change is similar to the one observed for aqueous species, i.e. increasing temperature favors less negatively charged species below a pH of 9 and more negatively charged species above a pH of 10. Comparison with the stability of As surface complexes with Fe suggests that surface complexes with Al are more stable.     

我国主要超镁铁岩蛇纹石化水的非大洋成因——(L-C)蛇纹岩的D/H和(18)O/(16)O

本文对贺根山、鲸鱼、东巧、罗布莎、玉石沟等地超镁铁岩中(L-C)蛇纹岩标本的氢、氧同位素组成进行了分析,其变化范围为:δD=-101—-146,δ~(18)O=1.0—7.5。产生蛇纹石化作用时平衡计算水的氢、氧同位素为:330℃时δD=-77—-122,δ~(18)O=1.4—7.9;200℃时δD=-67—-112,δ~(18)O=-1.3—5.2。根据大洋型(L-C)蛇纹岩和大陆蛇绿岩杂岩型(L-C)蛇纹岩的氢、氧同位素组成特征来看,本文所研究的蛇纹岩明显地属于大陆蛇绿岩杂岩型蛇纹岩。蛇纹石化时平衡计算水的氢、氧同位素特征表明水的成因类型为大气降水型地下水,而非大洋水。本文中超镁铁岩的蛇纹石化作用发生在超镁铁岩侵位于大陆壳之后,即超镁铁岩的蛇纹石化作用发生于大陆环境,而非大洋环境,而且超镁铁岩在侵位于陆壳之后的最初阶段应为新鲜的地幔岩石。     

我国曲阳的硼硅钇钙石(Hellandite)

1980年在河北曲阳县某碱性伟晶岩中发现一种含Y、Ce、Ca、Al为主的硼硅酸盐矿物。经光性及其它物性的测定、化学分析、X射线单晶及粉晶分析、红外光谱分析确定是在我国首次发现的硼硅钇钙石(hellandite)、空间群为P2/a,晶胞参数a=18.827×10~(-10)m;b=4.694;c=10.257;β=111.7°;单位晶胞分子式:(Ca,Y,RE)_(12)(Al,Fe~(3+))_2(OH)_4[Si_8(B,Be)_8O_(40)(OH)_4]。     

Zn_3(PhCH=CHCOO)_6(phen)_2·H_2O的纳米晶结构计算及环境属性

Zn3(PhCH=CHCOO)6(phen)2.H2O晶体具有与锰氧化物及锰氢氧化物类似的微结构,在生成环境与晶体化学微结构方面有明显的环境属性,是一种新生环境矿物.为研究其纳米晶结构、最佳纳米尺度和环境矿物属性,在溶液法合成该配合物晶体的基础上,采用纳米晶参数计算方法,对该配合物纳米级微粒的晶胞数、原子数、表面原子数和表面活性随微粒在纳米尺度范围内的变化进行了计算,对比锰氢氧化物结构,发现该配合物晶体活性、表面效应与颗粒尺度有密切关系,内部结构具有鲜明的环境属性.结合晶体颗粒的比表面积与总原子数相对颗粒尺度的变化关系,理论上确定了该颗粒最佳纳米化尺度为138nm,为此类物质纳米晶在环境方面的研究应用奠定了基础.     

几种新宝(玉)石原料的确认及产出条件与寻找方向

宝(玉)石原料靠现有的已开采多年的老矿山,尚供不应求。因此,除开采老矿山外,应大力开发新矿山和寻找新的宝石原料,尤其是中低档宝石原料是当前的主要任务。现就笔者近年来接触到的几个宝玉石介绍如下。1.工艺特性:包头矿外观如眼睛般乌黑,半透明,硬度大。产于特定的地质环境中。至今仅在中国和美国的两个稀土矿床附近的岩脉中发现过。作者于1978年磨制的一个包头矿弧     

Kampelite,Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O,a new very complex Ba-Sc phosphate mineral from the Kovdor phoscorite-carbonatite complex (Kola Peninsula,Russia)

Mineralogy and Petrology - Kampelite, Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O, is a new Ba-Sc phosphate from the Kovdor phoscorite-carbonatite complex (Kola Peninsula, Russia). It is orthorhombic, Pnma,...