Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

Leaching process and kinetics of manganese in low-grade manganese ore

Manganese was extracted from leaching low-grade manganese ore in sulfuric acid medium. The effects of granule diameter, leaching time, liquid/solid ratio (V/W) and the concentration of sulfuric acid were investigated through orthogonal and single factor experiments. The experimental results showed that the optimal leaching conditions are, size of 0.054mm, 120 minutes of reaction time, 3(V/W) of liquid/solid ratio and 30% of the concentration of sulfuric acid (g/g). Under those conditions, the leaching efficiency is 96.73%. The kinetics of the leaching process is in accordance with the characteristics of fractal reaction.     

Biomineral nanostructures of manganese oxides in oceanic ferromanganese nodules

Manganese oxides, which are widespread and of great practical importance, are formed and transformed by the active role of microorganisms. Manganese aggregates occur as both crystallized varieties and disordered fine-grained phases with significant ore grade and up to 50–60 vol % of X-ray amorphous components. X-ray amorphous nanosized Mn oxides in Fe-Mn nodules from the Pacific Ocean floor were examined from the standpoint of their biogenic origin. SEM examination showed abundant mineralized biofilms on the studied samples. The chemical composition of bacterial mass is as follows (wt %): 28.34 MnO, 17.14 Fe₂O₃, 7.11 SiO₂, 2.41 CaO, 17.90 TiO₂, 1.74 Na₂O, 1.73 Al₂O₃, 1.30 MgO, 1.25 P₂O₅, 1.25 SO₃, 0.68 CoO, 0.54 CuO, 0.53 NiO, and 0.50 K₂O. The chemical composition of fossilized cyanobacterial mats within the interlayer space of nodulesis as follows (wt %): 48.35 MnO, 6.23 Fe₂O₃, 8.76 MgO, 5.05 Al₂O₃, 4.45 SiO₂, 3.63 NiO, 2.30 Na₂O, 2.19 CuO, 1.31 CaO, and 0.68 K₂O is direct evidence for participation of bacteria in Mn oxide formation. This phase consists of mineralized glycocalix consisting of nanosized flakes of todorokite. Native metals (Cu, Fe, and Zn) as inclusions 10–20 μm in size were identified in ferromanganese nodules as well. The formation of nativemetals can be explained by their crystallization at highly reducing conditions maintained by organic matter.     

Transformations of ore minerals in genetically different oceanic ferromanganese rocks

Results of thermic transformations of ore minerals from genetically different oceanic ferromanganese rocks in the course of their heating up to 1000°C are considered. Manganese minerals with various types of crystalline lattice have different grades of thermic stability. Layered manganese minerals (buserite I, asbolane-buserite, and birnessite) are stable up to 120–150°C; asbolane up to 180°C, vernadite, up to ～500°C; todorokite and pyrolusite (minerals of the tunnel group), up to 600 and 670°C, respectively. Sorbed cations of heavy metals govern the transformation temperature and mineral composition of products of the calcination of ferromanganese rocks. Study of birnessite and todorokite demonstrated that genesis of ferromanganese rocks do not affect thermic properties of minerals in them.     

Kinetic and thermodynamic factors controlling manganese concentrations in oceanic waters

Data are presented describing the changes in the distribution of dissolved and particulate Mn observed over a 16-month period in the periodically anoxic waters of Saanich Inlet, a fjord located on the coast of Vancouver Island, British Columbia. During the spring and summer when the bottom waters were anoxic, a dense cloud of particulate Mn was found at mid-depths where Mn²⁺ enriched anoxic bottom waters were mixing with oxygenated waters; then, during the autumn aand winter following an intrusion which reoxygenated the bottom water, an intense precipitation of Mn was observed throughout the entire water column. During this latter period, dissolved Mn concentrations in the bottom water, which exceeded 1000 nmol/l under anoxic conditions, decreased towards a lower limit of 1.6 nmole/l, a value comparable to that observed in Pacific Ocean waters of similar pH and dissolved oxygen content. Mn in the particulate matter collected just above the oxic-anoxic interface was found to have an average oxidation number of +3.05; and, on this basis, it is proposed that dissolved Mn concentrations in oceanic waters are controlled by the precipitation of the metastable oxide mineral manganite (γ-MnOOH), a hypothesis consistent with the fact that dissolved Mn values in subsurface Pacific Ocean waters closely approach the equilibrium solubility of this phase. Temporal and spatial gradients in the particulate Mn distribution were used to calculate the in situ rate of Mn precipitation, and the results of these calculations then were fitted to theoretical rate equations which suggest that the precipitation of Mn is controlled by 2 parallel processes: bacterial oxidation and an inorganic autocatalytic oxidation reaction.     

南非LOMOTENG铁锰矿矿床成因及矿石加工技术性能评价

LOMOTENG铁锰矿床位于南非波斯特马斯堡—卡拉哈里南北向铁锰成矿带西矿带中段,矿层呈层状或透镜状产于阿斯别斯伯尔格组(Vg)中下部,有时与下伏那姆阿克拉斯组(Vgl)的不整合面直接接触,产状受地层控制,矿区可分为六个矿层,矿床类型为沉积变质型,矿石类型为铁矿石、富锰矿石和铁锰矿石,矿石工业类型属于高铁、低磷冶金用锰矿石,通过采用干、湿试永磁强选机进行一粗一扫进行分选试验,混合锰品位可提高5%~11%,矿山易采易选。本文着重分析该矿产的矿床成因,并对矿石的加工技术性能进行评价。     

Ion exchange properties of manganese and iron minerals in oceanic micronodules

The results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules (MN) from diverse bioproductive zones of the World Ocean are considered. It was found that the sorption behavior of these minerals is similar to that of ore minerals from ferromanganese nodules (FMN) and low-temperature hydrothermal crusts. The exchange complex of minerals in the MN includes the major (Na⁺, K⁺, Ca²⁺, Mg²⁺, and Mn²⁺) and the subordinate (Ni²⁺, Cu²⁺, Co²⁺, Pb²⁺, and others) cations. Reactivity of theses cations increases from Pb²⁺ and Co²⁺ to Na⁺ and Ca²⁺. Exchange capacity of MN minerals increases from the alkali to heavy metal cations. Capacity of iron and manganese minerals in the oceanic MN increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite Fe-vernadite + Mn-feroxyhyte. The data obtained supplement the available information on the ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in the redistribution of metal cations at the bottom (ooze) water-sediment interface during the MN formation and growth.     

Preparation of chemical manganese dioxide from low-grade rhodochrosite ore

The preparation of chemical manganese dioxide(CMD) from low-grade rhodochrosite ore(LGRO) in Xiushan,Chongqing,was studied and improved,including leaching with sulfuric acid,purifying,crystallizing and decomposing of MnCO3,and refining of primary MnO2.The product was characterized by X-ray diffraction.The results showed that the extraction ratio,the manganese recovery ratio of purifying,crystallization and refining reached 96.8%,93.9%,97.7%and 85.4%,respectively.The optimum conditions of refining were described as follows:liquid(H2SO4)/solid(primary MnO2) ratio was 3 L/g,the concentrations of NaClO exceeded 20%,and reaction time was 3 hours.Under the above conditions,the contents of MnO2and Mn in the obtained manganese dioxide were respectively 85.1%and 53.9%.The refined MnO2can be used as the super grade manganese dioxide mine powder in chemical industry.The XRD indicated that the structure of the product wasγ-MnO2.     

Geology and ore genesis of the manganese ore deposits of the Postmasburg manganese-field,South Africa

The Postmasburg Mn/Fe-ores occur exclusively in dolomitic Precambrian sinkhole structures with siliceous breccias and shales as hostrocks. The main manganese minerals are braunite and bixbyite, apart from secondary alteration products of the psilomelane-manganomelane family. Various generations of ore minerals could be identified. The ore mineralization is subdivided into three different genetic types. They are classified either as pure karst deposits or as combined formations of karst origin and shallow marine sedimentation due to the transgression of the Banded Iron Formation (BIF) sea. Post-sedimentary metamorphism is identified as very low grade. The development of the different ore types is illustrated schematically.     

中国锰矿勘查进展及需要解决的主要问题

锰矿是我国大宗紧缺矿产之一。近年来中国南华系、石炭系、二叠系、三叠系锰矿取得突破性进展,新增锰矿资源量达15亿吨,完成国家“358”锰矿战略目标,进一步丰富了“内源外生”等成矿理论。但目前锰矿远景资源量储备不足,锰矿科研工作尚需深入开展。本文较全面地总结了我国锰矿勘查工作及成矿理论的进展,提出需要解决的主要问题,指出了下一步工作部署的建议。     

锰铁废渣作为道路基层填料的试验研究

现代工业迅猛发展的同时，也随之产生大量的工业废渣。利用工业废渣修筑道路基层，既可以达到道路基层的强度标准，也可以解决大量废渣的处理问题，具有十分重要的现实意义。论文对锰铁废渣的化学成份进行了分析，对风积土的物理力学性质进行了试验研究，获得了大量的科学数据。同时利用石灰、锰铁废渣、碎石和风积砂土作为路面基层稳定土的原材料，进行了配比试验和性能测试。在试验过程中，运用均匀设计方法安排试验，测量稳定土的各项指标。依据试验结果，采用SPSS软件进行了回归分析，得到了稳定土无侧限抗压强度的回归方程。试验结果表明，利用锰铁废渣作为道路基层的填料是可行的，既可以节约原材料的能量消耗，又可以减少环境污染，具有广泛的应用前景和显著的社会效益、环境效益与经济效益。     

Detrital type manganese ore bodies in the iron ore group of rocks, Orissa, Eastern India

Detrital type of manganese ore bodies in the Precambrian Iron Ore Group of rocks occur in the Bonai-Keonjhar belt, Orissa besides stratiform (bedded type) and stratabound-replacement types of deposits. These ores appear in form of large boulders within lateritised aprons at various depths, often reaching beyond 30 m from the surface. Overprinting of primary structures, presence of mixed Fe-clasts and Mnooliths/pisoliths, mineral species of different generations and wide chemical variation amongst morphological varieties and from boulder to boulder are the characteristic hallmarks of such ore bodies. Features associated with ores occurring in different morphologies, namely: spongy, platy, recemented, and massive varieties from a typical profile of Orahari Mn-ore body in Keonjhar district are described. Recemented variety may be further classified into sub-varieties such as canga, agglomerate, and mangcrete. Common primary Fe-minerals are hematite, martite with relict magnetite. The secondary Fe-Mn phases are goethite, specularite, cryptomelane, lithiophorite, chalcophanite, manganite, and pyrolusite.These are ore bodies of allochthonous nature developed through a number of stages during terrain evolution and lateritisation. Secondary processes such as reworking of pre-existing crust through remobilisation, solution, precipitation, cementation, transport, etc. are responsible for the development of such detrital ore bodies in the Bonai-Keonjhar belt of Eastern India.     

Characteristic features of ore gabbro formation in the third layer of the oceanic crust

Peculiarities of ore gabbro formation in slow-spreading mid-ocean ridges exemplified by the non-transform Sierra Leone fault and Marathon fault areas are considered. The formation of ore gabbros is most often connected with the rheologically weakened oceanic lithosphere mainly with active fault zones, in which basic magmatic melts intruded. Those faults provide ways for migration of differentiated melts at different depth levels. When intruding and moving along fault zones, melts interacting with the mantle and crust host rocks are often already hydrated. Such interaction occurs largely in conditions of subsolidus deformations resulting in enrichment of melts with volatile components.     

西昆仑玛尔坎苏锰矿带博托彦南发现二叠纪锰矿

正1研究目的(Objective)西昆仑玛尔坎苏锰矿带是中国北方地区锰矿找矿勘查的重大突破,目前已发现奥尔托喀讷什锰矿、穆呼锰矿、玛尔坎土锰矿等一批大中型富锰矿,累计探获锰矿石资源量5000万t以上,具有较大的富锰矿找矿潜力。主要含锰岩系为一套晚石炭世的海相碎屑岩-碳酸盐岩建造(图1),长期以来在玛     

Manganese deposits: Communication 1. Genetic models of manganese ore formation

Major regularities in the formation of manganese rocks and ores have been established on the basis of available published and original data. The proposed genetic classification of main manganese deposits (with model examples) is as follows: sedimentary-diagenetic (Nikopol, Bol’she-Tokmak; Ukraine), (volcanogenic) hydrothermal-sedimentary (deposits of the Atasui area, Kazakhstan; Magnitogorsk Trough, South Urals), epigenetic (catagenetic) (deposits of the Kalahari manganese ore field, South Africa; Usinsk deposit, Kuznetsk Alatau), and supergene (residual, infiltrational, cavern filling, and pisolitic deposits in India, Brazil, South Africa, and Australia). The results suggest the following conclusions: (1) all primary manganese rocks and ores at the known deposits are hydrothermal- and diagenetic-sedimentary formations of marine environments; (2) manganese concentrations achieve the size of deposits at postsedimentary stages of the initial manganiferous sediment and manganese rock transformation (diagenesis, catagenesis, and retrograde diagenesis); (3) indispensable participation of the isotopically light carbon dioxide related to the destruction of organic matter (OM) is a characteristic feature of manganese carbonate formation during diagenesis; and (4) the role of organic carbon in manganese ore formation becomes notable since early stages of Mn accumulation in the Precambrian sedimentary basins (terminal Archean-initial Early Proterozoic).     

滇东南地区石炭系锰矿找矿新发现

锰矿是我国重要的战略紧缺资源。本文通过对云南省大平-鸣就地区矿产地质调查研究,首次发现在石炭系顺甸河组中赋存有工业锰矿。通过对矿区的岩相古地理、地质特征、地球化学特征的研究分析,表明该锰矿是在贫氧的环境下,形成于古陆边缘的浅海,属于台地边缘浅滩相的产物。该发现和研究为今后在该层位中寻找锰矿提供了重要线索和依据,为锰矿找矿工作提供了新方向。     

广西钦州-防城地区次生氧化锰矿床矿物学和地球化学研究及矿床成因意义

钦州-防城锰矿带是中国次生氧化锰矿的重要产地之一,其含锰岩系为上泥盆统榴江组含锰硅质岩。锰矿床主要赋存在以腐岩带为主的风化壳中,矿石的主要矿物为软锰矿、锰钡矿、隐钾锰矿、锂硬锰矿、钙锰矿等,与之伴生的其他表生矿物有赤铁矿、针铁矿、石英、高岭石和其他粘土矿物。矿石多呈葡萄状、块状、网脉状构造。与原生含锰硅质岩相比,次生氧化锰矿矿石的品位明显提高,Mn含量平均达到42.6%。矿石化学分析和单矿物电子探针成分分析表明,氧化锰矿石中还普遍出现Co、Ni、Cu、Zn等元素的富集,其平均含量分别为0.05%(最高0.40%)、0.09%(最高0.53%)、0.08%(最高0.53%)和1%(最高2.2%);它们主要以类质同象和吸附的形式赋存在锂硬锰矿及隐钾锰矿中。氧化锰矿石和锰氧化物的Mn/Fe比值均较高,一般大于6～10,说明该区化学风化强烈,铁、锰分离显著,有利于形成高品位的优质锰矿。有害杂质元素P主要存在于针铁矿等铁的氧化物中。氧化锰矿的形成和空间分布受气候、构造、含锰岩系及地形地貌等多种因素的影响和控制。