Transformation of magnetite to hematite and its influence on the dissolution of iron oxide minerals

Deformed rocks of the Itabira Iron Formation (itabirites) in Brazil show microstructural evidence of pressure solution of quartz and iron oxides; it appears that magnetite was dissolved and hematite precipitated. The dissolution of magnetite seems to be related to its transformation to hematite by oxidation of Fe²⁺ to Fe³⁺. The transformation of magnetite to hematite occurs along {111} planes, and results in the development of hematite domains along {111} that are parallel to the foliation. The difference in volume created by the transformation of magnetite to hematite and the shear stress acting on the interphase boundaries allow fluids to migrate along these planes. The dissolution of magnetite involves the hydrolyzation of the Fe²⁺—O bonds at interphase boundaries of high normal stress. The high fugacity of oxygen in the fluid phase promotes the reaction of Fe²⁺ (in solution) with oxygen. Fe²⁺ ions oxidize to Fe³⁺ and precipitate as hematite platelets with their longest axes oriented parallel to the direction of maximum stretching. The transformation of magnetite to hematite during deformation plays an important role in the fabric evolution of the iron formation rocks. The transformation along {111} creates planes of weakness that facilitate fracturing. The fracturing plus the dissolution result in a reduction of magnetite grain size, and the oriented precipitation results in layers of hematite platelets. These processes produce a new fabric characterized by a penetrative foliation and lineation.     

应用同步辐射技术解析黄色-红色石英质玉石中的致色矿物

质地细腻、颜色多彩的隐晶质-微粒脉石英在我国珠宝行业称为石英质玉石,颜色是石英质玉石价值判断的主要因素之一,揭示其致色矿物及致色机理对于研究石英质玉石的颜色评价指标和矿床成因具有重要意义,但前人并未直接获得致色矿物的准确信息。本文运用上海光源(SSRF)BL15U1线站的同步辐射硬X射线,使用μ-XRF和μ-XRD技术对黄色和红色隐晶质-微粒脉石英中的致色矿物进行了研究。结果表明,黄色石英质玉石由赋存于石英颗粒间或微裂纹中的针铁矿(特征衍射峰0.49574、0.41594、0.26887、0.25705、0.25189、0.24510、0.21806、0.17133 nm)或其集合体致色,红色石英质玉石由赋存于石英颗粒间或微裂纹中的赤铁矿(特征衍射峰0.36774、0.27091、0.25200 nm)或其集合体致色,黄色-红色石英质玉的颜色由针铁矿和赤铁矿共同致色,赤铁矿的显色能力要高于针铁矿。本文获得了石英质玉石中致色矿物的直接数据,为玉石结晶温度与致色机理的探讨、石英质玉石的品质评价提供了依据。     

新疆西天山式可布台铁矿地质、矿物化学和S同位素特征及其对矿床成因的约束

新疆西天山式可布台铁矿发育于伊犁裂谷内,赋存于上石炭统中酸性火山碎屑岩、浅变质片岩、千枚岩中,矿体呈层状、似层状以及透镜状顺层产出。金属矿物以赤铁矿、镜铁矿为主,含少量黄铁矿、菱铁矿;脉石矿物主要为碧玉、重晶石、石英以及少量方解石。矿石构造以条带状、纹层状和块状为主,矿物结构多为隐晶质结构、半自形结构以及充填结构。矿床分为4个成矿阶段,即黄铁矿-赤铁矿-铁碧玉-重晶石阶段、菱铁矿-软锰矿阶段、石英-镜铁矿阶段、氧化物阶段。矿体顺层产出和发育纹层状矿石构造指示矿床为沉积成因。电子探针分析显示:(1)块状赤铁矿Al2O3、Na2O、MgO、SiO2含量相对分散,推测这可能与块状矿石快速沉淀结晶有关,暗示了剧烈的流体喷流活动,而纹层状和条带状赤铁矿Al2O3、Na2O、MgO、Si O2含量相对集中则反映平静的沉积环境以及微弱的喷流活动,两者的比较可能暗示了成矿过程中流体喷溢速率以及沉积环境都不断改变;(2)黄铁矿中含有较高的Co、Ni比,显示其形成与火山作用关系密切;(3)菱铁矿的FeOT与Mn O+MgO含量呈负相关关系,并形成两个聚集区,与镜下其具有不同特征相吻合,可能暗示了成矿后期菱铁矿随热液析出时候发生了分异作用。黄铁矿(δ34S=-6.1‰~6.5‰)和重晶石(δ34S=12.9‰)硫同位素组成显示曾发生过硫酸盐和硫化物之间的硫同位素分馏作用,成矿热液的硫可能来源于岩浆硫。综合分析认为,式可布台铁矿可能为海相火山喷流沉积型铁矿床。     

Genesis of the channel iron deposits (CID) of the Pilbara region,Western Australia

Miocene fluvial goethite/hematite channel iron deposits (CID) are part of the Cenozoic Detritals 2 (CzD2), of the Western Australian Pilbara region. They range from gravelly mudstones through granular rocks to intraformational pebble, cobble and rare boulder conglomerates, as infill in numerous meandering palaeochannels in a mature surface that includes Precambrian granitoids, volcanics, metasediments, BIF and ferruginous Palaeogene valley fill. In the Hamersley Province of the Pilbara, the consolidated fine gravels and subordinate interbedded conglomerates, with their leached equivalents, are a major source of export iron ore. This granular ore typically comprises pedogenically derived pelletoids comprising hematite nuclei and goethite cortices (ooids and lesser pisoids), with abundant coarser goethitised wood/charcoal fragments and goethitic peloids, minor clay, and generally minimal porous goethitic matrix, with late-stage episodic solution and partial infill by secondary goethite, silica and siderite (now oxidised) in places. Clay horizons and non-ore polymictic basal and marginal conglomerates are also present. The accretionary pedogenic pelletoids were mostly derived from stripping of a mature ferruginous but apparently well-vegetated surface, developed in the Early to Middle Miocene on a wide variety of susceptible rock types including BIF, basic intrusives and sediments. This deep ferruginisation effectively destroyed most remnants of the original rock textures producing a unique surface, very different to those that produced the underlying CzD1 (Palaeogene) and the overlying CzD3 (Pliocene – Quaternary). The peloids were derived both intraformationally from fragmentation and reworking of desiccated goethite-rich muds, and from the regolith. Tiny wood/charcoal fragments replaced in soil by goethite, and dehydrated to hematite, formed nuclei for many pelletoids. Additionally, abundant small (≤10 mm) fragments of wood/charcoal, now goethite, were probably replaced in situ within the consolidating CID. This profusion of fossil wood, both as pelletoid nuclei and as discrete fragments, suggests major episodic wild fires in heavily vegetated catchments, a point supported by the abundance of kenomagnetite – maghemite developed from goethite in the pelletoids, but less commonly in the peloids. The matrix to the heterogeneous colluvial and intraformational components is essentially goethite, primarily derived from modified chemically precipitated iron hydroxyoxides, resulting from leaching of iron-rich soils in an organic environment, together with goethitic soil-derived alluvial material. Major variations in the granular ore CID after deposition have resulted from intermittent groundwater flow in the channels causing dissolution and reprecipitation of goethite and silica, particularly in the basal CID zones, with surface weathering of eroded exposures playing a role in masking some of these effects. However, significant variations in rock types in both the general CID and the granular ore CID have also resulted from the effects of varied provenance.     

纳米赤铁矿电极光电催化特性及苯酚降解活性研究

伴随环境污染问题日益加剧,借助半导体材料实现光能的光电转化在催化及环境领域引起广泛关注。本文借助电化学方法快速高效地合成不同沉积时间纳米赤铁矿薄膜电极。X射线衍射(XRD)、Raman光谱测试表明其成分为赤铁矿物相;原子力显微镜(AFM)观测颗粒尺寸约52.1(±1.48)nm×50.5(±1.49)nm,表面高度起伏分布于70~100 nm,且分布特征符合正态分布规律。紫外可见漫反射吸收谱显示电极可显著吸收350~600 nm波长范围可见光,计算得禁带宽度约2.0~2.1 e V。光电化学实验光电流密度-时间曲线及电流-电压曲线表明电极有良好的可见光光电催化活性,且反应符合Langmuir-Hinshelwood多相反应动力学模型。进一步选取效果较显著的沉积时间10 min电极研究其光电催化降解苯酚活性,0.65 V vs.SCE(饱和甘汞电极)恒电势光照条件下6 h苯酚降解率达62%,拟合一级动力学反应模型可知,反应速率常数k为0.16 h-1(R2=0.996)。综上,本文研究结果显示电化学法简单高效合成的纳米赤铁矿具有良好半导体性能且能够可见光光电催化降解苯酚等有机污染物。     

云南保山南红玛瑙矿物学特性及致色机理探究

通过光学显微镜、X射线粉晶衍射、X射线荧光光谱、电感耦合等离子体质谱、电子探针等测试分析手段对云南保山南红玛瑙的岩相学、矿物组成、化学成分等进行了系统研究,在此基础上进一步通过扫描电镜、X射线能谱元素面扫描、激光共聚焦显微拉曼分析了南红玛瑙致色矿物形貌、元素分布及矿物物相构成。研究结果表明,保山南红玛瑙主要矿物为石英(95%,质量分数),主要结构为粒状结构和纤维结构,次要矿物为斜硅石及方解石等,并含有吸附水和结构水两种状态水。致色矿物主要以小于1μm球状矿物颗粒、2~10μm絮状似球状集合体、针状矿物颗粒和不规则形态矿物集合体这4种类型存在,元素分析显示其为含铁矿物。显微拉曼进一步确认南红玛瑙的颜色是由含铁矿物所致,其中红色致色主要为赤铁矿,黄色致色主要为针铁矿,铁矿物的具体存在形式及其分布方式对南红玛瑙的价值具有决定性作用。本工作为南红玛瑙矿物学特性以及致色机理研究提供了有价值的参考信息,对完善其知识体系和推动南红玛瑙文化有重要意义,同时对借助共聚焦显微拉曼等微区表征技术推动宝玉石研究提供了新思路。     

Hematite spherules in basaltic tephra altered under aqueous, acid-sulfate conditions on Mauna Kea volcano, Hawaii: Possible clues for the occurrence of hematite-rich spherules in the Burns formation at Meridiani Planum, Mars

Iron-rich spherules (> 90% Fe₂O₃ from electron microprobe analyses) ∼10-100 μm in diameter are found within sulfate-rich rocks formed by aqueous, acid-sulfate alteration of basaltic tephra on Mauna Kea volcano, Hawaii. Although some spherules are nearly pure Fe, most have two concentric compositional zones, with the core having a higher Fe / Al ratio than the rim. Oxide totals less than 100% (93-99%) suggest structural H₂O and/or OH^− 1. The transmission Mössbauer spectrum of a spherule-rich separate is dominated by a hematite (α-Fe₂O₃) sextet whose peaks are skewed toward zero velocity. Skewing is consistent with Al³⁺ for Fe³⁺ substitution and structural H₂O and/or OH^− 1. The grey color of the spherules implies specular hematite. Whole-rock powder X-ray diffraction spectra are dominated by peaks from smectite and the hydroxy sulfate mineral natroalunite as alteration products and plagioclase feldspar that was present in the precursor basaltic tephra. Whether spherule formation proceeded directly from basaltic material in one event (dissolution of basaltic material and precipitation of hematite spherules) or whether spherule formation required more than one event (formation of Fe-bearing sulfate rock and subsequent hydrolysis to hematite) is not currently constrained. By analogy, a formation pathway for the hematite spherules in sulfate-rich outcrops at Meridiani Planum on Mars (the Burns formation) is aqueous alteration of basaltic precursor material under acid-sulfate conditions. Although hydrothermal conditions are present on Mauna Kea, such conditions may not be required for spherule formation on Mars if the time interval for hydrolysis at lower temperatures is sufficiently long.     

Characteristics and genesis of hematite in Chinese loess and paleosol sequences： Mineral genetic restriction for magnetic susceptibility as paleoclimate proxy and iron geochemistry

Hematite is an important iron oxide mineral in loess-paleosol sequences in central China. Investigation of the mineralogical characteristics, genetic mechanism and relationship of hematite with other iron oxides and Fe-bearing minerals will help understand the geochemical process before and after eolian deposit, paleocliamte significance of magnetic susceptibility and reconstruct paleoclimate in central China. So, hematite and related minerals of the loess and paleosol units from Chinese Loess Plateau were investigated using optical microscope, X-ray powder diffraction （XRD）, scanning electron microscopy （SEM）, and high-resolution transmission microscopy （HRTEM）. The results show that there are five genetic types of hematite in loess-paleosol sequences of central China： （1） weathering of Fe-bearing silicate minerals, for instance, chlorite, will release iron that is precipitated as aggregates of hematite nano-crystals on mineral surfaces; （2） hematite combined with eolian magnetite grains that resulted from partial oxidation of magnetite, even though the partial oxidation may occur in the original area; （3） phase transformation from eolian goethite to hematite; （4） hematite formed on the edge and surface of maghemite because of dissolution and hematite recrystallization; and （5） eolian detrial hematite. The hematite formed from chemical weathering of Fe-bearing silicates with nanoporous texture because of dehydration from iron hydroxide is the most important genetic mechanism. It is proposed that the fact that hematite was formed from chemical weathering of Fe-bearing silicates is a main reason for the redness in paleosol units. However, too intense pedogenesis and high amounts of precipitation will promote oxidation of eolian magnetite and maghemite dissolution, which may result in the decreasing of magnetic susceptibility.     

Opaque mineralogy and magnetic properties of selected banded iron‐formations,Hamersley Basin,Western Australia

The oxide mineralogy and rock magnetic properties of unmineralised banded iron‐formations in selected portions of four drillholes in the Hamersley Basin, Western Australia are reviewed. In all four drillholes, petrographic studies indicate that primary euhedral to subhedral hematite is partially replaced by magnetite as a result of subsolidus reduction. All drillholes show partial recrystallisation of the secondary magnetite, suggesting that early subsolidus reduction was probably a regional event occurring during prograde metamorphism. Incomplete replacement of primary hematite by magnetite within and between sedimentary band structures indicates that equilibration in the magnetite stability field was not reached even at the mesoband scale. Subsequent subsolidus oxidation of magnetite and the formation of a second‐generation hematite are documented in only two of the drillholes. Goethite‐filled veins and thick selvages of goethite around some veins reflect movement of circulating oxidising fluids. The absence of goethite and second‐generation hematite in two of the drillholes indicates that subsolidus oxidation is not a regional event, but very much localised. Rapid changes in down‐hole susceptibility measurements correlate directly with detailed petrographic results as susceptibility readings change with the hematite/magnetite ratio on a mesoband scale. Acquisition of the main remanence correlates with the formation of hematite as the primary oxide phase followed by partial replacement by magnetite as a result of subsolidus reduction, supporting regional models requiring pre‐folding remanence. The strong orientation of the primary hematite parent parallel to band structures in the banded iron‐formations has influenced the direction of crystallisation remanent magnetisation during subsolidus reduction to the magnetite daughter. The strong planar alignment has also produced a planar magnetic fabric and marked anisotropy of magnetic susceptibility. A natural remanent magnetisation overprint and reduction in anisotropy of magnetic susceptibility are only recorded in samples that have undergone subsolidus oxidation and the recognition of localised post‐metamorphic oxidation overprinting can also explain ore deposit models requiring post‐folding remanence. The relative timing of and between oxidising fluid events is not known, but both petrographic and rock magnetic evidence to date suggests that there was at least one and probably two post‐folding oxidising events in the area of study.     

鄂西高磷鲕状赤铁矿磁化还原矿物组成及分布规律

鄂西高磷鲕状赤铁矿原矿全铁品位47.56%,含P 0.93%,主要脉石矿物为绿泥石、磷灰石、石英、方解石、铁白云石,属难选铁矿石。通过磁化焙烧-磨矿-磁选优化工艺,最佳磁化焙烧条件为:焙烧温度800℃、焙烧时间90min、还原剂用量12%,焙烧矿磨矿细度-0.074mm占85.15%,经弱磁选可得到全铁品位为58.13%、磷含量0.70%,铁回收率为90.41%的粗精矿。对磁化焙烧-磁选过程的各产物组成分析表明,焙烧矿和粗精矿中主要矿物为磁铁矿,占比分别为65%和85%;主要脉石矿物为绿泥石、磷灰石、石英、铁白云石等。粗精矿矿物的嵌布粒度较细,-0.074mm粒级占85.15%,但部分矿物仍以相互浸染、包裹、鲕状碎屑、连晶等形式存在,矿物仍未完全单体解离,从而导致粗精矿中杂质磷、铝等含量较高。粗精矿细磨后粒度-0.022mm含量为80%时,磁铁矿的解离度为84.63%,可实现磁铁矿充分单体解离,经过深选可提高铁精矿质量。