磁铁矿中硅的赋存状态研究进展:兼论新疆雅满苏铁矿床中磁铁矿晶体化学特征

磁铁矿广泛出现于各种类型的岩石中,具有反尖晶石结构。Si与Fe无论是从离子半径还是从电子的获取能力上均存在较大区别,然而无论是利用电子探针分析还是湿化学法,很多研究均表明:磁铁矿晶体中含有一定数量的硅。目前,硅是否类似于Al、Mg、Ti等元素,以类质同象的方式进入磁铁矿晶格目前尚不明确。已有研究表明Si在磁铁矿中的含量对磁铁矿的生成环境(成矿环境)有较大的指示意义:热液环境中生成的磁铁矿晶体的SiO_2的含量可达6.19 wt%,而在一些正岩浆型的磁铁矿中,SiO_2的含量常常低于电子探针的检出限。结合实际研究资料,尝试阐明新疆哈密地区雅满苏矽卡岩型矿床磁铁矿晶体中硅的可能赋存状态。研究表明,新疆雅满苏矽卡岩型磁铁矿矿床中的磁铁矿中SiO_2的含量相对较高,而且Si的含量与Fe~(3+)含量呈明显的线性负相关关系;穆斯堡尔谱结果亦指示Si替换了四面体上Fe~(3+)的位置,并且在八面体位置上四极分裂愈大,类质同象替代愈加广泛。     

掺Fe和V的金红石电子结构的第一性原理计算研究

采用基于密度泛函理论的第一性原理计算方法,对掺杂Fe和(或)V的金红石型TiO2的电子结构进行了计算。理论模拟的结果表明,纯金红石的禁带宽度为1.98 eV;Fe掺杂金红石型TiO2的禁带宽度为2.18 eV,由Fe3d和O2p轨道杂化在禁带中间形成了两条杂质能级;V掺杂金红石型TiO2的禁带宽度减小为1.80 eV,由V3d和O2p轨道杂化形成的杂质能级位于金红石的导带底,引入了一个浅施主能级;Fe和V共掺杂的金红石禁带中存在一个较宽的杂质能带,禁带宽度减小为1.73 eV。杂质能级的出现以及禁带宽度的减小使得Fe和V掺杂的金红石具有更好的可见光响应能力。同时,Fe和V的类质同像替代使得金红石中MO6八面体具有较大的畸变程度,有助于表面缺陷的增加,从而为光催化反应提供天然活性位。为进一步深入揭示含铁、钒等杂质的天然金红石的可见光催化机制提供了理论支持。     

利用碳酸盐岩的Fe/Mn比值恢复海洋的氧化还原状态

碳酸盐岩的Fe/Mn元素比值,作为一项新的地球化学指标,可以用于恢复海洋的氧化还原状态.在氧化条件下,Fe³⁺和Mn⁴⁺均不可溶,因此氧化海水中的溶解Fe和Mn的含量均很低.Fe³⁺和Mn⁴⁺在还原条件下可以被细菌还原为可溶的Fe²⁺和Mn²⁺,而氧化还原电位的计算表明,Mn⁴⁺的还原要早于Fe³⁺的还原,因此细菌的Mn还原过程发生在沉积物的更浅层.可溶的Fe²⁺和Mn²⁺向上扩散到海水中,替代碳酸盐岩晶格里的Ca²⁺,因此碳酸盐岩晶格中的Fe²⁺和Mn²⁺的含量受控于来自沉积物孔隙水的扩散,而后者又与水岩界面的氧化还原状态相关.因此可以预测,随着海水变得逐渐缺氧,碳酸盐岩中的Fe/Mn比值会逐渐增高.为了验证这一假说,我们分析了中元古代高于庄组白云岩的Fe/Mn比值.研究发现,几乎所有的样品的Fe/Mn比值介于20～30之间,显著高于泥盆纪末期深水碳酸盐岩和浅水台地碳酸盐岩的Fe/Mn比值.高于庄组碳酸盐岩高的Fe/Mn比值一方面可能指示了中元古代低的大气氧气浓度和海洋的广泛缺氧,也可能反映了白云岩形成于缺氧的沉积物空隙水里.     

黔东柏松铅锌矿床闪锌矿LA-ICP-MS微量元素组成特征及其地质意义

黔东柏松铅锌矿床位于扬子板块东南缘的湘西–黔东成矿带。与该成矿带内其他铅锌矿床相比,柏松铅锌矿床地质地球化学研究程度较低,矿床成因类型以及Cd、Ge、Ga等关键金属元素在闪锌矿中的赋存状态尚不清楚。本文通过LA-ICP-MS对该矿床闪锌矿微量元素组成进行分析,结果显示:柏松铅锌矿床中闪锌矿富集Cd、Fe、Ge、Pb,亏损V、Co、Ni、Cu、Te、Bi等元素。结合闪锌矿微量元素含量和Zn/Cd、Zn/Fe值特征,认为该矿床形成温度较低,根据Fe、Ga、Ge、Mn和In估算其成矿温度在75～135℃之间。闪锌矿中Fe与Cd具有较明显的负相关性,表明它们主要以类质同象的形式赋存于闪锌矿中,替代机制为:Zn²⁺?Fe²⁺、Zn²⁺?Cd²⁺,而Ge主要的替代机制为2Zn²⁺?Ge⁴⁺+□(□为晶体空位),Ga与Cu替代机制为2Zn²⁺?Ga³⁺+Cu⁺,In与Cu可能存在(Cu⁺     

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。     

鄂尔多斯盆地南部旬邑-宜君地区直罗组古层间氧化带地球化学特征及水-岩作用探讨

鄂尔多斯盆地南部旬邑-宜君地区直罗组古层间氧化带具有明显分带特征,通过对不同分带砂岩主量、微量、稀土元素及环境敏感参数特征对比研究,将旬邑-宜君地区古层间氧化带发育的水-岩作用过程划分成两个阶段：古层间氧化带形成和大规模成矿阶段、二次还原改造阶段。(1)古层间氧化带形成和大规模成矿阶段：含氧水进入目的层砂体,使砂体中Fe²⁺氧化成Fe³⁺(Fe²⁺含量最低,Fe³⁺最高);砂体中的U被氧化为U⁶⁺,形成铀酰腐殖酸盐络合物发生迁移(U、Corg、S含量最低、Th/U比值最高);长石高岭土化使Si发生流失(SiO₂含量降低);携带大量U的氧化流体运移至氧化还原过渡带(Corg、∑S含量最高、Fe²⁺含量仅低于灰绿色砂体),还原剂(有机质和黄铁矿等)将U⁶⁺还原成U⁴⁺,形成沥青铀矿;U⁴⁺与SiO₄^4-发生反应形成铀石(Th/U比...     

澳大利亚昆士兰州ERNEST HENRY IOCG矿床中磁铁矿地球化学组成及其意义

<正>磁铁矿存在于世界上大多数IOCG矿床中(但不是全部IOCG)中。磁铁矿形成过程的研究将有助于定位新的靶区,或者是解释矿床形成过程中热液条件变化(Beaudoin,2009;Dupuis,2011;Nadoll,2012)。然而,由于磁铁矿中含有Fe3+和Fe2+大量的化学替代,因此磁铁矿的微量元素地球化学显得十分复杂(Deer,1992)。目前,对于磁铁矿中微量元素组成和磁铁矿形成过程中     

金在黄铁矿表面沉淀机理的实验研究

为了研究金在黄铁矿表面沉淀的机理,于室温、常压,在氯化物溶液中进行了黄铁矿粉末吸附金的实验。在不同pH的溶液中,黄铁矿均可吸附金,而且pH值明显地影响吸附速率。扫描电镜观察表明,反应后黄铁矿粒表面有金晶体形成。XPS研究得知,黄铁矿光片与含金氯化物溶液反应后表面有A⁰存在;硫在反应初期为S⁰、S₂O₃^2-,随后转变为SO₄^2-,而铁成为Fe³⁺.黄铁矿中的Fe²⁺和S₂^2-是溶液中金的还原剂。金在黄铁矿表面沉淀可能涉及吸附、还原和晶体生长等过程。     

Fe—Mn—Co—Cu体系尖晶石的结构和红外辐射特性

采用XRD、SEM／EDAX、IR等测试方法研究了Fe2O3-MnO2-Co2O3-CuO体系的结构及其形成过程，测试了该体系的红外辐射性能，分析了该体系的结构特征与其红外辐射特性的关系。研究结果表明，高温合成过程中过渡金属氧化物形成立方尖晶石固溶体。尖晶石结构的四面体位置主要分布有Fe^3 、Mn^2 、Cu^2 等离子，八面体位置主要被Mn3^ ,Co^3 ,Cu^2 ,Fe^2 ,Fe^3 等离子占据。体系组成的变化对过渡金属离子在四面体位置和八面体位置的分布状况产生影响。由于在四面体位置和八面体位置上均存在多种过渡金属离子，Fe-Mn-Co-Cu体系立方尖晶石固溶体在2．5－25μm波段内具有较高的红外辐射率。     

安徽庐枞盆地西湾铅锌矿床闪锌矿微量元素特征及其地质意义

庐枞火山岩盆地是长江中下游成矿带的重要组成部分，近年来在其北缘东马鞍山组中发现了大型西湾铅锌矿床。前人研究显示该矿床闪锌矿中富集一定的稀散元素，但对其含量及分布特征研究不够深入，且缺乏对稀散元素的综合评价。文章采用LA-ICP-MS分析手段研究了西湾铅锌矿床中Ⅳ、Ⅴ号矿体闪锌矿中微量元素特征，并探讨了其地质意义。结果表明：(1)闪锌矿中较为富集Fe、Mn、Cd、Pb元素，贫In、Tl、Se、Te、Sn元素，其中Cd稀散元素具有一定的综合利用价值；(2)闪锌矿中微量元素替代机制主要有单元素和多元素耦合，其中单元素替代机制主要有Fe²⁺替代Zn²⁺、Cd²⁺替代Zn²⁺等，而多元素耦合替代机制主要有(Cu⁺+Ge³⁺)替代2Zn²⁺、(2Cu⁺+Ge⁴⁺)替代3Zn²⁺等；(3)闪锌矿中Fe、Mn、Cd、In等微量元素(稀散元素)组成特征，显示西湾铅锌矿床的成矿温度为中低温...     

X-ray K-edge absorption spectra of Fe minerals and model compounds: Near-edge structure

Synchrotron radiation has been used to collect high-resolution Fe K absorption near-edge spectra of a suite of Fe minerals and compounds having a range of Fe environments. These spectra, along with those of previous workers, indicate that the number, position, and intensity of near-edge features are characteristic of Fe valence and general site geometry. For example, the crest of the K-edge for Fe²⁺ in a six-coordinated site in the oxides studied is about 3 eV lower in energy than that for Fe³⁺ in a similar site. The K-edge crest for Fe³⁺ in a four-coordinated site is 1 to 2 eV lower than for Fe³⁺ in a regular site. The shape of the edge crest is sensitive to the details of first-neighbor bonding distances, tending to be broader in species with irregular Fe sites and varying in energy according to the average bond length. Comparison with Ca²⁺ and Zn²⁺ spectra from the literature is made and the applicability and utility of edge measurements discussed.     

Texture, microstructure and geochemistry of magnetite from the Banduhurang uranium mine, Singhbhum Shear Zone, India — implications for physico-chemical evolution of magnetite mineralization

The Singhbhum Shear Zone in eastern India is one of the largest repositories of uranium and copper in India. Besides uranium and copper, apatite-magnetite mineralization is widespread in this shear zone. This study aims at deciphering the physico-chemical evolution of magnetite mineralization in relation to progressive shearing integrating field relations, micro-textures, structures and compositions of magnetite in the Banduhurang uranium mine. Apatite-magnetite ores occur as discrete patches, tongues, and veins in the strongly deformed, fine grained quartzchlorite schist. Textures and microstructures of magnetite indicate at least three stages of magnetite formation. Coarsegrained magnetite (magnetite-1) with long, rotational, and complex strain fringes, defined by fibrous and elongate quartz, is assigned to a stage of pre-/early-shearing magnetite formation. Medium grained magnetite (magnetite-2), characterized by single non-rotational strain fringe equivalent to the youngest fringe of magnetite-1, grew likely at the mid-/late-stage of shearing. Fine grained magnetite (magnetite-3) is generally devoid of any pressure shadow. This indicates even a much later stage of formation of this magnetite, presumably towards the closing stage of shearing. Some of the magnetite-1 grains are optically heterogeneous with a dark, pitted Cr-Ti-bearing core overgrown by lighter, fresh rim locally containing pyrite, chalcopyrite, and chlorite inclusions. The cores are also locally characterized by high Al and Si content. Homogeneous magnetite-1 is optically and compositionally similar to the overgrowth of heterogeneous magnetite-1. This homogeneous magnetite-1 that grew as separate phase is contemporaneous with the overgrowth on pitted core of heterogeneous magnetite-1. Magnetite-2 is compositionally very similar to homogeneous magnetite-1, but is devoid of sulfide inclusion. Magnetite-3 is generally devoid of any silicate or sulfide inclusion and is most pure with least concentrations of trace/minor elements. The high Al and Si content in some magnetite can be explained by coupled substitution that involves substitution of Si⁴⁺ for Fe³⁺ in the tetrahedral sites and Fe²⁺ for Fe³⁺ in the octahedral sites, with a simple substitution of Al³⁺ for Fe³⁺ in the octahedral sites. The mode of occurrences of apatite-magnetite ores indicates a predominantly hydrothermal origin of most magnetite. However, the Cr-Ti-bearing magnetite-1 cores and inferred mafic nature of the original protolith indicates that some magnetite was inherited from the original igneous rock. We propose that the pre-/early-shearing hydrothermal event of magnetite formation was associated with sulfide mineralization and alteration of existing magmatic magnetite. The second stage of magnetite formation at the mid-/late-stage of shearing was not associated with sulfide formation. Finally, fine-grained compositionally pure magnetite formed at the closing stage of shearing likely due to metamorphism of Fe-rich protolith.     

Titanian andradite in a metapyroxenite layer from the Malenco ultramafics (Italy): implications for Ti-mobility and low oxygen fugacity

Ti-andradite (melanite) has been found in a metapyroxenite layer in the upper part of the Malenco ultramafics(Italy), coexisting with clinochlore, diopside and magnetite. Field observations, as well as major and trace elementbulk-rock composition, strongly suggest a cumulate origin for the layer. Textural relationships indicate thatTi-andradite formed during two different metamorphic stages. Under peak metamorphic conditions (400–450°C, 5±2 kbar)Ti-andradite grew in an assemblage of diopside, clinochlore, magnetite and rare ilmenite and perovskite. Later, retrograde brittle deformationinduced formation of veins containing the paragenesis Ti-andradite, vesuvianite, diopside, chlinochlore, magnetite and accessory perovskite.The Ti-andradite varies considerably in TiO₂ (0.11–9.62 wt%), Fe₂O₃(14.3–30.5 wt%), Al₂O₃ (0.65–3.90 wt%), Cr₂O₃(>0.18–0.98 wt%) and SiO₂ (32.1–36.1 wt%); this is mostly, but not entirely, due to distinct zoning.Ti-andradite contains 0.32 to 0.66 wt% H₂O as determined by infrared spectroscopy and 0.83 to 1.76 wt% FeO. The CaO shows almost no variation (34.1±0.7 wt%) and Ca completely fills the dodecahedral site. Single crystal site refinements indicate that no tetrahedral Ti or Fe replaces Si. Titanium incorporation is attributed to similar degrees of substitution along the exchange vectors Ti³⁺ Fe³⁺, Ti⁴⁺ Al^IV Al _-1 ^VI Si_-1 and (Fe²⁺, Mn²⁺, Mg²⁺)Ti⁴⁺ 2Fe _-1 ³⁺ . The presence of mixed valence states of both Fe and Ti suggests a low oxygen fugacity during crystallization of Ti-andradite. Mass balance calculations indicate an isochemical origin of the first generation of Ti-andradite in the clinopyroxenite layer. Its occurrence is restricted to antigorite-free mineral assemblages containing clinochlore of 0.95X _Al>1.1. The hydrothermal crystallization of Ti-rich andradite in veins demonstrates Ti mobility in aqueous fluids under moderate P-T conditions. The zonation patterns indicate disequilibrium conditions during vein crystallization. As no fluorine-, carbonate- and phosphate-bearing minerals were found, OH^- is most probably the ligand complexing Ti.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

Cordierite III: the site occupation and concentration of Fe3+

Cordierite has the ideal formula (Mg,Fe)₂Al₄Si₅O₁₈ ^.x(H₂O,CO₂), but it must contain some Fe³⁺ to account for its blue color and strong pleochroism. The site occupation and concentration of Fe³⁺ in two Mg-rich natural cordierites have been investigated by EPR and ⁵⁷Fe Mössbauer spectroscopy. In addition, powder IR spectroscopy, X-ray diffraction, and TEM examination were used to characterize the samples. Single-crystal and powder EPR spectra indicate that Fe³⁺ is located on T₁1 in natural cordierites and not in the channels. The amount in Mg-rich cordierites is very small with an upper limit set by Mössbauer spectroscopy giving less than 0.004 cations per formula unit (pfu). Fe³⁺ in cordierite can, therefore, be considered insignificant for most petrologic calculations. Heat-treating cordierite in air at 1,000?°C for 2?days causes an oxidation and/or loss of Fe²⁺ on T₁1, together with an expulsion of Na⁺ from the channels, whereas heating at the Fe–FeO buffer produces little Fe³⁺ in cordierite. Heating at 1,000?°C removes all class I H₂O, but small amounts of class II H₂O remain as shown by the IR measurements. No evidence for channel Fe²⁺ or Fe³⁺ in the heat-treated samples was found. The blue color in cordierite arises from a broad absorption band (E//b and weaker with E//a) around 18,000?cm^?1 originating from charge-transfer between Fe²⁺ in the octahedron and Fe³⁺ in the edge-shared T₁1 tetrahedron. It therefore appears that all natural cordierites contain some tetrahedral Fe³⁺. The brown color of samples heated in air may be due to the formation of very small amounts of submicroscopic magnetite and possibly hematite. These inclusions in cordierite can only be identified through TEM study.     

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.     

Characterization of a natural magnetite

Single crystals of a rock magnetite were separated from steatite cobbles collected in a geological site near the city of Serro (18° 36′ 47′′ S 43° 22′ 46′′ W), Minas Gerais, Brazil. A typically well-shaped magnetite single crystal was characterized by chemical analysis, ⁵⁷Fe Mössbauer spectrometry at 300, 77 and 4 K and under an applied magnetic field of 6 T at 10 K, magnetization measurements and electronic microprobe. From Mössbauer data, the sample is stoichiometric with a tetrahedral and octahedral site occupancy ratio of 1:2. Elemental chemical analysis and point-to-point electron microscope probing show some inclusions of lamellar ilmenite (≤ 1 mass%) randomly distributed throughout the magnetite matrix, and also that the magnetite matrix is constituted only by Fe²⁺ and Fe³⁺, with no isomorphic substitution. Results are discussed on the basis of the magnetization curve and of the temperature dependence of the AC magnetic susceptibility. The Verwey transition occurs in the temperature range of 100–115 K, observed by a sudden change in the temperature dependence of the magnetization.     

Mineralogy,petrology, and phase relations of glaucophane-lawsonite zone blueschists from the Tavşanli Region,Northwest Turkey

Glaucophane-lawsonite facies blueschists representing a metamorphosed sequence of basic igneous rocks, cherts and shales have been investigated northeast of the district of Tav?anli in Northwest Turkey. Sodic amphiboles are rich in magnesium reflecting the generally high oxidation states of the blueschists. Lawsonite has a very uniform composition with up to 2.5 wt.% Fe₂O₃. Sodic pyroxenes show an extensive range of compositions with all the end-members represented. Chlorites are uniform in their Al/(Al+Fe+Mg) ratio but show variable Fe/ (Fe+Mg) ratios. Garnets from metacherts are rich in spessartine (>50%) whereas those from metabasites are largely almandine. Pistacite rich epidote is found in metacherts coexisting with lawsonite. Phengites are distinctly higher in their Fe, Mg and Si contents than those from greenschist facies. Hematites with low TiO₂ are ubiquitous in metacherts. Fe²⁺/Mg partitioning between chlorite and sodic amphibole is strongly controlled by the calcium content of the sodic amphibole and ranges from 1.1 for low calcium substitution to 0.8 for higher calcium substitution. The Al/Fe³⁺ partition coefficient between sodic amphibole and sodic pyroxene is 2.1. A model system has been constructed involving projections from lawsonite, iron-oxide and quartz onto a tetrahedron with Na, Al, Fe²⁺ and Mg at its apices. Calcite is treated as an indifferent phase. The model system illustrates the incompatibility of the sodic pyroxene with chlorite in the glaucophanelawsonite facies; this assemblage is represented by sodic amphibole. Sodic amphibole compositions are plotted in terms of coexisting ferromagnesian minerals. Five major areas on the sodic amphibole compositional field are delineated, each associated with one of the following minerals: chlorite, stilpnomelane, talc, almandine, deerite.     

Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe_1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe²⁺, small quantity of Fe³⁺, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe³⁺ and a form of high-spin Fe²⁺ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe²⁺ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe³⁺ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e_g band of singlet Fe²⁺ along with minor contributions attributable to high-spin Fe²⁺ and Fe³⁺. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe³⁺ species and sulphur in oxidation state between +2 and +4.     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.