Nickel geochemistry of a Philippine laterite examined by bulk and microprobe synchrotron analyses

The Ni geochemistry of limonite and saprolite laterite ores from Pujada in the Philippines has been investigated using a mixture of laboratory and synchrotron techniques. Nickel laterite profiles are typically composed of complicated mineral assemblages, with Ni being distributed heterogeneously at the micron scale, and thus a high degree of spatial resolution is required for analysis. This study represents the first such analysis of Philippine laterite ores. Synchrotron bulk and microprobe X-ray absorption spectroscopy (XAS), comprising both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, together with synchrotron microprobe X-ray fluorescence microscopy (XFM) and diffraction (XRD) have been applied to provide quantitative analysis of the mineral components and Ni speciation.Synchrotron microprobe EXAFS spectroscopy suggests that the limonite Ni is associated with phyllomanganate via adsorption onto the Mn oxide layers and substitution for Mn within these layers. Laboratory scanning electron microscopy, coupled to electron dispersive spectroscopy analyses, indicates that Ni is also associated with concentrated Fe containing particles and this is further confirmed by synchrotron bulk and microprobe investigation. Linear combination fitting of the bulk EXAFS limonite data suggests 60 ± 15% of the Ni is associated with phyllomanganate, with the predominant fraction adsorbed above vacancies in the MnO₆ layers with the remainder being substituted for Mn within these layers. The remaining 40 ± 10% of the Ni in the limonite ore is incorporated into goethite through replacement of the Fe. In the saprolite ore, 90 ± 23% of the Ni is associated with a serpentine mineral, most likely lizardite, as a replacement for Mg. The remaining Ni is found within phyllomanganate adsorbed above vacancies in the MnO₆ layers.     

Hydrothermal Mobilization and Enrichment of Iron in the Iron Deposits of the Middle—Lower Yangtze Valley District

There are two main types of iron deposits in the Middle-Lower Yangtze Valley district.Both of them underwent post-magmatic hydrothermal processes during ore formation.Iron in the hydrothermal ore bodies was derived largely through mobilization from substantially consolidated diroitic intrusives.Wall-roch alteration zonation indicates that iron-mobilizing hydrothermal fluids evolved in a trend of decreasing alkalinity,which is suggested by regularly distributed wall-rock alterations formed by iron-mobilizing hydrothermal fluids and is in contradiction with the current chloride,chloride complex and bicarbonate models for iron mobilization.The close association of carbonatization with iron ores and the high concentrations of reduced gases such as CO,CH4 and H2 in fluid inclusions suggest that iron is most probably transported in the form of iron carbonyls during post-magmatic hydrothermal processes. In the light of the iron carbonyl mobilization model,explanations are made of the constraints on ores of some geologic factors such as melanocratic alteration,carbonatization,carbonate strata,structural fractures,cyptoexplosive pipes and embryo ores.     

Geochemical Fingerprint and Iron Ore Potential of the Siliceous Itabirite from Palaeoproterozoic Nyong Series,Zambi Area,Southwestern Cameroon

The study area forms part of an emerging iron ore province of southern Cameroon. Geochemistry analyses reveal that the siliceous itabirite has a very simple chemical composition, with Fe₂O₃ and SiO₂ representing more than 96 wt.% of the average composition; suggesting chemical precipitates of silica and iron. Low Al₂O₃ and TiO₂ concentrations and a weak positive correlation between them point to a minor detrital component in the precipitated marine sediments. The Si/Al ratio (average 52.7) indicates the hydrothermal origin of the studied itabirite. The Al–Si discrimination diagram supports this interpretation through the plot of all data in the hydrothermal field. The studied samples have low iron content (about 39.32% Fe), high gangue content (40.97% SiO₂ and 1.3 % Al₂O₃) and low concentration of the deleterious elements (0.16 % P and < 0.01% S). The main gangue mineral is silica which can be efficiently removed from iron ores during preparation of raw materials for the blast furnace process. According to commercial standards for crude iron ores, it may be concluded that the Zambi iron ores are a low‐grade magnetic ore that can be profitably exploited for the production of iron for steel production.     

Development of machine vision-based ore classification model using support vector machine (SVM) algorithm

The product of the mining industry (ore) is considered to be the raw material for the metal industry. The destination policy of the raw materials of iron mine is highly dependent on the class of iron ores. Thus, regular monitoring of iron ore class is the urgent need at the mine for accurately assigning the destination policy of raw materials. In most of the iron ore mines, decisions on ore class are made based on either visual inspection by the geologist or laboratory analyses of the ores. This process of ore class estimation is time consuming and also challenging for continuous monitoring. Thus, the present study attempts to develop an online vision-based technology for classification of iron ores. A laboratory-scale transportation system is designed using conveyor belt for online image acquisition. A multiclass support vector machine (SVM) model was developed to classify the iron ores. A total of 2200 images were captured for developing the ore classification model. A set of 18 features (9-histogram-based colour features in red, green and blue (RGB) colour space and 9-texture features based on intensity (I) component of hue, saturation and intensity (HSI) colour space) were extracted from each image. The performance of the SVM model was evaluated using four confusion matrix parameters (sensitivity, accuracy, misclassification and specificity). The SVM model performance was also compared with the other methods like K-nearest neighbour, classification discriminant, Naïve Bayes, classification tree and probabilistic neural network. It was observed that the SVM classification model performs better than the other classification methods.     

Composition and origin of lateritic nickel ore at Tagaung Taung,Burma

The recently discovered lateritic nickel ore deposit on the summit area of the Tagaung Taung contains about 40 million DMT nickel-saprolite ore with approximately 2% Ni. The serpentinite massif is covered with a thick weathering mantle consisting of saprolite, limonite, and an allochthonous lateritic surface layer. The thickness, nickel content, and physical properties of the ore are very variable. The main minerals in the nickel saprolite ore are nickeliferous serpentine and smectite. Microprobe analyses show a strong depletion of Mg with increasing nickel content in the serpentine minerals; smectite generally contains less nickel than serpentine. Chemical analyses of samples from more than 100 drill holes are used to calculate the mean chemical compositions, mean accumulation factors, and gain and loss of major and trace elements for the various layers. This permits a quantitative approach to be made to the genetic history of the weathering mantle. Gain and loss determinations on the basis of constant chromium content and of constant volume give nearly identical results for the saprolite layer. Calculations on the basis of Ni/Cr ratios indicate that three-quarters of a former 20-m-thick limonite layer has been eroded away. Only the lower part of the original limonite layer with a relatively high SiO₂ content is preserved. The kaolinite- and illite-rich surface layer is a mixture of limonite and weathered clayey material, which was probably derived from adjacent rocks. Part of the autochthonous weathering section is contaminated with infiltrated allochthonous surface material. It is not possible that colluvial-alluvial deposition of clayey material from nonultramafic rocks could have taken place under the present geomorphic regime. Thus, lateritization of the serpentinite and deposition of siallitic material must have occurred before exposure of the Tagaung Taung in its present form.     

Mineralogy,geochemistry and the origin of high-phosphorus oolitic iron ores of Aswan,Egypt

The Coniacian-Santonian high-phosphorus oolitic iron ore at Aswan area is one of the major iron ore deposits in Egypt. However, there are no reports on its geochemistry, which includes trace and rare earth elements evaluation. Texture, mineralogy and origin of phosphorus that represents the main impurity in these ore deposits have not been discussed in previous studies. In this investigation, iron ores from three localities were subjected to petrographic, mineralogical and geochemical analyses. The Aswan oolitic iron ores consist of uniform size ooids with snowball-like texture and tangentially arranged laminae of hematite and chamosite. The ores also possess detrital quartz, apatite and fine-grained ferruginous chamosite groundmass. In addition to Fe₂O₃, the studied iron ores show relatively high contents of SiO₂ and Al₂O₃ due to the abundance of quartz and chamosite. P₂O₅ ranges from 0.3 to 3.4 wt.% showing strong positive correlation with CaO and suggesting the occurrence of P mainly as apatite. X-ray diffraction analysis confirmed the occurrence of this apatite as hydroxyapatite. Under the optical microscope and scanning electron microscope, hydroxyapatite occurred as massive and structureless grains of undefined outlines and variable size (5–150 μm) inside the ooids and/or in the ferruginous groundmass. Among trace elements, V, Ba, Sr, Co, Zr, Y, Ni, Zn, and Cu occurred in relatively high concentrations (62–240 ppm) in comparison to other trace elements. Most of these trace elements exhibit positive correlations with SiO₂, Al₂O₃, and TiO₂ suggesting their occurrence in the detrital fraction which includes the clay minerals. ΣREE ranges between 129.5 and 617 ppm with strong positive correlations with P₂O₅ indicating the occurrence of REE in the apatite. Chondrite-normalized REE patterns showed LREE enrichment over HREE ((La/Yb)_N = 2.3–5.4) and negative Eu anomalies (Eu/Eu* = 0.75–0.89). The oolitic texture of the studied ores forms as direct precipitation of iron-rich minerals from sea water in open space near the sediment-water interface by accretion of FeO, SiO_2, and Al₂O₃ around suspended solid particles such as quartz and parts of broken ooliths. The fairly uniform size of the ooids reflects sorting due to the current action. The geochemistry of major and trace elements in the ores reflects their hydrogenous origin. The oolitic iron ores of the Timsha Formation represent a transgressive phase of the Tethys into southern Egypt during the Coniacian-Santonian between the non-marine Turonian Abu Agag and Santonian-Campanian Um Barmil formations. The abundance of detrital quartz, positive correlations between trace elements and TiO₂ and Al₂O₃, and the abundance mudstone intervals within the iron ores supports the detrital source of Fe. This prediction is due to the weathering of adjacent land masses from Cambrian to late Cretaceous. The texture of the apatite and the REE patterns, which occurs entirely in the apatite, exhibits a pattern similar to those in the granite, thus suggesting a detrital origin of the hydroxyapatite that was probably derived from the Precambrian igneous rocks. Determining the mode of occurrence and grain size of hydroxyapatite assists in the maximum utilization of both physical and biological separation of apatite from the Aswan iron ores, and hence encourages the use of these ores as raw materials in the iron making industry.     

Geochemical Characteristics and Genetic Significance of Datangpo‐Type Manganese Ore Deposits during the Cryogenian Period

The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al₂O₃ and TiO₂, SiO₂, K₂O, and Na₂O, and strong negative correlations between Al₂O₃ and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K₂O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ¹³C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO₃^? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.     

论安徽省姑山铁矿床的热液成矿特征

姑山铁矿床产在燕山期辉石闪长岩与中三叠统黄马青组砂页岩的接触带上。矿石具有典型的斑状、球颗状和骨架状结构。镜下研究表明,这些结构不是矿浆结晶的产物,而是热液成因微晶赤铁矿在后期地质过程中发生变晶生长所致。矿床中的蚀变和矿化自下而上呈现规律性的分带。碳酸盐化是特征性的蚀变类型,其形成与成矿密切有关,并可作为一种近矿找矿标志。在热液成矿过程中,辉石闪长岩中的铁很可能以羰基络合物的形式发生活化转移。在热液演化过程中由于氧逸度的升高和碱度、压力的降低,羰基络合物发生分解而使铁在接触带附近沉淀成矿。     

新疆西天山智博铁矿床磁铁矿成分对其成矿机制的指示

智博铁矿床位于新疆西天山阿吾拉勒成矿带东段,主要赋矿围岩为石炭系大哈拉军山组安山岩、玄武质安山岩和火山碎屑岩.该矿床主要有东、中、西3个矿区,其中以东矿区为主矿区.矿体主要呈层状、似层状、厚板状和透镜状.金属矿物以磁铁矿为主,含有少量黄铁矿、赤铁矿和黄铜矿.矿石构造以块状和浸染状构造为主,此外还有角砾状构造、条带状构造...     

高磷铁矿石成分分析标准物质研制

高磷铁矿石的分析测试过程需要基体组分相似、含量适中、定值组分全的标准物质进行质量监控,目前我国没有高磷铁矿石标准物质,现有铁矿石标准物质因基体组分不尽相同,磷元素含量大部分低于0.25%,而高磷铁矿石中磷含量均高于0.25%,这些标准物质难以满足高磷铁矿石产品的分析测试质量监控要求。基于此,本文研制了3个高磷铁矿石成分分析标准物质,样品分别采集于鄂西地区湖北宜昌秭归县野狼坪矿区、湖北恩施长岭矿区(武钢矿区)、湖北宜昌长阳县火烧坪矿区(宝钢长阳矿区),磷和铁含量均呈一定梯度,基本覆盖高磷铁矿的含量范围。均匀性和稳定性对SiO_2、Al_2O_3、TiO_2、P、K_2O、Na_2O、Fe、MnO、CaO、MgO、FeO、LOI、S、Cu、Pb、Zn、Cr、Ni、Co、Cd、Sr、Ba、V、As、Hg共25个组分进行检验,均匀性检验采用方差分析F检验法和测试结果的相对标准偏差进行评价,稳定性检验采用直线拟合,t检验法进行评估。经检验,样品均匀性、稳定性良好;定值采用11家实验室协作,采用2种以上不同原理的方法进行测试,定值组分包括主量元素、微量元素共25项,其中24项提供认定值及不确定度,Hg提供参考值。磷的含量分别为0.285%、不确定度0.010%,0.735%、不确定度0.020%,1.73%、不确定度0.05%,总铁含量分别为35.18%、不确定度0.20%,41.46%、不确定度0.20%,51.44%、不确定度0.13%。本次研制的高磷铁矿石标准物质可用于高磷铁矿的勘查、评价和综合利用开发中对标准物质的需求。     

微波消解-电感耦合等离子体质谱法测定铁矿石中15个稀土元素

分析地质样品中稀土元素的含量,现有的方法都受到基体干扰和共存元素干扰,电感耦合等离子体质谱(ICP-MS)已在痕量元素分析中得到广泛应用,通过条件优化可准确测定稀土元素。本文建立了ICP-MS同时测定铁矿石中钇镧铈镨钕钐铕钆铽镝钬铒铥镱镥15个稀土元素的方法,样品用盐酸、硝酸和氢氟酸高温密闭消解,消解完全后转移定容,在线加入¹⁰³Rh、¹¹⁵In、¹⁸⁵Re内标液进行测定,方法回收率为95%~104%,精密度(RSD)≤3.5%。对12个国家24个代表性主产区进口的铁矿石样品进行检测,分析其稀土元素的配分模式特征为右倾型轻稀土富集,现阶段的进口铁矿粉多为多产区复合配矿。本方法较其他传统方法大幅降低能耗,提高了分析效率,初步探讨的稀土元素丰度特征可为研究主产区铁矿石的矿床成因、提高我国烧结球团矿的加工工艺提供依据。     

Rare Earth Element Enrichment in Late Archean Manganese Deposits from the Iron Ore Group,East India

The major, trace and rare earth element (REE) composition of Late Archean manganese, ferromanganese and iron ores from the Iron Ore Group (IOG) in Orissa, east India, was examined. Manganese deposits, occurring above the iron formations of the IOG, display massive, rhythmically laminated or botryoidal textures. The ores are composed primarily of iron and manganese, and are low in other major and trace elements such as SiO₂, Al₂O₃, P₂O₅ and Zr. The total REE concentration is as high as 975 ppm in manganese ores, whereas concentrations as high as 345 ppm and 211 ppm are found in ferromanganese and iron ores, respectively. Heavy REE (HREE) enrichments, negative Ce anomalies and positive Eu anomalies were observed in post‐Archean average shale (PAAS)‐normalized REE patterns of the IOG manganese and ferromanganese ores. The stratiform or stratabound shapes of ore bodies within the shale horizon, and REE geochemistry, suggest that the manganese and ferromanganese ores of the IOG were formed by iron and/or manganese precipitation from a submarine, hydrothermal solution under oxic conditions that occurred as a result of mixing with oxic seawater. While HREE concentrations in the Late Archean manganese and ferromanganese ores in the IOG are slightly less than those of the Phanerozoic ferromanganese ores in Japan, HREE resources in the IOG manganese deposits appear to be two orders of magnitude higher because of the large size of the deposits. Although a reliable, economic concentration technique for HREE from manganese and ferromanganese ores has not yet been developed, those ores could be an important future source of HREE.     

西昆仑赞坎铁矿床地质特征、形成时代及高品位矿石的成因

新疆赞坎铁矿床位于西昆仑塔什库尔干地块西段,是近年新发现的一个大型沉积变质型磁铁矿床。赋矿岩系布伦阔勒群主要由黑云母石英片岩、斜长角闪片岩、变粒岩、硅质岩及磁铁石英岩等组成。目前探明工业矿体4条,单个矿体长度大于2.5km,矿体厚10~70m;局部见高品位铁矿段(mFe50%),长度达900m,厚度40m左右。矿石类型主要为2种,一种为原生的条纹-条带状磁铁矿(为主);另一种为热液改造形成的块状(高品位铁矿石)及浸染状磁铁矿。矿石稀土元素配分(PAAS)表明,原生条纹-条带状铁矿石Ce和Y元素异常不明显(~1.15、~0.94),Eu具正异常(~1.69),Y/Ho平均值为25,稀土配分模式与沉积变质型铁矿相似。而受改造的矿石中,浸染状矿石具有较高的稀土总量,明显富集轻稀土,La和Ce显示正异常(~1.46、~1.17),Y显示负异常(=0.66~0.72),Eu表现为强烈的正异常(~4.37),稀土配分模式明显不同于原生条纹-条带状铁矿石。矿体围岩斜长角闪片岩(变沉积岩)中的碎屑锆石U-Pb年龄为591±1Ma,结合前人对矿区内侵入体的年代学研究(霏细斑岩,533Ma),大致反映沉积铁矿的形成时代为新元古代至早寒武世。电子探针显示,条带状磁铁矿中的TiO_2、AL_2O_3、MgO、MnO含量较低,标型组分含量与沉积变质型磁铁矿颇为接近,在磁铁矿单矿物成因图解中,条带状磁铁矿整体显示磁铁矿为沉积变质型铁矿;浸染状矿石和块状矿石的组成与典型沉积变质型铁矿的偏离反映了后期岩浆-构造热事件对条带状铁矿石的改造;上述结果显示赞坎铁矿整体属于沉积变质型铁矿(BIF)。调查发现赞坎高品位铁矿体与早寒武世侵入的霏细斑岩联系密切,高品位矿石及其围岩发育一定程度的矽卡岩化,如阳起石化、碳酸盐化和黄铁矿化。本文推测高品位铁矿石的成因可能为霏细斑岩的岩浆热液溶解并运移早期沉积变质铁矿中的含铁物质,在构造发育处充填交代形成块状磁铁富矿石。在早寒武世侵入到矿区中部的霏细斑岩体中,同时发育有角砾状磁铁矿和脉状磁铁矿,因此,岩浆热液改造原生条带状铁矿石形成高品位铁矿石的时代应为早寒武世。     

河南舞阳铁山庙式BIF铁矿的矿物学与地球化学特征及对矿床成因的指示

河南舞阳铁矿位于华北克拉通南缘.铁山庙式铁矿是舞阳铁矿的一部分,赋存于新太古界太华杂岩铁山庙组表壳岩中.本文根据铁山庙式铁矿中三种不同类型矿石(条带状石英-辉石-磁铁矿、块状辉石-磁铁矿、块状石英-磁铁矿)中磁铁矿的矿物成分、全岩/矿的主量元素及微量元素特征,探讨铁山庙式铁矿床的成因.磁铁矿单矿物成分分析表明,条带状石英-辉石-磁铁矿矿石中磁铁矿的FeOT含量90.6％ ～93.1％,平均91.8％;块状辉石-磁铁矿矿石中磁铁矿的FeOT含量90.7％～91.2％,平均91.0％;块状石英-磁铁矿矿石中磁铁矿的FeOT含量92.0％～93.0％,平均92.4％.上述平均值均与磁铁矿FeOT的理论值(93.1％)接近.三种类型矿石的其它元素如TiO2、MgO、MnO、CaO、Al2O3 Cr2O3 NiO等含量均＜0.1％,无明显区别,表明该区磁铁矿为含杂质极少的纯磁铁矿,表现出沉积变质成因磁铁矿的特征.矿石中斜方辉石-单斜辉石及近矿围岩紫苏辉石-长石-石英矿物组合,表明铁山庙式矿床经受了高级变质作用,石英、磁铁矿等矿物普遍发生变质重结晶,颗粒粗大,但仍保存原有的地球化学组成.元素地球化学分析显示,三种类型矿石中SiO2 、TiO2 Al2O3、P2O5的含量相近;块状辉石-磁铁矿较其它二者相对贫铁、富钙、镁,这是由于块状辉石-磁铁矿石中富含铁普通辉石和铁次透辉石所致;矿石中TiO2、Al2O3含量都极低,说明该区成岩成矿过程中未受到碎屑物质的混染.三种不同类型矿石的主量元素含量总体上都与世界典型BIF的相近.对于稀土元素,三种类型矿石均具有轻稀土亏损、重稀土富集((La/Yb)PAAS=0.29～0.995＜1),La、Eu、Y的正异常(La/La*=1.10～1.89;Eu/Eu* =1.30～2.23;Y/Y* =1.47～1.84),较高的Y/Ho比值(39.7 ～51.3),具有现代海水及高温热液混合特征.因此,我们认为铁山庙式铁矿三种不同类型的矿石是极少受到陆源碎屑混染的化学沉积成因,虽遭受后期变质作用,但仍属BIF型铁矿.     

Iron–phosphorus relationship in the iron and phosphorite ores of Egypt

Iron and phosphorite ores are very common in the geological record of Egypt and exploitable for economic purposes. In some cases these deposits belong together to the same geographic and geologic setting. The most common deposits include phosphorites, glauconites, and iron ores. Phosphorites are widely distributed as a belt in the central and southern part of Egypt. Sedimentary iron ores include oolitic ironstone of Aswan area and karstified iron ore of Bahria Oasis. Glauconites occur in the Western Desert associated with phosphorites and iron ores. As these ores are exploitable and phosphorus in iron ores and iron in phosphorites are considered as gangue elements, the iron–phosphorus relationship is examined in these deposits to clarify their modes of occurrences and genetic relationship based on previously published results.Phosphorus occurs mainly as carbonate fluorapatite (francolite). Iron, on the other hand, occurs in different mineralogical forms such as glauconites, hematite, limonite and goethite.In P-rich rocks (phosphorites) no relationship is observed between iron and phosphorus, which in turn indicates that the FeP model is unlikely to interpret the origin of the late Cretaceous phosphorites and the association of phosphorites and glauconites in Egypt. In Fe-rich rocks (iron ores and glauconites) also no relationship between iron and phosphorus is observed. The present work, therefore, does not support the hypothesis that there is a genetic relationship between phosphorus and iron in sedimentary rocks.     

陕西略阳张家山金矿成矿作用及Au-Se矿物形成物理化学条件研究

陕西略阳煎茶岭金矿矿集区中的张家山金矿主要由破碎蚀变岩型、角砾岩型和含金石英黄铁矿脉型矿石组成。含金石英-黄铁矿脉型矿石产于断层下盘的石英菱镁岩中。黄铁矿发育富As黄铁矿边,环边受As含量的变化呈现一定的韵律变化,自然金赋存在富As黄铁矿中。在断裂发育形成断层角砾岩的过程中,流体充填破碎石英菱镁岩的裂隙中形成热液矿物,包括硫化物、硒化物以及自然金。石英菱镁岩发生破碎形成的网状裂隙被含金石英-方解石-黄铁矿脉充填。破碎蚀变岩型矿石中,自然金主要分布在含金石英-黄铁矿脉的石英之中或靠近热液脉的菱镁矿或石英间隙。随着大量方解石脉沿裂隙贯入,进一步促进石英菱镁岩的破碎及岩石角砾的分离,形成由石英菱镁岩碎屑、石英和褐铁矿组成的复成分角砾岩,自然金和硒化物呈浸染状分布在角砾岩中。笔者在角砾岩型矿石中发现了灰硒汞矿、直硒镍矿、硒铅矿等硒化物,这些硒化物往往与自然金密切共生。结合矿物组合以及相关化学反应关系,通过热力学计算,构建了该矿床在不同温度条件下的热力学相平衡关系图,限定了硒化物与其他相关矿物稳定存在的物理化学条件。硒化物一般与自然金和石英共生,高的f(Se2)值和f(Se2)/f(S2)比值是控制硒化物形成的关键因素。     

Mössbauer spectroscopy studies of the valence state of iron in chromite from the Luobusa massif of Tibet: implications for a highly reduced deep mantle

Mössbauer spectroscopy was applied to study the valence state of iron in chromite from massive, nodular and disseminated podiform chromitite ores of the Luobasa ophiolite massif of Tibet. The results show that Fe³⁺/ΣFe = 0.42 in chromite from massive ore, and Fe³⁺/ΣFe = 0.22 in chromite from nodular and disseminated ores. The massive ore records traces of ultra high pressure mineralogical assemblages, such as diamond inclusions in OsIr alloys, exsolution lamellae of coesite and diopside in chromite, inclusions of metal‐nitrides, native iron and others, which suggests a strongly reducing environment. In contrast, chromite from nodular and disseminated ore contains abundant low‐pressure OH‐bearing mineral inclusions whose formation requires a more oxidizing environment. The high value of Fe³⁺/ΣFe in the ‘reduced’ massive ore is explained by crystallographic stabilization of Fe³⁺ in a high‐pressure polymorph of chromite deep in the upper mantle despite low ambient fO₂ conditions. The presence of high‐pressure phases within the massive chromitite ore requires that the latter, together with its host peridotite, was transported in the solid state from a highly reduced deep mantle environment to shallow depths beneath an ocean spreading centre. It is suggested that in the low‐pressure environment of the spreading centre, the deep‐seated, reduced, massive chromitites partially reacted with their host peridotite in the presence of hydrous melt, yielding the nodular and disseminated chromitite ores. The preponderance of evidence suggests that the latter interaction involved boninitic melts in a supra‐subduction zone environment as proposed previously.     

Mineralogy,geochemistry and origin of Mn in the high-Mn iron ores,Bahariya Oasis,Egypt

Although Mn is one of the major impurities in the economic iron ores from the Bahariya Oasis, information on its modes of occurrence and origin is lacking in previous studies. High-Mn iron ores from El Gedida and Ghorabi–Nasser iron mines were subjected to detailed mineralogical, geochemical, and petrographic investigations using X-ray diffraction (XRD), infrared absorption spectrometry (IR), Raman spectroscopy, X-ray fluorescence (XRF), scanning electron microscopy (SEM), and electron probe microanalyzer (EPMA) to clarify the modes of occurrence of Mn in these deposits and its origin. The results showed that the MnO₂ contents range between 0.03 and 13.9 wt.%. Three mineralogical types have been identified for the Mn in the high-Mn iron ores, including: (1) inclusions within the hematite and goethite and/or Mn accumulated on their active surfaces, (2) coarse-grained and crystalline pyrolusite, and (3) fine-grained cement-like Mn oxide and hydroxide minerals (bixbyite, cryptomelane, aurorite, romanechite, manjiroite, and pyrochroite) between the Fe-bearing minerals. The Mn carbonate mineral (rhodochrosite) was detected only in the Ghorabi–Nasser high-Mn iron ores. Since IR patterns of low-Mn and high-Mn samples are almost the same, a combination of XRD analysis using non-filtered Fe-Kα radiations and Raman spectroscopy could be the best way to identify and distinguish between different Mn minerals.Assuming that both Fe and Mn were derived from the same source, the occurrence of high-Mn iron ores at the base of the stratigraphic section of the deposits overlain by the low-Mn iron ores indicated a supergene origin of the studied ores by descending solutions. The predominance of Mn oxide and hydroxide minerals in botryoidal shapes supports this interpretation. The small grain size of Mn-bearing minerals as well as the features of microbial fossils such as spherical, elliptical, and filamentous shapes of the Fe-bearing minerals suggested a microbial origin of studied iron ores.Variations in the distribution and mineralogy types of Mn in the iron ores of the Bahariya Oasis demanded detailed mineralogical and petrographic characterizations of the deposits before the beneficiation of high-Mn iron ores from the Bahariya Oasis as feedstock for the ironmaking industries in Egypt by magnetizing reduction. High Mn contents, especially in the Ghorabi–Nasser iron ore and occurrence of Mn as inclusions and/or accumulated on the surface of the Fe-bearing minerals would suggest a possible utilization of the high-Mn iron ores to produce ferromanganese alloys.     

Problems of Iron and Phosphorus Geochemistry in the Precambrian

The localization of economic sedimentary iron ore and phosphorite resources is discussed in comparative aspects. It is shown that the major economic resources of iron ore are hosted in Precambrian rocks, whereas the phosphorites are related to Upper Phanerozoic. High-temperature hydrothermal solutions served as an important source of iron for jaspilite ores. The low P₂O₅content therein indicates that the phosphorus deposition was only weakly related to the hydrothermal activity. Thus, the hydrothermal origin of phosphorite is denied from the geochemical standpoint.     

无汞重铬酸钾-自动电位滴定法准确测定矿石中的全铁含量

铁矿石样品采用Na2O2碱熔进行前处理,自动电位滴定法准确测定矿石中全铁的含量。对于样品溶液Fe3+的还原方式,考察了SnCl2-HgCl2、SnCl2、TiCl3、SnCl2-TiCl3四种方式,确定选用SnCl2-TiCl3联合还原,不仅避免了有毒试剂的使用,而且滴定终点电位突跃明显。自动电位滴定法的相对误差(RE)为0.13%,精密度(RSD)为0.22%,优于手动滴定法,避免了手动滴定受终点颜色判断误差、分析者水平等因素影响的不足。将建立的SnCl2-TiCl3-K2Cr2O7自动电位滴定法应用于6个铁含量大于30%的矿石标准物质分析,RE<0.2%,RSD<0.3%(n=10)。该方法对于钒钛磁铁矿样品GBW 07226a、GBW 07224无需分离,可直接测定,样品分解方法简单快捷,适用性强,样品不会飞溅且分解完全,适用于需要较高准确度的铁矿石尤其是高含量铁矿石样品的分析工作。