Mode of Occurrence and Characteristics of Mn-ore Bodies in Iron Ore Group of Rocks, North Orissa, India and Its Significance in Resource Evaluation

Abstract. Several meso‐scale manganese ore bodies, scattered within Jone's horse‐shoe shaped synclinorium, in Bonai‐Keonjhar region of north Orissa are well known in the mineral map of India. Different grades of manganese ores are being exploited from this region by various agencies over a few decades. However, deceptive nature of ore bodies and complexity in control of mineralisation greatly confuse the exploration geologists for evaluation of these resources. In a recent study, the authors have classified Mn‐ore bodies of this region into three broad categories such as stratiform, stratabound (‐replacement) and lateritoid types based on mode of occurrence and their other chemical characteristics. Mn‐ore bands occur in close association with BIF and iron ores. Volcaniclastic shale in large geographic extension encloses these ore bodies. In the stratiform category of ore bodies (BMnF, analogous of BIF), manganese and shale bands, in variables thickness, alternate with each other and extend to a great depth. Such ore bodies generally constitute marginal to low‐grade ores, are characterised by low Mn/Fe ratio (～2) and have relatively lower abundance of trace (1500 to 2500 ppm) and relatively higher REE constituents. The stratabound‐replacement types of ore bodies are of intra‐stratal nature, occurring within tuffaceous shale. These are mostly shear‐controlled ore bodies extending along a zone of certain width. Increase in average Mn/Fe ratio (～6) and trace content (5000 to 8500 ppm) by 5 to 2.5 order of magnitude respectively or more above stratiform category are characteristic of these deposits. The lateritoid ore bodies have limited depth persistency. Such deposits are usually very low in Mn/Fe ratio (<1), trace (<2000 ppm) and REE contents. Different methods of exploration techniques are suggested for various categories of Mn‐ore bodies. In this context, the above findings would be the database for the exploration geologists to evaluate the potential of newer/existing Mn‐ore resources in this part of north Orissa.     

Enzyme leach anomalies associated with deep Mississippi Valley-type zinc ore bodies at the Elmwood Mine, Tennessee

Deeply buried Mississippi Valley-type deposits that have been or are currently being mined in North America were initially discovered by drilling. Conventional geochemical methods are ineffective for detecting these ‘blind' deposits when they occur deep within sequences of stable-platform carbonates and shales. The ‘enzyme' leach is a selective analytical technique for determining trace elements associated with amorphous Mn oxide coatings in soils. In many areas of the world, the enzyme leach method is useful for detecting low-level geochemical anomalies in soils, which are associated with blind mineral deposits. Enzyme leach analysis of soils, collected at the Elmwood Mine, Tennessee, revealed high-contrast anomalies over ore bodies 370 m below the surface. In areas where the soils are in chemical equilibrium, ‘combination' anomalies occur over Zn ore bodies. These are characterized by asymmetrical halogen halos which occur around a halogen ‘central low'. Commodity metals (Zn and Pb) and trace elements associated with the ore (Cd, Ba, and Mn) form apical anomalies, which occur over the ore bodies and within the halogen halo. Under most circumstances, agricultural practices do not affect enzyme leach results. However, agricultural activity in central Tennessee appears to have altered the proportion of amorphous Mn oxides in the soils in some locations. Where the MnO₂-form equilibrium of the soil has been disturbed, enzyme leach data are erratic. In the one instance where this was encountered, ratioing the data to Mn reveals anomalies which bracket the blind ore bodies.     

Geological and Geochemical Investigation of Three Ophiolite‐Hosted Manganese Prospects,Southeast of Birjand,South Khorasan,East of Iran

The studied ophiolite‐hosted manganese prospects are located in southeast of Birjand, South Khorasan, in the east of Iran. The manganese ores within the ophiolitic sequence in this region occur as small discrete patches, associated with radiolarian chert and shale. Manganese ores in the host rocks are recognizable as three distinct syngenetic, diagenetic, and epigenetic features. The syngenetic manganese ores occurred as bands associated with light‐red radiolarian chert. The diagenetic Mn ores occurred as lenses accompanied by dark‐red to brown radiolarian chert. The epigenetic Mn ores occurred as veins/veinlets within the green radiolarian shale. The major manganese ore minerals are pyrolusite, braunite, bixbyite, ramsdellite, and romanechite showing replacement, colloidal, and brecciated textures. The high mean values of Mn/Fe (15.32) and Si/Al (15.65), and the low mean concentration values of trace elements, such as Cu (85.9 ppm), Ni (249.9 ppm), and Zn (149 ppm), as well as the high concentration values of Si, Fe, Mn, Ba, Zn, Sr, and As in the studied manganese ores furnished sufficient evidence to postulate that the sea‐floor Mn‐rich hydrothermal exhalatives were chiefly responsible for the ore formation, and the hydrogenous processes had negligible role in generation of the ores. The further geological and geochemical evidence also revealed that the ores deposited on the upper parts of the ophiolitic sequence by submarine exhalatives. The intense hydrothermal activities caused leaching of elements such as Mn, Fe, Si, Ba, As and Sr from the basaltic lavas (spilites). After debouching of the sea‐floor exhalatives, these elements entered the sedimentary basin. The redox conditions were responsible for separation of Fe from Mn.     

Germanium in Magnetite: A Preliminary Review

Magnetite is a very common mineral in various types of iron deposits and some sulfide deposits. Recent studies have focused on the use of trace elements in magnetite to discriminate ore types or trace ore-forming process. Germanium is a disperse element in the crust, but sometimes is not rare in magnetite. Germanium in magnetite can be determined by laser ablation ICP-MS due to its low detection limit (0.0X ppm). In this study, we summary the Ge data of magnetite from magmatic deposits, iron formations, skarn deposits, iron oxide copper-gold deposits, and igneous derived hydrothermal deposits. Magnetite from iron formations contains relatively high Ge (up to ~250 ppm), whereas those from all other deposits mostly contains Ge less than 10 ppm, indicating that iron formations can be discriminated from other Fe deposits by Ge contents. Germanium in magmatic/hydrothermal magnetite is controlled by a few factors. Primary magma/fluid composition may be the major control of Ge in magnetite. Higher oxygen fugacity may be beneficial to Ge partition into magnetite. Sulfur fugacity and temperature may have little effect on Ge in magnetite. The enrichment mechanism of Ge in magnetite from iron formations remains unknown due to the complex ore genesis. Germanium along with other elements (Mn, Ni, Ga) and element ratios (Ge/Ga and Ge/Si raios) can distinguish different types of deposits, indicating that Ge can be used as a discriminate factor like Ti and V. Because of the availability of in situ analytical technique like laser ablation ICP-MS, in situ Ge/Si ratio of magnetite can serve as a geochemical tracer and may provide new constraints on the genesis of banded iron formations.     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

贵州省松桃县道坨超大型锰矿床的发现及其成因探讨

贵州省松桃县道坨锰矿床是新发现的一个超大型全隐伏锰碳酸盐矿床。文章阐述了该矿床的发现概况及基本的地质和地球化学特征,并应用锰矿石和含锰黑色页岩的元素和碳同位素地球化学特征对菱锰矿的形成机制提出了制约。道坨超大型锰矿床的发现是填图及对区域地质资料综合分析的结果。该矿床具有品位高、厚度大、呈层性好及展布广等特点。其锰矿石的主量元素特征为Al2O3、TiO2、Fe2O3含量较低,P2O5中等程度富集,MnO、MgO含量相对较高,Fe/Mn比值低。在微量元素方面,锰矿石显示出较为明显的Co富集,含锰黑色页岩则显示出较为明显的Co、Mo富集;在稀土元素方面,锰矿石具有较高的稀土元素总量,轻微的"帽式"稀土元素PAAS标准化配分模式及明显的Ce正异常,含锰黑色页岩的稀土元素总量与PAAS接近,其稀土元素PAAS标准化配分模式较为平坦,无Ce异常。碳同位素测试结果显示出菱锰矿富集碳的轻同位素,表明在菱锰矿形成过程中存在有机碳的参与。文章表明,道坨锰矿床内的锰是以氧化物或氢氧化物的形式沉淀,菱锰矿是在缺氧且富含有机物质的成岩环境中转化而成。     

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.     

Tourmaline in the central Swedish ore district

More than 40 recently discovered tourmaline occurrences have been investigated in the Mid-Proterozoic Bergslagen ore district of central Sweden. Some are spatially associated with ores, others with zones of leaching, remobilization and migmatization. Among the tourmaline-bearing ore deposits are the Dammberg ZnPb-Fe sulphide deposit, the Sala Pb-Zn-Ag deposit, the Dalkarlsberg, Pershyttan and Håksberg Fe oxide deposits, the Leja Cu deposit, and the Zinkgruvan Zn-Pb-Ag deposit. Tourmaline has been recorded a) as tourmalinites and tourmaline-bearing chemical sediments; b) in tourmaline-bearing skarns; c) in tourmaline-quartz veins; d) as disseminations along the foliation in schists; e) in tourmaline pegmatites; f) in tourmalinized haloes in metavolcanites along tourmaline pegmatites; and g) in late joints. Tourmalinites, tourmaline-bearing chemical sediments and tourmaline-bearing skarns are spatially associated with sulphide and oxide mineralizations. The dravite components in these tourmalines are proportional to the size of Zn-Pb sulphide mineralizations. Tourmalines from quartz veins close to and within ore deposits contain high Zr and Cr contents. With increasing distance away from these deposits, the Zr and Cr contents fall significantly. Tourmalines from pegmatites have inherited a number of trace element enrichments through partial melting and assimilation of volcaniclastic sediments into granitic melts. Despite magmatic homogenization, Zn contents in these tourmalines reflect the proximity of Zn-Pb-sulphide deposits, decreasing away from them. Tourmalines from late joints with Zn contents above the 100 ppm level are also indicative for the proximity of Zn-Pb sulphide mineralizations. Thus, some trace elements in these tourmalines may represent suitable exploration tools.     

甘肃北山红山铁矿区硅质岩地球化学特征及其成因意义

甘肃北山地区红山铁矿区硅质岩与铁矿体紧密伴生,且有些硅质岩本身就是铁矿石。常量元素分析表明:硅质岩普遍具有高Si、高Fe、低Al特征,K2O含量普遍高于Na2O,且Fe/Ti值为57.14～218.74,(Fe+Mn)/Ti值为57.54～224.16,Al/(Al+Fe+Mn)值为0.05～0.14,均符合热水沉积硅质岩的特征,但存在少量陆源物质介入。稀土微量元素分析表明:硅质岩大部分微量元素相对于克拉克值亏损,稀土元素总量低,经北美页岩标准化后,Ce异常明显或微明显,Eu呈现明显的正异常,重稀土相对轻稀土富集;δCe值为0.93～1.05,平均为0.99;La/Ce值为0.43～0.49,平均为0.44,更接近于大陆边缘硅质岩的特征。综合以上地球化学特征,硅质岩具有明显的热水沉积成因属性,同时有陆源组分的加入,进而得出红山铁矿为与热水沉积成因有关的铁矿床,当时形成环境为大陆边缘环境。     

Ore Genesis for Stratiform Ore Bodies of the Dongfengnanshan Copper Polymetallic Deposit in the Yanbian Area, NE China：Constraints from LA-ICP-MS in situ Trace Elements and Sulfide S–Pb Isotopes

The Dongfengnanshan Cu polymetallic deposit is one representative deposit of the Tianbaoshan ore district in the Yanbian area, northeast(NE) China. There occur two types of ore bodies in this deposit, the stratiform ore bodies and veintype ones, controlled by the Early Permian strata and the Late Hercynian diorite intrusion, respectively. Due to the ambiguous genetic type of the stratiform ore bodies, there has been controversy on the relationship between them and veintype ore bodies. To determine the genetic type of stratiform ore bodies, laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) in situ trace elements and S–Pb isotope analysis have been carried on the sulfides in the stratiform ore bodies. Compared with that in skarn, Mississippi Valley-type(MVT), and epithermal deposits, sphalerite samples in the stratiform ore bodies of the Dongfengnanshan deposit are significantly enriched in Fe, Mn, and In, while depleted in Ga, Ge, and Cd, which is similar to the sphalerite in volcanic-associated massive sulfide(VMS) deposits. Co/Ni ratio of pyrrhotites in the stratiform ore bodies is similar to that in VMS-type deposits. The concentrations of Zn and Cd of chalcopyrites are similar to those of recrystallized VMS-type deposits. These characteristics also reflect the intermediate ore-forming temperature of the stratiform ore bodies in this deposit. Sulfur isotope compositions of sulfides are similar to those of VMS-type deposits, reflecting that sulfur originated from the Permian Miaoling Formation. Lead isotope compositions indicate mixed-source for lead. Moreover, the comparison of the Dongfengnanshan stratiform ore bodies with some VMStype deposits in China and abroad, on the trace elements and S–Pb isotope characteristics of the sulfides reveals that the stratiform ore bodies of the Dongfengnanshan deposit belong to the VMS-type, and have closely genetic relationship with the early Permian marine volcanic sedimentary rocks.     

贵州遵义二叠纪锰矿地球化学特征与沉积环境分析：以遵义谢家坝富锰矿床为例

为分析贵州遵义二叠纪锰矿的沉积环境,对谢家坝锰矿床进行常量元素、微量和稀土元素地球化学研究。研究认为：谢家坝锰矿赋存于茅口组顶部含锰岩系中,可分为下矿层豆状、角砾状菱锰矿、似层状菱锰矿,以及上矿层碎屑状、块状菱锰矿的二元结构矿石类型组合,可广泛代表遵义锰矿的矿石特征。谢家坝锰矿上下矿层之间主量元素和稀土元素含量差异较大,常量元素SiO2、TiO2、S、Fe2O3含量上矿层均大于下矿层,MnO、MgO与 Al2O3之间均呈负相关关系;上矿层Fe/Mn值较高,属高Fe低P型锰矿,而下矿层Fe/Mn值较低,属中低Fe低P型锰矿。上矿层稀土元素PAAS标准化配分后呈现较明显的重稀土亏损、弱的轻稀土富集、右倾配分的特征,具有弱的Ce正异常,类似海底铁锰结核稀土元素特征;下矿层呈现弱的中稀土富集,轻、重稀土亏损,弱的帽式分配特征,具明显的Ce负异常,类似典型深部海水沉积稀土元素特征。微量元素Th/U、Ni/Co、V/Cr、V/（V+Ni）、AU等沉积环境古氧相分析指标和稀土元素PAAS标准化配分模式指示,谢家坝锰矿下矿层是在贫氧-厌氧条件下Mn2+与CO32-直接形成菱锰矿,上矿层在常氧-贫氧环境下Mn3+、Mn4+以氧化物或氢氧化物形式沉淀。     

Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

西昆仑北缘主乌鲁克锰矿床地质特征及成因探讨

主乌鲁克锰矿床位于西昆仑北缘晚古生代陆缘裂谷恰尔隆弧盆系的北部,含锰层位为下石炭统他龙群细碎屑岩夹碳酸盐岩,锰矿层为黑色泥质碳质页岩夹铁锰质泥晶灰岩。锰矿体严格受地层的控制,呈NWW向展布,延伸较为稳定,规模较大,共见有13条锰矿体,其中有3个矿体较大构成主矿体;锰矿石以原生菱锰矿为主体,氧化矿石不多。该矿床与近年发现的玛尔坎苏地区锰矿床既有相似之处,又有明显不同,矿床类型为在深海-半深海陆缘裂谷环境中形成的与黑色碳质页岩有关的沉积型锰矿床,锰矿的成矿时代为早石炭世。由于下石炭统他龙群是西昆仑地区新发现的含锰层位,具有较大的找矿潜力,应加强矿床外围及深部的找矿工作。     

Improved methods for selective dissolution of Mn oxides: applications for studying trace element associations

The association of rare earth and other trace elements with Fe and Mn oxides was studied in Fe-Mn-nodules from a lateritic soil from Serra do Navio (Northern Brazil). Two improved methods of selective dissolution by hydroxylamine hydrochloride and acidified hydrogen peroxide along with a classical Na–citrate–bicarbonate–dithionite method were used. The two former reagents were used to dissolve Mn oxides without significant dissolution of Fe oxides, and the latter reagent was used to dissolve both Mn and Fe oxides. Soil nodules and matrix were separated by hand. Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry after fusion with lithium metaborate, and X-ray diffraction were used to determine the elemental and mineralogical composition of the nodules and soil matrix. The latter was composed of kaolinite, gibbsite, goethite, hematite, and quartz. In the nodules, lithiophorite LiAl₂(Mn^IV₂Mn^III)O₆(OH)₆ was detected in addition to the above-mentioned minerals. The presence of hollandite (BaMn₈O₁₆) and/or coronadite (PbMn₈O₁₆) in the nodules is also possible. In comparison to the matrix, the nodules were enriched in Mn, Fe, K, and P, and relatively poor in Si, Al, and Ti. The nodules were also enriched in all trace elements determined. Phosphorus, As and Cr were associated mainly with Fe oxides; Cu, Ni, and V were associated with both Fe and Mn oxides; and Ba, Co, and Pb were associated mainly with Mn oxides. Distribution of rare earth elements indicated a strong positive Ce-anomaly in the nodules, compared to the absence of any anomaly in the matrix. Some of Ce was associated with Mn oxides. The improved methods achieved almost complete release of Mn from the sample without decreasing the selectivity of dissolution, i.e., without dissolving significant amounts of Fe oxides and other minerals, and provided reliable information on associations of trace elements with Mn oxides. These methods are thus proposed to be included in sequential extraction schemes for fractionation of trace elements in soils and sediments.     

大厂锡—多金属矿床热液喷气沉积成因的证据——容矿岩石的微量元素及稀土元素地球化学

对大厂锡矿床容矿岩石稀土元素地球化学研究表明，本矿区主要容矿岩石——硅质岩、富长石岩及电气石岩稀土元素总量低，具弱的Ce亏损，明显的Eu负异常。这些特点与某些 有代表性矿床中的热液喷气沉积岩一条带状燧石岩及电气石岩十分相似，证明了它们属于喷气沉积成因。相反，与主要容矿岩石互成条带的部分绢云母岩，含绢云母的长石岩等则稀土总量高，轻重稀土分馏明显，与北美页岩相似，具有陆源沉积或混合成因的特征。运用聚类分析的方法，这些岩石的微量元素地球化学分类与上述结果完全一致，为其成因进一步提供了佐证。     

3D Modeling and Determination of Factors Responsible for Zinc-Lead Mineralization in the Mehdiabad Deposit, Central Iran, based on Statistical Analysis of Geochemical Data

Although the Mehdiabad zinc-lead deposit is one of the most well-known deposits in the central Iran structural zone, the genesis of the deposit remains controversial. The host rock of the ore is a dolomitic limestone of the Lower Cretaceous Taft Formation. In the two main orebodies of the deposit, which includes the Black Hill and East Ridge ore zones, the oxide and sulfide ores are observed at the surface and at depth, respectively. The elements Zn, Fe, Mn and Mg are more abundant in the East Ridge ore zone (in both sulfide and oxide ores), with Ba, Pb, Ag and Cu being more abundant in the Black Hill oxide ore. Based on the distribution of elements and their correlation with each other in these ore zones, the elements are divided into three general groups, that of terrigenous elements, chemically-deposited elements and ore-forming (hydrothermally deposited) elements, a division that is supported by the results of factor analyses. The spatial distribution of elements is jointly affected by contact with host rocks, the boundary of oxide-sulfide ores and fault zones. The main factors governing the distribution of elements are the mechanical transfer of detrital sediments, chemical sedimentation, transfer by hydrothermal fluids, oxidation and surface dissolution, all of which affected the spatial distribution of elements. The ore-forming elements are mostly affected by hydrothermal fluids and oxidation. This study not only provides additional information about the genesis of the Mehdiabad deposit, but also could assist in the exploitation of ore and further exploration purposes. The results of this study can aid in the exploration and exploitation of the Mehdiabad deposit and similar deposits in the region.     

Manganese minerals and associated fine particulates in the streambed of Pinal Creek,Arizona, U.S.A.: a mining-related acid drainage problem

The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O₂ is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed.Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek.In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn₃O₄ to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO₃ and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn₄O₉ · (3H₂O)) and takanelite ((Mn,Ca)Mn₄O₉ · (3H₂O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO₃ from an anoxic groundwater that contained CO₂ HCO₃, and precipitated Mn₃O₄ and subsequently MnOOH from an oxic surface water from which most of the dissolved CO₂ had been removed.It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the MnFe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO₃, 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.     

In-situ LA-ICP-MS trace elemental analyses of magnetite: Fe–Ti–(V) oxide-bearing mafic–ultramafic layered intrusions of the Emeishan Large Igneous Province,SW China

The Taihe, Baima, Hongge, Panzhihua and Anyi intrusions of the Emeishan Large Igneous Province (ELIP), SW China, contain large magmatic Fe–Ti–(V) oxide ore deposits. Magnetites from these intrusions have extensive trellis or sandwich exsolution lamellae of ilmenite and spinel. Regular electron microprobe analyses are insufficient to obtain the primary compositions of such magnetites. Instead, laser ablation ICP-MS uses large spot sizes (~ 40 μm) and can produce reliable data for magnetites with exsolution lamellae. Although magnetites from these deposits have variable trace element contents, they have similar multi-element variation patterns. Primary controls of trace element variations of magnetite in these deposits include crystallography in terms of the affinity of the ionic radius and the overall charge balance, oxygen fugacity, magma composition and coexisting minerals. Early deposition of chromite or Cr-magnetite can greatly deplete magmas in Cr and thus Cr-poor magnetite crystallized from such magmas. Co-crystallizing minerals, olivine, pyroxenes, plagioclase and apatite, have little influence on trace element contents of magnetite because elements compatible in magnetite are incompatible in these silicate and phosphate minerals. Low contents and bi-modal distribution of the highly compatible trace elements such as V and Cr in magnetite from Fe–Ti oxide ores of the ELIP suggest that magnetite may not form from fractional crystallization, but from relatively homogeneous Fe-rich melts. QUILF equilibrium modeling further indicates that the parental magmas of the Panzhihua and Baima intrusions had high oxygen fugacities and thus crystallized massive and/or net-textured Fe–Ti oxide ores at the bottom of the intrusive bodies. Magnetite of the Taihe, Hongge and Anyi intrusions, on the other hand, crystallized under relatively low oxygen fugacities and, therefore, formed net-textured and/or disseminated Fe–Ti oxides after a lengthy period of silicate fractionation. Plots of Ge vs. Ga + Co can be used as a discrimination diagram to differentiate magnetite of Fe–Ti–(V) oxide-bearing layered intrusions in the ELIP from that of massif anorthosites and magmatic Cu–Ni sulfide deposits. Variable amounts of trace elements of magmatic magnetites from Fe–Ti–(P) oxide ores of the Damiao anorthosite massif (North China) and from Cu–Ni sulfide deposits of Sudbury (Canada) and Huangshandong (northwest China) demonstrate the primary control of magma compositions on major and trace element contents of magnetite.     

Geology,geochemistry and genesis of the Godar Sabz Mn deposit in the Baft region,Iran

The Godar Sabz Mn deposit is located in the Nain-Baft ophiolitic belt in the northeast margin of the Sanandaj-Sirjan zone, Iran. The Nain-Baft back-arc extensional basin resulted from the subduction of the oceanic crust of Neo-Tethys under the southern margin of the Iranian Plate in the Early Cretaceous and hosts several mineral deposits, including volcanogenic massive sulfide, chromite, and Mn deposits. The mineralization in the Godar Sabz Mn deposit occurred predominantly as stratabound, massive, banded, layered, and lenticular orebodies in radiolarian cherts within Baft ophiolitic complex. The main ore minerals are pyrolusite, braunite, with minor amounts of todorokite. The significant geochemical features of the Godar Sabz ores, such as the high MnO content (21.82–80.65 wt%, average = 64.91 wt%), high Mn/Fe (average = 278), Si/Al ratios (average = 92.6), high Ba contents (average = 4495.6 ppm), the low average contents of Cu (81.8 ppm), Ni (106.2 ppm), Co (29.4 ppm), LREE > HREE, and trace element discrimination diagrams indicate a hydrothermal-exhalative source for mineralization. Chondrite-normalized REE patterns of studied ores have negative Ce and slightly positive Eu anomalies, which are similar to hydrothermal Mn deposits. The REE patterns of Mn ores coincide with basaltic lavas, suggesting that the Mn-mineralization in the Godar Sabz deposit was genetically related to the leaching of basaltic lavas. The Godar Sabz Mn deposit has many similarities with the main characteristics of the hydrothermal exhalative Mn deposits, including tectonic setting, host rock type, the morphology of orebodies, ore textures, mineralogy, and chemical features of ores.     

Ferromanganese oxide deposits from the Central Pacific Ocean,I. Encrustations from the Line Islands Archipelago

Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO₂ and amorphous FeOOHxH₂O. Compositionally, they are similar to δMnO₂ nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO₂ is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO₂xH₂O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher $\text{Mn}\text{Fe}$ ratios than deeper crusts, which are compositionally constant. The higher $\text{Mn}\text{Fe}$ ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher $\text{Mn}\text{Fe}$ ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The $\text{Mn}\text{Fe}$ ratios of the crusts thus reflect the composition of suspended oxides at similar depths.