Transmission electron microscopy on iron monosulfide varieties from the Suizhou meteorite

Transmission electron microscopy on the iron monosulfide (FeS) varieties from the Suizhou meteorite (Hubei, China) reveals the intergrowth of primary hexagonal 2C troilite and minor monoclinic 4C pyrrhotite (SG: F2/d) phases as nanometer-scale domain microstructure. In addition, anti-phase domain boundaries are found to present in the 2C troilite superstructure with the displacement vector 1/4[001]_2C, which is expected to form during the translational symmetry breaking during cooling from higher symmetry, high-temperature modification of the NiAs-type (SG: P6₃/mmc) structure. Furthermore, 60° rotation twinning about the pseudo-hexagonal c-axis is observed in the 4C pyrrhotite superstructure, which may result from rotation symmetry reduction induced by the ordered arrangements of metal vacancies through solid-state transformation during further cooling. All the above microstructural characteristics are discussed with consideration to the thermal metamorphism history experienced by the Suizhou meteorite.     

Draa Sfar, Morocco: A Visean (331 Ma) pyrrhotite-rich, polymetallic volcanogenic massive sulphide deposit in a Hercynian sediment-dominant terrane

Draa Sfar is a Visean, stratabound, volcanogenic massive sulphide ore deposit hosted by a Hercynian carbonaceous, black shale-rich succession of the Jebilet terrane, Morocco. The ore deposit contains 10 Mt grading 5.3 wt.% Zn, 2 wt.% Pb, and 0.3 wt.% Cu within two main massive sulphides orebodies, Tazakourt (Zn-rich) and Sidi M'Barek (Zn–Cu rich). Pyrrhotite is by far the dominant sulphide (70 to 95% of total sulphides), sphalerite is fairly abundant, chalcopyrite and galena are accessory, pyrite, arsenopyrite and bismuth minerals are rare. Pyrrhotite is monoclinic and mineralogical criteria indicate that it is of primary origin and not formed during metamorphism. Its composition is very homogeneous, close to Fe₇S₈, and its absolute magnetic susceptibility is 2.10^− 3 SI/g. Ar–Ar dating of hydrothermal sericites from a coherent rhyolite flow or dome within the immediate deposit footwall indicates an age of 331.7 ± 7.9 Ma for the Draa Sfar deposit and rhyolite volcanism.The Draa Sfar deposit has undergone a low-grade regional metamorphic event that caused pervasive recrystallization, followed by a ductile–brittle deformation event that has locally imparted a mylonitic texture to the sulphides and, in part, is responsible for the elongated and sheet-like morphology of the sulphide orebodies. Lead isotope data fall into two compositional end-members. The least radiogenic end-member, (²⁰⁶Pb/²⁰⁴Pb = 18.28), is characteristic of the Tazakourt orebody, whereas the more radiogenic end-member (²⁰⁶Pb/²⁰⁴Pb  18.80) is associated with the Sidi M'Barek orebody, giving a mixing trend between the two end-members. Lead isotope compositions at Draa Sfar testify to a significant continental crust source for the base metals, but are different than those of the Hajar and South Iberian Pyrite Belt VMS deposits.The abundance of pyrrhotite versus pyrite in the orebodies is attributed to low fO₂ conditions and neither a high temperature nor a low aH₂S (below 10^− 3) is required. The highly anoxic conditions required to stabilize pyrrhotite over pyrite are consistent with formation of the deposit within a restricted, sediment-starved, anoxic basin characterized by the deposition of carbonaceous, pelagic sediments along the flank of a rhyolitic flow-dome complex that was buried by pelitic sediments. Deposition of sulphides likely occurred at and below the seafloor within anoxic and carbonaceous muds.Draa Sfar and other Moroccan volcanogenic massive sulphide deposits occur in an epicontinental volcanic domain within the outer zone of the Hercynian belt and formed within a sedimentary environment that has a high pelagic component. In spite of the diachronous emplacement between the IPB deposits (late Devonian to Visean) and Moroccan deposits (Dinantian), all were formed around 340 ± 10 Ma following a major phase of the Devonian compression.     

铜陵冬瓜山矿床磁黄铁矿的矿物学特征及其指示意义

磁黄铁矿是铜陵冬瓜山矿床中最重要的矿石矿物之一,其标型特征不仅反映其自身形成环境,对矿床成因也具有指示意义。本文选取矿床中不同层位的磁黄铁矿矿石样品,利用矿相学、X射线衍射、电子探针和同位素分析等手段对磁黄铁矿标型形态、成分、结构以及物质来源进行了分析。研究表明：磁黄铁矿主要分布在矿体的中部,根据磁黄铁矿与其共生矿物之间的交代关系,认为金属矿物的生成顺序是黄铁矿→磁黄铁矿→黄铜矿→磁铁矿。X射线衍射显示磁黄铁矿以六方和单斜相为主,近岩体处主要是六方晶系;远岩体处则以单斜晶系为主。且见单斜沿六方磁黄铁矿的边部有交代现象,显示出热液交代作用的特征。电子探针测试显示磁黄铁矿的Fe元素含量为58.435％～60.978％,平均值为59.737％;S元素含量为38.297％～39.891％,平均值为38.696％,分子式为Fe₄S₅～Fe₉S₁₀,也显示磁黄铁矿有六方和单斜两个相,单颗粒成分剖面显示其核部为六方相,边部为单斜相。磁黄铁矿的δ³⁴S组成均为-0.7‰～+13.5‰之间,δ⁵⁷Fe的总体分布范围为0.49‰～0.52‰,Fe同位素和S同位素显示它们均来源于岩浆及其热液。说明磁黄铁矿具有岩浆成因和热液交代成因。支持冬瓜山矿床是与燕山期岩浆活动有关的矽卡岩型矿床观点。     

Crystal chemistry of Fe-containing sphalerites

 Cell dimensions and solvus properties of Fe-containing sphalerites, depending on temperature and sulfur fugacity, were investigated using equilibrated powdered materials synthesized from elements and binary sulfides under vacuum. The Fe solvus in sphalerite, determined by optical microscopy and microprobe analysis, are directly correlated with increasing temperature and decreasing sulfur fugacity controlled by solid-state buffers. The increase of lattice parameters with Fe correlates with an increase of FeS independent of sulfur fugacity up to 10 mol% FeS within ZnS. Above about 10 mol% the lattice parameters are strongly depending on the sulfur fugacity controlled Fe³⁺/Fe²⁺ ratios. The Fe³⁺/Fe²⁺ ratios determined by Moessbauer spectroscopy and involving metal vacancies depend on the sulfur fugacity. The critical Fe²⁺ content determined by experimental simulations as well as the minimal Fe³⁺/ Fe²⁺ ratios agree with the required minimal Fe content for CuFeS₂-DIS in sphalerite. The critical Fe²⁺ content also agrees with the change of Moessbauer signal from a singlet to a doublet for Fe²⁺ containing sphalerite. Pyrrhotite exsolutions in sphalerite caused by higher sulfur fugacity show orientationally intergrown with the sphalerite matrix. Density data calculated from lattice parameters and composition are compared with experimental density measurements. Received: 25 April 2001 / Accepted: 14 February 2003     

黄铁矿加热过程中的矿相变化研究——基于磁化率随温度变化特征分析

对采自河南嵩县祁雨沟7号角砾岩筒的黄铁矿样品进行了详细的磁化率随温度变化特征研究，加热的最高温度为700℃，结果表明黄铁矿受热分解最终生成磁黄铁矿.黄铁矿通过两个可能的途径转变为磁黄铁矿：一个是黄铁矿颗粒首先经表面吸附氧的氧化转变为磁铁矿，随温度升高新生成的磁铁矿与黄铁矿晶格中挥发出的硫进一步反应转变为磁黄铁矿；另一可能途径是黄铁矿直接脱硫转变为磁黄铁矿，此反应为磁黄铁矿的主要来源.氩气环境下加热过程中，从约380℃开始即有磁铁矿生成，但直到约535℃才有磁黄铁矿的生成.在535℃～560℃的加热过程中生成的磁黄铁矿居里温度不稳定，直到加热至高于约560℃时才生成居里温度稳定的磁黄铁矿.氩气环境下，黄铁矿受热生成的磁性矿物的类型仅受最高温度的控制，与高温段的滞留时间无明显关系，而其生成量同时受最高温度和高温段滞留时间的控制.     

磷灰石中磁黄铁矿出溶结构的发现

中国东部苏鲁地区(江苏赣榆)出露大理岩-榴辉岩块体,其菱镁矿大理岩中保存的白云石分解结构表明地壳物质俯冲深度达到-200公里。在与该大理岩共生的榴辉岩中,我们发现了磷灰石的磁黄铁矿出溶结构。磷灰石是该榴辉岩的主要副矿物,其自形程度较高,与石榴石共生。样品中几乎所有磷灰石均发育出溶结构,至少存在两组相互垂直的出溶棒,它们各自严格沿同一个方向分布。出溶棒形状规则,宽度相近(<1μm),但长度变化大(5-50μm)。利用高分辨能谱仪测定其能谱,结果表明,出溶棒主要由Fe和S两种元素组成,但不能准确地确定其Fe/S比值。我们把这种出溶棒初步确定为磁黄铁矿(Fe1-xS)。磷灰石由于含大量稀土元素和挥发性组分如OH、F、Cl等以及我们所观察到的S,它的深循环因此可能对地球的水、硫以及其它挥发性组分的全球平衡具有重要影响。本文报道的磷灰石中磁黄铁矿出溶结构为深入探讨这个基本科学问题提供了一个新的突破口。     

Synthesis of PGE sulfide standards for laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

Sulfide compositions with known Re, Os, Ir, Ru, Rh, Pt, and Pd contents are synthesized to be used as standards for noble metal analysis in solid solution in sulfides. Major elements were added as metals and elemental S. The noble metals, i.e. 35 and 60 ppm each, were added as solutions by micro syringe. Following synthesis at 1 atm the sulfides were sintered at 1.5 to 2 GPa to obtain pellets with theoretical density. Aliquots of the pellets were analysed by isotope dilution ICP-MS for bulk Re and platinum-group elements (PGE). The spatial noble metal distribution was investigated with an ArF excimer laser coupled to a single collector ICP mass spectrometer. Sample homogeneity is shown to depend on the metal/S spectrum and the major element composition of the sulfide, as well as on more subtle factors like oxygen partial pressure during synthesis, run temperature, and degree of partial melting. The most homogeneous sulfide composition is a (Fe,Ni)_{1 − x} S monosulfide with 5 wt % Ni and 1-sigma variations in ³⁴S-normalized noble metal count rates of <3.6%. Nearly as homogeneous is a pure Fe_{1 − x} S monosulfide with 1-sigma variations in ³⁴S-normalized noble metal count rates of <5.8 %. A Cu-bearing Fe_{1 − x} S monosulfide with 2 wt % Cu was found to be considerably more heterogeneous, suggesting that Cu in solid solution in monosulfides promotes noble metal heterogeneity. The sulfide composition least suitable for the synthesis of noble metal sulfide standards is NiS.