Off‐Mount Calibration and One New Potential Pyrrhotite Reference Material for Sulfur Isotope Measurement by Secondary Ion Mass Spectrometry

Sulfur isotope measurements in three sulfide (two pyrite and one pyrrhotite) samples on two epoxy mounts showed that the mount‐to‐mount variation of raw δ³⁴S values was negligible when secondary ion mass spectrometry (SIMS) analytical settings remained stable. In consequence, an off‐mount calibration procedure for SIMS sulfur isotope analysis was applied in this study. YP136 is a pyrrhotite sample collected from northern Finland. Examination of thin sections with a polarising microscope, backscattered electron image analyses and wavelength dispersive spectrometry mapping showed that the sample grains display no internal growth or other zoning. A total of 318 sulfur isotope (spot) measurements conducted on more than 100 randomly selected grains yielded highly consistent sulfur isotope ratios. The repeatability of all the analytical results of ³⁴S/³²S was 0.3‰ (2s, n = 318), which is the same as that of the well‐characterised pyrite reference materials PPP‐1 and UWPy‐1. Its δ³⁴S value determined by gas mass spectrometry was 1.5 ± 0.1‰ (2s, n = 11), which agrees with the SIMS data (1.5 ± 0.3‰, 2s) calibrated by pyrrhotite reference material Po‐10. Therefore, YP136 pyrrhotite is considered a candidate reference material for in situ sulfur isotope determination.     

辽宁红透山块状硫化物矿床中沉积磁黄铁矿的变质和流体作用

辽宁红透山太古宙块状硫化物型铜-锌矿床经历过高角闪岩相变质作用。矿石结构研究表明,矿床中的磁黄铁矿主要是海底喷流沉积后受到变质退火和重结晶的产物。在进变质过程中形成的磁黄铁矿的变形结构绝大部分已被峰期变质作用所清除,目前所见到的变形结构和矿石糜棱岩主要是退变质阶段的产物。流体的存在促进了磁黄铁矿的变形和退火。退变质流体以较高的氧逸度为特征。     

矿山铁的硫化物矿物处理皮革厂含铬废水的研究

为了全面提升内蒙古大型硫铁矿的综合利用价值,尝试将其主要成分磁黄铁矿和黄铁矿分别用于处理含铬废水,找到了天然硫铁矿和改性硫铁矿处理Cr(Ⅵ)的最佳实验条件。与已有的研究相比,本研究所使用的矿样粒径减少到80~100目,用量减少了70%,所处理的含铬废水浓度增大到50 mg/m L。将处理含铬废水后的硫铁矿经XPS扫描分析后发现,天然黄铁矿在pH值分别为1.84、4.15和10.87的反应体系中处理Cr(Ⅵ)后,大部分的Cr(Ⅲ)以Cr2S3的物相出现,分别占总铬物相的77.99%、86.53和100%。天然磁黄铁矿在pH值为6.5,加热500℃改性后的黄铁矿在pH值为4.15时,也有相当量的三价铬以Cr2S3的物相出现。用已经获得的处理含铬Cr(Ⅵ)的最佳条件,直接用于处理某皮革厂高浓度的含Cr(Ⅲ)实际废水,去除率达73%。本研究为综合处理含铬废水提供了思路,成为矿山资源化的途径之一。     

Ore Mineralogy and Mineral Chemistry of the Ashanti Gold Deposit at Obuasi, Ghana

Abstract: The gold deposit at Ashanti occurs in the Proterozoic Birimian formation of Ghana. Two main ore types mined from the deposit are gold-bearing quartz veins, and gold-sulfide disseminations in metasediments and metavolcanics. The main sulfide minerals in the gold-sulfide disseminated ores are arsenopyrite, pyrite and pyrrhotite, and to a very minor extent, sphalerite and tetrahedrite. Carbonate alteration and sericitization are prominent in the metavolcanics and the metasediments, respectively. In the quartz veins, pyrite and arsenopyrite commonly occur in small amounts, but gold mostly occurs in contact with tetrahedrite, chalcopyrite, galena, aurostibite, and sphalerite. Pyrrhotite is absent in the quartz veins.
Microprobe studies indicate that As content of homogeneous arsenopyrite grains ranges from 27. 0 to 31. 7 atm%, and gives mineralization temperatures from 170 to 430°C, although mostly from 300 to 400°C. Chlorite geothermometry using temperature dependence of substitution of Al for Si in the tetrahedral site gives formation temeratures of 330 to 400°C, comparable to the arsenopyrite temperatures. Applying sphalerite–pyrite–pyrrhotite geobarometry to sphalerite with FeS contents from 13. 6 to 12. 5 mol%, the pressure was estimated to be in a range from 5. 9 to 7. 0 kb at the stage of elevated temperatures.
Mineralogical observations, especially absence of pyrrhotite in the quartz veins, together with microprobe data for gold and associated minerals suggest that the fluids having ascended through fissures in the Ashanti deposit were reduced by the reaction with carbonaceous materials in the metasediments during the declining stage of the regional metamorphism.     

Diffusion of osmium in pyrrhotite and pyrite: implications for closure of the Re–Os isotopic system

In order to better constrain the extent to which common sulfide minerals will retain their osmium isotopic composition subsequent to crystallization, we have conducted experiments to quantify the diffusion behavior of osmium in pyrite and pyrrhotite. Experiments consisted of either (1) isothermal soaking of diffusion couples consisting of natural pyrite or pyrrhotite crystals packed against powdered Os-bearing Fe-sulfide or (2) ‘relaxation’ of initially high near-surface osmium concentrations produced in the latter experiments (pyrite only). Osmium penetration into samples was characterized by depth profiling using Rutherford backscattering spectroscopy (RBS) (pyrite) or electron microprobe analyses across sectioned run products (pyrrhotite). Results of the first type of diffusion experiment involving pyrite show only limited osmium penetration into sample surfaces, with the extent of penetration uncorrelated with run duration. Images of pyrite samples using atomic force microscopy show roughening of initially smooth surfaces as a consequence of step formation and suggest that osmium incorporation into the near-surface occurred by solute uptake during step growth and not by volume diffusion. Prolonged (1000⁺ h) ‘relaxation’ experiments revealed no additional osmium penetration into pyrite surfaces and based on the depth resolution for RBS, a maximum diffusion coefficient of 2.5×10⁻²³ m²/s at 500°C was calculated. Experiments involving pyrrhotite over the temperature range of 950–1100°C showed extensive osmium uptake and osmium concentration gradients that conform with Fickian diffusion behavior. We found that pyrrhotite Fe/S could be varied by changes in the composition of the starting material and osmium source and over the range of Fe/S produced in experiments (molar Fe/S=0.83–0.90), we observed no systematic variation in the osmium diffusion coefficient. Diffusion coefficients measured parallel to the a crystallographic axis were on average 1.4× higher than values measured parallel to c and regression of the c-axis data yielded the Arrhenius relation:

The application of these diffusion data to simple models of diffusive exchange during static or polythermal time–temperature histories is used to assess the conditions under which radiogenic osmium will be retained. During isothermal annealing, calculations indicate that the cores of millimeter-sized spherical pyrrhotite crystals undergoing diffusive exchange with an external osmium reservoir will have their initial compositions perturbed in ≤0.5 Ma at temperatures exceeding 400°C. Pyrite undergoing the same process at 500°C requires in excess of 10 Ma before crystal cores are affected. The relatively short ‘core retention’ time-scales for pyrrhotite indicates that this mineral may be prone to isotopic resetting following relatively brief crustal thermal events, thus possibly accounting for the scatter that commonly occurs in Re–Os isochrons generated from massive sulfide samples. Calculated closure temperatures (T_c) for osmium exchange in pyrrhotite yielded values of 300–400°C for grain sizes ranging from 10 to 1000 μm. These values of T_c are similar to those calculated for Ar retention in biotite, and considerably lower than for Sr in apatite and plagioclase, for example. Such low closure temperatures for pyrrhotite suggest this mineral will date the final stage in the cooling of a magmatic system and possibly be susceptible to open system osmium exchange in the presence of late-stage hydrothermal fluids. This latter result infers that caution be applied when interpreting elevated initial osmium isotopic ratios as a product of crustal assimilation at the magmatic stage.     

攀西基性岩中共生的陨硫铁和磁黄铁矿的穆斯堡尔效应研究

使用穆斯堡尔效应研究攀西基性岩中共生的陨硫铁和磁黄铁矿。陨硫铁的分子式为Fe_(1.009)S,晶胞参数a_0=5.96,c_0=11.74,根据Wuensch表示法,可以把它归结为1B,1C型。与陨硫铁共生的磁黄铁矿的分子式为Fe_(0.892)S,属于六方磁黄铁矿。本文确定了共生的陨硫铁和磁黄铁矿的穆斯堡尔参数,它们的谱分别是由一组磁六线谱和三组磁六线谱组成。比较攀西陨硫铁和人工合成陨硫铁及陨石中陨硫铁,可以得出结论,它们之间没有明显差别。     

金川铜镍硫化物矿床中特富矿分布特征及成因

块状特富矿是深部熔离-贯入型矿石的典型代表。通过地质模型来直观了解金川铜镍硫化物矿床中块状特富矿的空间分布:平面上分布于Ⅱ矿区33~41行之间,垂直方向上分布于1 150~1 500m标高范围内;根据其与Ⅱ矿区Ⅱ-②矿体的超基性岩的空间关系,将块状特富矿划分为岩体内部型和岩体边部型。通过对块状特富矿及其附近细脉浸染状矿的矿物成分测试,结果表明:块状矿石由98%以上的金属硫化物组成,金属矿物主要为磁黄铁矿、黄铁矿、黄铜矿、镍黄铁矿,其中,镍黄铁矿较发育,没有方黄铜矿;矿石中的磁黄铁矿均为单斜晶系,说明特富矿晶出温度很低,为100℃~320℃。首次对金川各类矿石中长石或石英进行液体包裹体测试,结果证明其成矿期晚于其他深部熔离-贯入型岩浆矿体。通过对成矿物质来源、成矿期次、控矿因素、成矿标志等的研究,指出块状特富矿分布受构造控制,与细脉浸染状矿石、含矿化辉绿岩脉密切相关,并认为NE向平推断层发育、且有细脉浸染状矿石或含矿化辉绿岩脉产出的部位是寻找块状特富矿的重点区域。     

含金石英脉中黄铁矿固态分解的组构特征

胶东新城及陕西小秦岭地区含金石英脉中，微晶磁黄铁矿交代置换黄铁矿并发育了一种特征的蠕虫状显微多孔构造，前人文献中尚未见报道。基于矿相学和矿物学研究，我们认为微晶磁黄铁矿及其特征的组构是黄铁矿固态等化学分解的产物，其显微多孔构造与体积收缩和硫的逸失有关。     

吉南地区晚震旦世震积岩特征

在吉南地区晚震旦世地层序列中,普遍发育有一套地震事件沉积物,其在垂向上由振动注伦泥昌碳酸盐脉灰岩,卷曲变形灰岩,阶梯状断层,海啸颗粒灰岩,津浪丘状交错层灰岩及钙屑浊积岩组成。