磁铁矿的穆斯堡尔谱研究

我们对大冶、马坑、大顶、黄沙坪、鞍山五个矿区的七个铁矿石样品中的磁铁矿作了室温~(57)Fe和~(119)Sn穆斯堡尔谱测定,并根据穆斯堡尔数据和化学分析推算出磁铁矿的非理想配比的分子结构式. 初步研究表明,不同的成矿条件和Zn、Mg等二价阳离子的类质同像替代的多少,明显地影响晶胞参数和穆斯堡尔参数.文中讨论了它们的变化规律性.     

广西茶山辉铁锑矿的初步研究

辉铁锑矿产于广西茶山矿区28号脉。脉中主要矿物共生组合是毒砂-黄铁矿,方铅矿-闪锌矿,辉铁锑矿-辉锑矿及石英-辉锑矿。其爆裂温度为:265—210℃,203—187℃,202—180℃,124—120℃。此外,还有少量石英-白钨矿及铅锑硫盐矿物组合。 辉铁锑矿呈柱状或针状自形晶,具强的双反射和反射多色性。计算分子式为Fe_(0.93-1.07) Sb_(2-2.17)S_4,含少量As、Sn、Au.X射线衍射的强线有、(100)3.6405,(80)3.1643,(80)2.9901,(80)2.5996。晶胞参数 α=11.46,b=14.04,c=3.74。 辉铁锑矿的穆斯堡尔谱是一个对称的四级双峰。其同质异能位移=0.788—0.822mm/s,四级分裂=2.66—2.727mm/s,穆斯堡尔谱的研究表明,辉铁锑矿中的铁为Fe~(2 )并处于畸变八面体中;Fe~(2 )与S为离子键合。这与晶体结构的研究是一致的。     

矿物穆斯堡尔谱学研究动态

穆斯堡尔效应(Mbssbauer effect)是一种无反冲的核γ射线的共振吸收现象.自六十年代初发现~(57)Fe的能量为14.4Kev的γ射线无反冲共振吸收后,在物理,化学等部门逐渐得到广泛的应用.由于铁在地壳中分布非常广泛,多数矿物都含有铁,所以六十年代中以后,Fe穆斯堡尔效应应用于矿物研究,十多年来发展很快,到现在,Fe穆斯堡尔效应已成为矿物研究的一种重要工具.新近矿物穆斯堡尔谱学研究有如下几个方面:1.用穆斯堡尔方法测定矿物中阳离子位置分布矿物中阳离子位置分布和有序—无序现象是矿物学研究的重要课题.穆斯堡尔方法,为研究矿物中Fe~(2+)—Mg~(2+)位置分布及有序—无序现象提供一种简便而有效的方法,并将     

岫岩玉的穆斯堡尔谱学研究

岫岩玉是我国的主要玉种之一,属于蛇纹石玉。在X射线衍射、红外光谱、可见光吸收谱,及电子显微镜等项研究确切查明主体矿物为叶蛇纹石的基础上,选两个优质玉样进行~(57)Fe穆斯堡尔谱学研究。岫岩玉的穆斯堡尔谱由两组四级双峰构成,第一组双峰(δ=1.12,△=2.73与2.72mm/s)系由镁氧八面体中的Fe~(2+)形成,另组双峰(δ=0.35与0.36,△=0.63与0.55mm/s)反映的是镁氧八面体中的Fe~(3+),Fe~(3+)/Fe~(2+)分别为0.90与0.78。铁是参与叶蛇纹石晶格的组分;Fe~(3+)与Fe~(2+)均处镁氧八面体中;Fe~(3+)/Fe~(2+)近于与小于1是制约它呈绿色的主要因素。     

几种锡矿物的穆斯堡尔谱研究

本文对我国一些地区的锡石、黄锡矿、辉锑锡铅矿等锡矿物样品进行了化学成分分析、穆斯堡尔谱测试,并利用穆斯堡尔谱方法区分了这些锡矿物中锡的价态。实测结果表明,锡石中的锡全是Sn~(4+)(六配位),黄锡矿中的锡是Sn~(4+)(四配位),辉锑锡铅矿中的锡有Sn~(4+)及少量 的Sn~(2+)。钙铁榴石中的锡是Sn~(4+),它是以类质同像替换方式进入[Y]位替换Fe~(3+)。同时,讨论了同质异能位移值与价态的关系,I.S值的增大顺序为:Sn~(4+)→Sn~0→Sn~(2+)。根据经验公式,估算了一些锡矿物中氧和硫配位基的电负性,     

东疆红山Cu-Au矿床氧化带硫酸盐矿物穆斯堡尔谱特征及其意义

穆斯堡尔谱对确定铁离子占位、核外环境及氧化态方面有着独特的优势。在红山铜金矿床氧化带硫酸盐矿物的XRD、TA、湿法化学分析和红外光谱测试的基础上,测定了板铁矾、针绿矾等8种硫酸盐矿物的室温57Fe穆斯堡尔谱,并根据常温下硫酸盐矿物穆斯堡尔谱参数和其晶体结构中Fe3+和Fe2+的占据位置对其谱峰进行了指派。结果表明本矿床氧化带硫酸盐矿物的穆斯堡尔谱的同质异能位移较小、四级矩分裂值分布范围较大、无磁超精细分裂等特征,且硫酸盐矿物结构中存在着共价键。通过与青海锡铁山铅锌矿氧化带硫酸盐矿物的穆斯堡尔谱相比较,两者在近地表风化及氧化过程中所处的物理化学条件基本相同,酸性和氧化性的环境为硫酸盐矿物的产生和保存提供了良好条件,但红山矿床更为干旱少雨,导致两者硫酸盐的穆斯堡尔谱参数略有不同。     

辉锑锡铅矿的穆斯堡尔谱及其晶体化学研究

辉锑锡铅矿是结构复杂而尚未确定,以及晶体化学尚有争议的一种稀有矿物。X射线衍射结果表明其结构是由假四方亚层(称T层)和假六方亚层(称H层)穿插组成的层状结构。T层的化学成分具有MeS形式,H层则具有MeS_2形式。本文通过广西大厂的辉锑锡铅矿的穆斯堡尔谱研究,确定了矿物中Sn的大部分为Sn~(4+),而Sn~(2+)只占较少的部分;Fe中含有Fe~(3+)和Fe~(3+)。它们在T层和H层中的分布为Sn~(2+)(T)占5.6%,Sn~(4+)(T)占25.9%,Sn~(4+)(H)占68.5%,Fe~(2+)(T)占59.5%,Fe~(3+)(H)占40.5%。从Sn、Fe的穆斯堡尔谱参数还可看出H层的共价性比T层的强。     

华南某矿区磁铁矿的谱学研究

从~（57）Fe和~（119）Sn无反冲共振吸收谱分析,配合x射线衍射分析等方法,获知华南某铁矿-多金属矿区,两种铁矿石中磁铁矿的组份。从穆斯堡尔谱峰面积法,推算出非正分的磁铁矿晶体结构式,并由此算出其中Fe~（2+）和Fe~（3+）的含量比。综合矿石产状及铁的氧化态分析,获得不同铁矿石的成因信息。     

多硅白云母中Fe2+的高压有序效应

21个多硅白云母来自4个低温高压变质带。用电子探针、X射线粉末衍射及穆斯堡尔谱测定其化学成分、b0值及Fe²⁺占位。建立Fe²⁺(M1)/Fe²⁺(M2)对b0值相关图,发现Fe²⁺在八面体晶位有序化并解释其有序机理。     

矿物样品的穆斯堡尔谱拟合方法

近年来穆斯堡尔效应在我国矿物学研究工作中得到了广泛的应用。因此,编写一种收敛快、计算迅速的优化拟合程序就显得特别重要。 矿物样品的穆斯堡尔谱数据是由m道分析器(一般为200—500道)读出的m个读数(强度计数)所构成的。一般认为,穆斯堡尔谱是由NL个洛伦兹峰的叠加。     

异性石中平面四配位Fe^2＋的穆斯堡尔谱研究

除硅铁钡矿之处，性石是迄今仅知的另一种含有平面四配位Ｆｅ＾２＋的矿物，异性石晶体样品为玫瑰色，透明，有油脂光泽，取自一花岗岩标本，异性石中平面四配位Ｆｅ＾２＋的穆斯堡尔参数：化学位移＝０．７８５（ｍｍ／ｓ）（相对天然铁），四极矩分裂＝０．４１９（ｍｍ／ｓ），明显地低于大多数硅酸矿物中的Ｆｅ＾２＋，但和硅铁钡矿的Ｆｅ＾２＋十分相近，本文对硅酸盐矿物Ｆｅ＾２＋的穆斯堡尔参数与配位数之间的关系做了讨论。     

广西大黎铜钼矿石英二长(斑)岩年代学、地球化学特征及其地质意义

大黎石英二长(斑)岩岩体出露于广西壮族自治区大瑶山地区藤县大黎镇南部一带,LA-ICP-MS测得石英二长岩和石英二长斑岩的U-Pb年龄分别为(102.8±0.9)Ma和(101.7±1.2)Ma。岩体SiO2含量为60.09%～62.91%,Na2O和CaO的含量分别为2.90%～3.08%,3.32%～4.35%,A/CNK=0.83～0.93,均小于1.0,100Fe3+/(Fe3++Fe2+)的值为37.76～42.93,里特曼指数σ变化范围为2.94～3.07,属于钙碱性、准铝质花岗岩系列。稀土元素总体显示轻稀土元素富集,轻、重稀土元素分馏明显,总体呈具有弱Eu异常右倾的稀土配分模式。微量元素总体显示相对富集Rb、Th、U、K、La、Ce、Pb等大离子亲石元素,亏损Nb、Ta、P、Ti等高场强元素。综合分析表明,大黎石英二长(斑)岩为壳幔混合源I型花岗岩;结合区域构造演化历史,认为大黎石英二长(斑)岩是燕山晚期早白垩世晚期后碰撞阶段张性构造环境的产物,与印度板块在该时期北移所引起的古太平洋板块高角度俯冲所导致的弧后拉张有关。通过论述区域构造演化,探讨该岩体的基本属性、成因、形成环境,分析了有利成矿条件:①I型石英二长(斑)岩为有利的成矿母岩;②矿区具有相对较高的Cu、Mo、Pb、Sn成矿元素背景值;③研究区的深大断裂和井字形断裂系统是控矿的有利地质构造。推测本矿区斑岩型铜钼矿的成矿年龄与成岩年龄基本一致,为100Ma左右的早白垩世晚期。     

桂东北姑婆山岩体矿物学和年代学特征及其成岩成矿意义

为揭示桂东北姑婆山一带花岗岩的成岩成矿特征，本文对姑婆山岩体进行了黑云母矿物化学成分分析和锆石U-Pb年代学研究。花岗岩中黑云母化学成分分析结果表明：黑云母具有富铁镁、贫钙钠的特征，w（TFeO）为26.78%~31.06%、w（MgO）为2.98%~6.60%，且w（TFeO）与w（MgO）呈明显的负相关性，说明其结晶过程中主要发生了Fe²⁺←→Mg²⁺的置换反应；黑云母的含铁指数为0.68~0.84，属于高铁黑云母，氧逸度为-17.0~-15.5，结晶温度为680~705℃，平均为695℃；黑云母的全铝压力计显示黑云母结晶的压力为69~179 MPa，平均为115 MPa，对应的侵位深度相当于2 621~6 755 m，平均深度为4 331 m。年代学分析结果显示，采自姑婆山岩体的两个代表性花岗岩样品形成年龄分别为（162±3）和（163±2）Ma，为燕山早期，与华南中生代大规模岩浆-成矿作用时代一致。综合上述分析，姑婆山岩体形成于较高温度、低氧逸度、较浅的环境，显示出良好的锡成矿性，具有良好的找矿前景。     

Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries,Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ⁵⁶Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ⁵⁶Fe value: the δ⁵⁶Fe values of SPM in summer were lower than in winter. The seasonal variation in δ⁵⁶Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ⁵⁶Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ⁵⁶Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ⁵⁶Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ⁵⁶Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.     

The structural state of iron in oxidized vs. reduced glasses at 1 atm: A57Fe Mössbauer study

A general model for the structural state of iron in a variety of silicate and aluminosilicate glass compositions in the systems Na₂O-Al₂O₃-SiO₂-Fe-O, CaO-Al₂O₃-SiO₂-Fe-O, and MgO-Al₂O₃-SiO₂-Fe-O is proposed. Quenched melts with variable Al/Si and NBO/T (average number of nonbridging oxygens per tetrahedrally coordinated cation), synthesized over a range of temperatures and values of oxygen fugacity, are analyzed with⁵⁷Fe Mössbauer spectroscopy. For oxidized glasses with Fe³⁺/∑Fe>0.50, the isomer shift for Fe³⁺ is in the range ～0.22–0.33 mm/s and ～0.36 mm/s at 298 K and 77 K, respectively. These values are indicative of tetrahedrally coordinated Fe^3?. This assignment is in agreement with the interpretation of Raman, luminescence, and X-ray,K-edge absorption spectra. The values of the quadrupole splitting are ～0.90 mm/s (298 K and 77 K) in the Na-aluminosilicate glasses and compare with the values of 1.3 mm/s and 1.5 mm/s for the analogous Ca- and Mg-aluminosilicate compositions. The variations in quadrupole splittings for Fe³⁺ are due to differences in the degree of distortion of the tetrahedrally coordinated site in each of the systems. The values of the isomer shifts for Fe²⁺ ions in glasses irrespective of Fe³⁺/∑Fe are in the range 0.90–1.06 mm/s at 298 K and 1.0–1.15 mm/s at 77 K. The corresponding range of values of the quadrupole splitting is 1.75–2.10 mm/s at 298 K and 2.00–2.35 mm/s at 77 K. The temperature dependence of the hyperfine parameters for Fe²⁺ is indicative of noninteracting ions, but the values of the isomer shift are intermediate between those values normally attributable to tetrahedrally and octahedrally coordinated Fe²⁺. The assignment of the isomer-shift values of Fe²⁺ to octahedral coordination is in agreement with the results of other spectral studies. For reduced glasses (Fe³⁺/∑Fe≈<0.50), the value of the isomer shift for Fe³⁺ at both 298 K and 77 K increases and is linearly correlated with decreasing Fe³⁺/∑Fe in the range of \(f_{O_2 } \) between 10^?3 and 10^?6 atm when a single quadrupole-split doublet is assumed to represent the absorption due to ferric iron. The increase in value of the isomer shift with decreasing \(f_{O_2 } \) is consistent with an increase in the proportion of Fe³⁺ ions that are octahedrally coordinated. The concentration of octahedral Fe³⁺ is dependent on the \(T - f_{O_2 } \) conditions, and in the range of log \(f_{O_2 } \) between 10^?2.0 and 10^?5 a significant proportion of the iron may occur as iron-rich structural units with stoichiometry similar to that of inverse spinels such as Fe₃O₄, in addition to isolated Fe²⁺ and Fe³⁺ ions.     

Using cocrystallization coefficients of isomorphous admixtures for determination of element concentrations in ore-forming solutions (by the example of Mn/Fe ratio in magnetite)

The cocrystallization coefficient of Mn and Fe (D_Mn/Fe) in magnetite crystals is determined in hydrothermal-growth experiments with internal sampling at 450 and 500 °C and 100 MPa (1 kbar). It is weakly dependent on temperature in the studied PT-region and is constant over a wide range of Mn/Fe values. This permits using the magnetite composition as an indicator of Mn/Fe in the fluid under equilibrium: (Mn/Fe)_aq ≈ 100 (Mn/Fe)_mt. Since Mn is often a macrocomponent of the fluid and a microcomponent of magnetite, local analysis of fluid inclusions for Mn might help to determine Fe even in iron minerals. This will permit evaluation of the contents of other ore metals if the D_Me/Fe values are known. For fine crystals (< 0.1–0.2 mm) with low contents of Mn (< 0.01–0.02%), it is necessary to take into account the fractionation of Mn into the surficial nonautonomous phase, in which its content can reach several percent. Comparison of these data with earlier data on the distribution of Mn in the system magnetite–pyrite–pyrrhotite–greenockite–hydrothermal solution shows that D_Mn/Fe remains constant in the presence of sulfur and sulfides. Precipitation of magnetite, in which Mn is a compatible admixture, cannot affect radically Mn/Fe in the solution because of the low D_Mn/Fe value. This effect is still more unlikely for pyrrhotite and pyrite, in which Mn is an incompatible admixture. The most probable mechanism of Mn fractionation into the solid phase is crystallization of FeOOH at lower temperatures. This is indirectly supported by the strong fractionation of Mn into the nonautonomous oxyhydroxide phase on the surface of magnetite crystals. The necessity of a more rigorous validation of “the new Fe/Mn geothermometer for hydrothermal systems” is substantiated.     

Phyllosilicate and rutile compositions as indicators of Sn specialization in some southeastern Australian granites

Biotites from unaltered Sn granites in southeastern Australia are highly ferroan, Fe/(Fe+Mg+Mn) >0.75, whereas biotites from barren granites are less Ferich, Fe/(Fe+Mg+Mn)<0.65. Similar distinctions between Sn-specialized and barren granites can be observed in the other phyllosilicates, especially chlorite. Biotites and muscovites from Sn granites have greater Be, Cs, (F), Li, Mo, Rb, Sc, Sn, Tl, (Y) and Zn and lesser Ba abundances than corresponding micas from barren granites in the same district. Alteration of barren granites also results in similar enrichments in micas. Of these elements, Sn and Zn, because of their abundance and retention during degradation of biotite to chlorite, are the best trace element discriminants between barren granites and Sn granites/altered granites, with the Sn content of phyllosilicates being a better indicator than Zn. Rutile inclusions within phyllosilicates from unaltered Sn granites have Nb₂O₅ contents up to 26%. The Ta content tends to increase with Nb content but especially high Ta contents occur in the rutile inclusions of granites that give rise to pegmatitic deposits. The rutile inclusions in Sn granites may also have substantial Sn and W contents. The rutiles of barren granites have low Nb, Ta, Sn and W contents but Sn and W increase with alteration. Together, the ratio Fe/(Fe+Mg+Mn) and Sn contents in phyllosilicates and rutile compositions can be used to identify the Sn mineralization potential of a granite.     

Geochronology,geochemistry and Sr–Nd–Hf–S–Pb isotopes of the Early Cretaceous Taoxihu Sn deposit and related granitoids,SE China

The Taoxihu deposit (eastern Guangdong, SE China) is a newly discovered Sn polymetallic deposit. Zircon U-Pb dating yielded 141.8 ± 1.0 Ma for the Sn-bearing granite porphyry and 145.5 ± 1.6 Ma for the biotite granite batholith it intruded. The age of the granite porphyry is consistent (within error) with the molybdenite Re–Os isochron age (139.0 ± 1.1 Ma) of the Sn mineralization, indicating a temporal link between the two. Geochemical data show that the granite porphyry is weakly peraluminous, contain high Si, Na and K, low Fe, Mg, Ca and P, and relatively high Rb/Sr and low K/Rb values. The rocks are enriched in Rb, Th, U, K, and Pb and depleted in Ba, Sr, Ti and Eu, resembling highly fractionated I-type granites. They contain bulk rock initial ⁸⁷Sr/⁸⁷Sr of 0.707371–0.707730 and εNd(t) of −5.17 to −4.67, and zircon εHf(t) values from −6.67 to −2.32, with late Mesoproterozoic T_DM2 ages for both Nd and Hf isotopes. This suggests that the granite porphyry was likely formed by the partial melting of the crustal basement of Mesoproterozoic overall residence age with minor mantle input.δ³⁴S_CDT values of the Taoxihu chalcopyrite and pyrite range from 0.1 to 2.1‰ (average: 0.9‰), implying a dominantly magmatic sulfur source. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of the Taoxihu sulfide ores are 18.497–18.669, 15.642–15.673 and 38.764–38.934, respectively, indicating a mainly upper continental crustal lead source with minor mantle contribution. The highly fractionated and reduced (low calculated zircon Ce⁴⁺/Ce³⁺ and Eu_N/Eu_N¹ values) nature of the ore-forming granitic magma may have facilitated the Sn enrichment and played a key role in the Sn mineralization. We propose that the ore-forming fluids at Taoxihu were of magmatic-hydrothermal origin derived from the granite porphyry, and that both the granite porphyry and the Sn mineralization were likely formed in an extensional setting, possibly related to the subduction slab rollback of the Paleo-Pacific Plate.     

南秦岭大型钡成矿带中硫钒铜矿的特征及成因意义

在南秦岭下寒武统硅岩建造中的毒重石-重晶石矿床中,产出大量硫钒铜矿.硫钒铜矿呈正方形,长方形及不规则状,粒度大小变化较大,一般为0.01 mm～1 mm,最大可达7 mm.反光显微镜下为淡柠檬黄色,显微硬度134.5 kg/mm2～139.8 kg/mm2,相当于摩氏硬度3.46～3.50.主要化学成分为:Cu 47.18～52.02(平均50.44),V 6.50～14.32(平均11.95),Sn 0.00～12.85(平均2.15),S 31.77～34.34(平均33.29),As 0.00～5.12(平均0.86).Fe 0.00～3.27(平均0.77),部分样品含有极少量的Fe,Ni,Co,Sb,Se,Te,In.相应的平均化学分子式为Cu3.04(V0.90,Sn0.07,Fe0.05,As0.04,Sb0.01)1.07(S3.98,Se0.02)4.00,简化式为:Cu3(V,Sn,As,Fe)S4.矿物为等轴晶系.晶胞参数值a=0.539 2nm.成矿带中硫钒铜矿的形成与钒的富集,与有机质演化受热和生物降解作用有密切联系.