Crystal chemical significance of chemical zoning in dissakisite-(Ce)

Dissakisites from Trimouns dolomite mine, France, have two kinds of single crystals: chemical-zoned and homogeneous types. Back-scattered electron microprobe (BSE) images of these dissakisites reveal both Ca–Al rich dark zones and Fe-ΣREE rich bright zones. Crystal structures of three dark and two bright zones in a chemical-zoned dissakisite and of a homogeneous zone in unzoned dissakisite were refined to individual R indices (about 3.0–5.0%) based on 1,400 observed [|F ₀| > 4σF ₀] reflections measured with MoKα X-radiation using the single crystal diffractometer. The differences in brightness between their BSE images arise from those in coupled substitutions of the elements occupying A2 and M3 sites. The main reason for these differences is that ten-coordinated A2 polyhedra and M3 octahedra are directly linked through their shared edge, which creates a great potential for making this coupled substitution. This zoning indicates that formation of the whole zoned crystal, where each zone could be grown steadily with its crystallographic axes mutually parallel to each other, may be identified as autoepitaxy.     

Cu–Fe Bearing Zinc Sulfide from Laloki Stratabound Massive Sulfide Deposit, Papua New Guinea: Chemical Characterization

Abstract: A strange, unidentified, Cu-Fe bearing zinc sulfide occurs in the Laloki massive sulfide deposit, Papua New Guinea. The mineral is optically uniform in texture but is chemically variable and zoned even within a single grain. Copper contents vary from 0.1 up to 8.85 wt%. Iron reaches 18.31 wt% at maximum and decreases as Cu increases. It is remarkable, however, that the total Fe+Cu remains essentially unchanged between roughly 18 and 20 wt%. Zn and S are least variable, giving 45.85–47.84 wt% and 33.48–34.58 wt%, respectively. Other trace elements such as Cd and Mn are in general less than 0.2 wt%. It is strongly suggested that the mineral in question constitutes a unique Fe-Cu substitutional solid solution series belonging essentially to the Zn–Fe–Cu–S system.
The ideal chemical formula of the solid solution series can well be presented as Zn₁₀(Fe, Cu)₅S₁₅ or Zn₂(Fe, Cu)S₃, where Fe is always greater than Cu. It is intriguing that chalcopyrite blebs are recognizable restrictively only in nearby portions of the Cu-rich end member with the ideal composition close to Zn₁₀Fe₃Cu₂S_15. It has been confirmed by vacuum-sealed heating experiments that this mineral is decomposed to produce chalcopyrite and Fe-bearing normal sphalerite at temperatures below 200C. This would provide another evidence for the existence of such distinct phase as suggested here.     

岩浆型磷灰石结构四面体替换特征的标型意义

根据文献中列了的５６个产于碳酸岩－碱性岩磷灰石的成分数据，讨论了这些岩浆型磷灰石结构四面体替换特征的标型意义，并定义出四面体替换指数，（ＴＳＩ＝（Ｓｉ＋ＳＣ）／Ｐ，单位晶胞原子数百分比），以区别侵入相碳酸岩磷灰石，喷发相碳酸岩磷灰石和碱性岩磷灰石：ＩＡＰ的ＴＳＩ为０－６．９，平均３．６２，仅少量Ｃ进入Ｔ位置；     

Structure refinement of astrophyllite

The crystal structure of astrophyllite K₂Na(Fe, Mn, Mg,□)₇[Ti₂(Si₄O₁₂)₂|O₃](OH, F)₄ has been refined. The dimensions of the triclinic unit cell are: a = 0.5359(2) nm,b = 1.1614(4) nm, c = 1.1861(4) nm, α= 113.16(2)°, β= 103.04(2)°,γ= 94.56(2)°,V = 0.6495(5) nm³, Z= 1, space group P1, R=0.057 for 5308 reflections |F_o|>3σ|F_o|. According to structural and compositional differences the monoclinic astrophyllite K₂NaNa(Fe, Mn)₄Mg₂Ti2[Si₄O₁₂]₂(OH)₄(OH, F)₂ and astrophyllite should be considered as two different mineral species. Astrophyllite, monoclinic astrophyllite, bafertisite and lamprophyllite contain heteropolyhedral sheets which topologically are related with Si, O sheets of mica where one or several SiO₄ tetrahedra are replaced by TiO _n polyhedra. Therefore this heterophyllotitanosilicate series represents a kind of functional substitution in inorganic crystals.     

Modeling of dioctahedral 2:1 phyllosilicates by means of transferable empirical potentials

 Dioctahedral 2:1 phyllosilicates with different interlayer charge have been studied theoretically by using transferable empirical interatomic potentials. The crystal structures of pyrophyllite, muscovite, margarite, beidellite, montmorillonite, and different smectites and illites have been simulated. The interatomic potentials were able to reproduce the experimental structure of phyllosilicates with high, medium and low interlayer charge. The calculated structures are in agreement with experiment for the main structural features of the crystal lattice. The effect of the cation substitution in the octahedral and tetrahedral sheets on the structural features has been also studied. Good linear relationships have been found, and the calculated effects are consistent with experimental results. Some unknown structural features of the crystal structures of clays are predicted in this work. Received: 8 March 2000 / Accepted: 19 September 2000     

SALES TAX AS PROPERTY TAX RELIEF? THE SHIFTING ONUS OF LOCAL REVENUE GENERATION

Local governments are under pressure to develop alternative revenue sources to their already strapped property tax bases. Throughout the 1970s, municipal governments nationwide restructured their local taxes by substituing sales tax for property tax revenue. A tax accounting model identified two sources of sales-for-property tax substitution: changes in the tax rates and normal economic growth and decline. Most of the sales-for-property tax substitution experienced in Illinois city finance was attributable to economic change. The critical determinant of this substitution appreared to be the municipality's share of the regional retail market. Cities in higher density metropolitan areas were less likely to experience sales-for-property tax substitution through economic growth than those cities in lower density, less competitive environments.     

广西大厂锡多金属矿田西矿带稀散元素铟的富集规律研究——来自矿石组构和闪锌矿地球化学的证据

广西大厂锡多金属矿田是世界最主要的铟产地之一,对其的富集机制还有很大争议。文章以大厂矿田西矿带高峰矿床和铜坑矿床中的闪锌矿为研究对象,在野外和室内矿相显微观察的基础上,应用高精度电子探针与等离子体质谱分析手段,研究稀散元素铟的空间分布规律、赋存状态及与主成矿元素的关系,揭示其在闪锌矿中的富集规律。实验结果表明,铜坑矿床中闪锌矿内稀散元素铟的含量随深度增加而减少,而高峰矿床中铟含量却保持稳定;铟主要以类质同象形式赋存,与铜以双替代锌的形式进入闪锌矿晶格中,也不排除铟以微细包体形式赋存的可能。结合前人研究,推断燕山晚期复式岩体岩浆演化末期花岗斑岩侵位冷却过程中,岩浆结晶产生的富铟、铜等流体对早期生成的闪锌矿进行交代并富集。这一研究结果为寻找稀散元素铟指示了方向。     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

江西雅山花岗岩长石中磷的分布及意义

雅山富氟高磷花岗岩具较高的全岩磷含量（０．１５％～０．５５％）,长石是磷的主要赋存矿物,磷以ＰＡｌＳｉ－２替换方式进入长石结构中。各种结晶习性的长石的磷含量各不相同。早世代钠长石和雪球结构中钠长石包裹体的结晶较早,平均磷含量分别为０．１８％和０．１９％,而晚世代钠长石和环带钾长石中钠长石嵌晶的结晶稍晚,具较高的平均磷含量（分别为０．２５％和０．２３％）。钾长石的磷含量相对于钠长石总体上较低,早期结晶的雪球结构主晶钾长石和环带钾长石的磷含量最低,分别为０．０４％和０．０２％,晚期细粒钾长石的平均磷含量略高（０．１９％）。长石对全岩磷的贡献率还与磷锂铝石等磷酸盐副矿物是否达到饱和有关,当无磷锂铝石结晶时,长石磷的贡献率约为７６％,反之则约为３１％。