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.     

Mineralogy, chemistry and genesis of Nishikhal manganese ores of South Orissa, India

Manganese ores of Nishikhal occur as distinctly conformable bands in the khondalite suite of rocks belonging to the Precambrian Eastern Ghats complex of south Orissa, India. Manganese minerals recorded are cryptomelane, romanechite, pyrolusite, with minor amounts of jacobsite, hausmannite, braunite, lithiophorite, birnessite and pyrophanite. Goethite, graphite, hematite and magnetite are the other opaque minerals and quartz, orthoclase, garnet, kaolinite, apatite, collophane, fibrolite, zircon, biotite and muscovite are the gangue minerals associated with these ores. The mineral chemistry of some of the phases, as well as the modes of association of phosphorous in these ores have been established. The occurrence of well-defined bands of manganese ore; co-folding of manganese ore bands and associated metasedimentary country rocks; the min-eral assemblage of spessartite-sillimanite-braunite-jacobsite-hausmannite; the geochemical association of Mn-Ba-Co-Ni-Zn together with the Si versus Al and Na versus Mg plots of the manganese ores suggest that the Nishikhal deposit is a metamorphosed Precambrian lacustrine deposit. Continental weathering appears to be the source for manganese and iron. After deposition and probable diagenesis, the manganese-rich sediments were metamorphosed along with conformable psammitic and pelitic sediments under granulite facies conditions, and subsequently underwent supergene enrichment to produce the present deposit. Received: 14 March 1995 / Accepted: 11 April 1996     

Reworked manganese ore bodies in Bonai-Keonjhar belt,Singhbhum Craton,India: Petrology and genetic study

The genetic evolution of three types of reworked manganese ore bodies namely: Detrital, Concretionary (Mangcrete) and Wad in the Precambrian Iron Ore Group occurring in Bonai-Keonjahr belt, Singhbhum Craton, India are reported. All the reworked Mn-ore bodies are developed in a restricted area and have a limited resource. Mangcrete and wad are commonly exposed at the surface and extend to a maximum depth of 10 m while detrital ores are observed below 10–20 m from the surface.Detrital ore bodies occur as large boulders and are buried under a thick zone of laterite. Mangcrete is concretionary in nature; oolitic, spherulitic and nodular in shape. Broken fragmented of ooloids and pisoloids, often observed in mangcrete, are indications of reworking. Wad exposures are noticed above low to medium-grade bedded manganese ore bodies. Among three reworked ore types, the detrital is of low to medium-grade having Mn:Fe ratio > 5, while wad and mangcrete are of sub-grade (Mn:Fe ~ 1) and off-grade type (Mn:Fe < 1) respectively.Detrital ore bodies are of allochthonous nature and developed through several stages such as fragmentation of pre-existing ore, leaching and cementation followed by transportation and deep burial. Mangcrete represent chemogenic precipitates at several stages of contemporary Mn-Fe-Al rich fluid under supergene environment. Wad is of bio-chemogenic origin and developed in a swampy region under marine environment due to slow chemical precipitation of Mn-Fe enriched fluid, in several stages nucleating quartz/hematite/cryptomelane detritals.     

Manganese oxide mineralogy,petrography and genesis,Pilbara Manganese Group,Western Australia

Supergene manganese oxides, occurring in shales, breccias and dolomites of Proterozoic Age, in the Western Australian Pilbara Manganese Group, have Mn/Fe ranging from 1.9 to 254 and Mn⁴⁺ to Mn (Total) of 0.49–0.94. The manganese mineralogy is dominated by tetravalent manganese oxides, especially by cryptomelane, with lesser amounts of pyrolusite, nsutite, manjiroite, romanechite and other manganese oxide minerals. The manganese minerals are commonly associated with iron oxides, chiefly goethite, indicating incomplete separation of Mn from Fe during Tertiary Age arid climate weathering of older, manganiferous formations. These manganese oxides also contain variable amounts of braunite and very minor hausmannite and bixbyite. The braunite occurs in three generations: sedimentary-diagenetic, recrystallised sedimentary-diagenetic, and supergene. The mode of origin of the hausmannite and bixbyite is uncertain but it is possible that they resulted from diagenesis and/or low-grade regional metamorphism. The supergene manganese deposits appear to have been derived from manganiferous Lower Proterozoic banded iron formations and dolomites of the Hamersley Basin and overlying Middle Proterozoic Bangemali Basin braunite-containing sediments.     

Contribution à la connaissance des romanéchites et des cryptomélanes — coronadites — hollandites. Traits essentiels et paragenèses

Chemical, thermal, X Ray analysis, and microscopic observation of romanechites, cryptomelanes, and coronadites indicate some specific features for each of these oxide.Structural calculation shows a theoretical ratio Ba/H₂O close to 12 for romanechite, slightly different for samples from cuirass. In the group cryptomelane, coronadite, hollandite the ratio: (Ba, K, Pb)/H₂O equals generaly 11, exceptionnally 12 under supergene conditions.Thermogravimetric curves indicate some weight loss starting at low temperature for romanechite and cryptomelane and higher temperature for coronadite and hollandite.Optical properties of these oxides seem to be more influenced by the evolution of the ore complex than by their own chemical particularities.The microscopic anisotropy is higher for romanechite and coronadite than for cryptomelane.Romanechite, cryptomelane, and coronadite present a great stability under surface conditions, where these oxides generally replace pyrolusite.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

鄂东北鹰咀山锰矿床地质特征及找矿标志

鹰咀山锰矿床产出在桐柏—大别造山带中，目前已发现有4条锰矿（化）体，其产出受控于红安群黄麦岭组和七角山组。本文基于矿区锰矿勘查工作和室内观察、测试研究相结合等手段，对研究区含矿岩系（建造）特征、矿体及矿石矿物特征、成矿过程和找矿标志等方面进行了分析探讨。结果表明：鹰咀山锰矿为沉积变质型矿床，锰矿（化）体主要赋存在黄麦岭组云母石英片岩夹硅质（有时含少量泥质）大理岩建造的岩性段中；矿石类型主要为片岩型锰矿石和大理岩型锰矿石，矿石中锰矿物主要为硬锰矿、软锰矿、菱锰矿、锰白云石和黑锰矿等；初步认为锰矿的形成经历了沉积、变质改造和次生氧化富集的成矿阶段；含锰硅质大理岩和含锰云母石英片岩可作为该地区锰矿的典型找矿标志，该标志对鄂东北地区锰矿找矿具有重要意义。     

Mineralogy, geochemistry, and origin of hydrothermal manganese veins at Wadi Maliek, Southern Eastern Desert, Egypt

The present work deals with the geology, mineralogy, geochemistry, and origin of the metagabbroic-hosted manganese deposits at Wadi Maliek in the southern Eastern Desert of Egypt. The manganese veins are found in the shear zones and channel ways of the fault planes within the metagabbroic rocks pointing to those hydrothermal solutions carrying manganese and iron load penetrating along these fractures. These faults are striking N 80° E?CS 80° W with dipping 65°. These veins vary in thickness from 15?cm up to 125?cm wide; each vein may show difference in thickness from bottom to top. Microscopic examinations, X-ray diffraction, infrared spectral, differential thermal (DTA), thermogravimetric (TGA), and ESEM-EDAX analyses revealed that the manganese minerals consist mainly of pyrolusite, psilomelane, and ramsdellite. Goethite and hematite are the common iron minerals. Petrographically, the manganese deposits can be classified into three ore types based on the predominance of manganese and iron minerals: manganese, manganese?Ciron, and iron ore types. The geochemistry of Maliek deposits indicated that the total averages of some major oxides in manganese, manganese?Ciron, and iron ore types are respectively as follows: SiO₂ (15.64%, 11.52%, and 20.58%), MnO (39.9%, 17.81%, and 0.77%), FeO* (7.13%, 33.31%, and 37.08%), CaO (5.89%, 5.82%, and 5.32%), and Na₂O (1.04%, 1.61%, and 1.53%). With regard to trace elements, the Maliek manganese deposits are rich in Zn, Ba, Pb, Sr, and V. Based on the geological, mineralogical, and geochemical results, the studied manganese deposits are considered to be precipitated from hydrothermal solution.     

High-grade iron ore at Windarling, Yilgarn Craton: a product of syn-orogenic deformation, hypogene hydrothermal alteration and supergene modification in an Archean BIF-basalt lithostratigraphy

Banded iron formation (BIF)-hosted iron ore deposits in the Windarling Range are located in the lower greenstone succession of the Marda–Diemals greenstone belt, Southern Cross domain, Yilgarn Craton and constitute a total hematite–martite–goethite ore resource of minimum 52 Mt at 60 wt.% Fe (0.07 P). Banded iron formation is interlayered with high-Mg basalts at Windarling and precipitated during episodes of volcanic quiescence. Trace element content and the rare earth element (REE) ratios Y/Ho (42 to 45), Sm/Yb (1.5), together with positive La and Gd anomalies in ‘least-altered’ hematite–magnetite–metachert–BIF indicate the precipitation from Archean seawater that was fertilised by hydrothermal vent fluids with a basaltic HREE-Y signature. Hypogene iron ore in sub-greenschist facies metamorphosed BIF formed during three distinct stages: ore stage 1 was a syn- to post-metamorphic, syn-D₁, Fe–Ca–Mg–Ni–Co–P–REE metasomatism that produced local Ni–REE-rich Fe–dolomite–magnetite alteration in BIF. Hydrothermal alteration was induced by hot fluid flow controlled by brittle–ductile reactivation of BIF-basalt margins and crosscutting D₁ faults. The Ni–Co-rich content of dolomite and a shift in REE ratios in carbonate-altered BIF towards Archean mafic rock signature (Y/Ho to 31 to 40, Sm/Yb to 1 to 2 and Gd/Gd* to 1.2 to 1.4) suggest that high-Mg basalts in the Windarling Range were the primary source of introduced metals. During ore stage 2, a syn-deformational and likely acidic and oxidised fluid flow along BIF-basalt margins and within D₁ faults leached carbonate and precipitated lepidoblastic and anhedral/granoblastic hematite. High-grade magnetite–hematite ore is formed during this stage. Ore stage 3 hydrothermal specular hematite (spcH)–Fe–dolomite–quartz alteration was controlled by a late-orogenic, brittle, compressional/transpressional stage (D₄; the regional-scale shear-zone-related D₃ is not preserved in Windarling). This minor event remobilised iron oxides, carbonate and quartz to form veins and breccia but did not generate significant volumes of iron ore. Ore stage 4 involved Mesozoic(?) to recent supergene oxidation and hydration in a weathering environment reaching down to depths of ～100 to maximum 200 m below surface. Supergene ore formation involved goethite replacement of dolomite and quartz as well as martitisation. Important ‘ground preparation’ for supergene modification and upgrade were mainly the formation of steep D₁ to D₄ structures, steep BIF/basalt margins and particularly the syn-D₁ to syn-D₂ carbonate alteration of BIF that is most susceptible to supergene dissolution. The Windarling deposits are structurally controlled, supergene-modified hydrothermal iron ore systems that share comparable physical, chemical and ore-forming characteristics to other iron ore deposits in the Yilgarn Craton (e.g. Koolyanobbing, Beebyn in the Weld Range, Mt. Gibson). However, the remarkable variety in pre-, syn- and post-deformational ore textures (relative to D₁ and D₂) has not been described elsewhere in the Yilgarn and are similar to the ore deposits in high-strain zones, such as of Brazil (Quadrilátero Ferrífero or Iron Quadrangle) and Nigeria. The overall similarity of alteration stages, i.e. the sequence of hydrothermal carbonate introduction and hypogene leaching, with other greenstone belt-hosted iron ore deposits supports the interpretation that syn-orogenic BIF alteration and upgrade was crucial in the formation of hypogene–supergene iron ore deposits in the Yilgarn Craton and possibly in other Archean/Paleoproterozoic greenstone belt settings worldwide.     

Manganese ore deposits in Koira-Noamundi province of Iron Ore Group, north Orissa, India: In the light of geochemical signature

Several small Mn–Fe oxide and Mn-oxide ore bodies associated with Precambrian Iron Ore Group of rocks are located within Koira-Noamundi province of north Orissa, India. These deposits are classified into in situ (stratiform), remobilized (stratabound) and reworked categories based on their field disposition. Volcaniclastic/terrigenous shale in large geographic extension is associated with these ore bodies.The in situ ore bodies are characterised by cryptomelane-, romanechite- and hematite-dominating minerals, low Mn/Fe ratio (1.1) and relatively lower abundance of trace (1500–2500 ppm) constituents. In such type of deposits the stratigraphic conformity of oxides with the tuffaceous shale suggests precipitation of Mn and Fe at a time of decreased volcaniclastic/terrigenous contribution. The minor and trace elements were removed from solution by adsorption rather than by precipitation. Both Mn and Fe oxides when precipitated adsorb trace elements strongly but the partitioning of elements takes place during diagenesis. The inter-elemental relationship reveals that Cu, Co, Ni, Pb and Zn were adsorbed on precipitating hydrous Mn oxides and form manganates. Some of these elements probably get desorbed from Fe oxide because of their inability to substitute for Fe³⁺ in the lattice of its oxide. However, P, V, As and Mo were less partitioned and retained in Fe-oxide phase. Positive correlation between Al₂O₃ and SiO₂, MgO, Na₂O, TiO₂ and some traces like Li, Nb, Sc, Y, Zr, Th and U points to their contribution through volcaniclastic/terrigenous detritus of both mafic and acidic composition.The remobilized ore bodies are developed in a later stage through dissolution, remobilization and reprecipitation of Mn oxides in favorable structural weak planes under supergene environment. Increase in average Mn/Fe ratio (8) and trace content (5000–8500 ppm) by 5–2.5 orders of magnitude, respectively, or more above its abundance in adjoining/underlying protore is characteristic of these deposits. The newly formed Mn ores constituting lithiophorite, cryptomelane/romanechite and goethite get quantitatively enriched in traces like Cu, Co, Ni, Pb and Zn. Positive correlation between Mn, Li, Co and Zn is due to the formation of mineral of lithiophorite–chalcophanite group during redistribution and reconcentration of Mn oxide. P and V, which were present in Fe oxide, also get dissolved and reprecipitate with Fe oxyhydroxide in these ores. Some other elements like Y, Th and U show positive relation with Fe. This is probably due to leaching of these elements during chemical weathering of associated shale and getting re-adsorbed in Fe-oxyhydroxide phase.However, under oxidizing environment selective cations like Ba, K, etc. resorb from Mn-structure, resulting in the development of pyrolusite (Mn/Fe>20). In such transformation, trace metals from pyrolusitic structure expels out, resulting thereby in a considerable reduction in total trace value (<3000 ppm).The reworked ore bodies are allochthonous in nature and developed through a number of stages during terrain evolution and lateritisation. Secondary processes such as reworking of pre-existing crust; solution and remobilization; precipitation and cementation and transport, etc. are responsible for their development. Such deposits are usually very low in Mn/Fe ratio (3) and trace content (<2000 ppm).     

Gold Mineralization in Banded Iron Formation in the Amalia Greenstone Belt,South Africa: A Mineralogical and Sulfur Isotope Study

The Blue Dot gold deposit, located in the Archean Amalia greenstone belt of South Africa, is hosted in an oxide (± carbonate) facies banded iron formation (BIF). It consists of three stratabound orebodies; Goudplaats, Abelskop, and Bothmasrust. The orebodies are flanked by quartz‐chlorite‐ferroan dolomite‐albite schist in the hanging wall and mafic (volcanic) schists in the footwall. Alteration minerals associated with the main hydrothermal stage in the BIF are dominated by quartz, ankerite‐dolomite series, siderite, chlorite, muscovite, sericite, hematite, pyrite, and minor amounts of chalcopyrite and arsenopyrite. This study investigates the characteristics of gold mineralization in the Amalia BIF based on ore textures, mineral‐chemical data and sulfur isotope analysis. Gold mineralization of the Blue Dot deposit is associated with quartz‐carbonate veins that crosscut the BIF layering. In contrast to previous works, petrographic evidence suggests that the gold mineralization is not solely attributed to replacement reactions between ore fluid and the magnetite or hematite in the host BIF because coarse hydrothermal pyrite grains do not show mutual replacement textures of the oxide minerals. Rather, the parallel‐bedded and generally chert‐hosted pyrites are in sharp contact with re‐crystallized euhedral to subhedral magnetite ± hematite grains, and the nature of their coexistence suggests that pyrite (and gold) precipitation was contemporaneous with magnetite–hematite re‐crystallization. The Fe/(Fe+Mg) ratio of the dolomite–ankerite series and chlorite decreased from veins through mineralized BIF and non‐mineralized BIF, in contrast to most Archean BIF‐hosted gold deposits. This is interpreted to be due to the effect of a high sulfur activity and increase in fO₂ in a H₂S‐dominant fluid during progressive fluid‐rock interaction. High sulfur activity of the hydrothermal fluid fixed pyrite in the BIF by consuming Fe²⁺ released into the chert layers and leaving the co‐precipitating carbonates and chlorites with less available ferrous iron content. Alternatively, the occurrence of hematite in the alteration assemblage of the host BIF caused a structural limitation in the assignment of Fe³⁺ in chlorite which favored the incorporation of magnesium (rather than ferric iron) in chlorite under increasing fO₂ conditions, and is consistent with deposits hosted in hematite‐bearing rocks. The combined effects of reduction in sulfur contents due to sulfide precipitation and increasing fO₂ during progressive fluid‐rock interactions are likely to be the principal factors to have caused gold deposition. Arsenopyrite–pyrite geothermometry indicated a temperature range of 300–350°C for the associated gold mineralization. The estimated δ³⁴S_ΣS (= +1.8 to +2.5‰) and low base metal contents of the sulfide ore mineralogy are consistent with sulfides that have been sourced from magma or derived by the dissolution of magmatic sulfides from volcanic rocks during fluid migration.     

Physicochemical formation conditions of banded iron formations and high-grade iron ores in the region of the Kursk Magnetic Anomaly: Evidence from isotopic data

The oxygen and carbon isotopic compositions of minerals from banded iron formations (BIFs) and high-grade ore in the region of the Kursk Magnetic Anomaly (KMA) were determined in order to estimate the temperature of regional metamorphism and the nature of rock-and ore-forming solutions. Magnetite and hematite of primary sedimentary or diagenetic origin have δ¹⁸O within the range from +2 to 6‰. During metamorphism, primary iron oxides, silicates, and carbonates were involved in thermal dissociation and other reactions to form magnetite with δ¹⁸O = +6 to +11‰. As follows from a low δ¹⁸O_av = ?3.5‰ of mushketovite (magnetite pseudomorphs after hematite) in high-grade ore, this mineral was formed as a product of hematite reduction by organic matter. The comparison of δ¹⁸O of iron oxides, siderite, and quartz from BIFs formed at different stages of the evolution of the Kursk protogeosyncline revealed specific sedimentation (diagenesis) conditions and metamorphism of the BIFs belonging to the Kursk and Oskol groups. BIF of the Oskol Group is distinguished by a high δ¹⁸O of magnetite compared to other Proterozoic BIFs. Martite ore differs from host BIF by a low δ¹⁸O = ?0.2 to ?5.9‰. This implies that oxygen from infiltration water was incorporated into the magnetite lattice during the martite formation. Surface water penetrated to a significant depth through tectonic faults and fractures.     

Pyrolusite surface transformations measured in real-time during the reactive transport of Co(II)EDTA2−

Oxidation of Co(II)EDTA²⁻ to Co(III)EDTA⁻ by manganese and iron hydrous oxide minerals enhances the transport of ⁶⁰Co in subsurface environments. Until now, reduction of the oxidant MnO₂ has not been identified in hydrodynamic systems, leaving the fate and transport mechanisms involving ⁶⁰Co in natural environments unresolved. We investigated the transport of Co(II)EDTA²⁻ through packed beds of β-MnO₂ and identified the reaction mechanism using a novel hydrodynamic flow cell coupled with X-ray absorption near edge structure (XANES) spectroscopy. Using this technique we are able to determine both solution and solid-phase species of cobalt and manganese in real-time. Co(II)EDTA²⁻ is produced while Mn(IV) is reduced to Mn(III) which forms an α-Mn₂O₃layer on pyrolusite. This layer passivates the surface after an initial reaction period and ultimately limits the production of Co(III)EDTA⁻. As a consequence, the enhanced transport of ⁶⁰Co by oxidative processes may be diminished by continual exposure to pyrolusite—an advantage from an environmental quality perspective. It has also been clarified that Mn(III) is formed rather than Mn(II) resulting in formation of a stable trivalent manganese solid (α-Mn₂O₃).     

Manganocummingtonite from the mesoproterozoic,Sausar fold belt,central India

Manganocummingtonite occurs with spessartine, quartz and pyrolusite in the Chikmara area, Sausar fold belt, central India. Its composition is [Ca_0.3–0.35(Mg_3.3–3.5Mn_1.6–1.8Fe²⁺ _1.4–1.5)(Si_{7.931–7.997}Al^iv _{0.003–0.069})O₂₂(OH_1.5–2.0F_0.0–0.5)] being fairly rich in Ca, which is indicative of metamorphic temperature in the amphibolite facies. The garnet contains 77.5% spessartine, 13% almandine and minor andradite, grossular and pyrope components. Unusually, there is no carbonate, pyroxene, pyroxmangite, rhodonite, magnetite or hematite. The available Al in the rock stabilized garnet and this mineral incorporated minor Fe³⁺ present in the rock as andradite component. The manganocummingtonite-garnet pairs developed at ～600°C during amphibolite facies metamorphism in low $X_{CO_2 } $ system, stabilized with $X_{Mn/(Mn + Fe^{2 + } + Mg)} $ = 0.25 to 0.28 in the amphibole and 0.85 in the garnet and formed under unusually low fO ₂ conditions for the Sausar region, near channelized fluids which deposited quartz may have controlled the fO ₂ .     

Genesis of superimposed hypogene and supergene Fe orebodies in BIF at the Madoonga deposit, Yilgarn Craton, Western Australia

The Madoonga iron ore body hosted by banded iron formation (BIF) in the Weld Range greenstone belt of Western Australia is a blend of four genetically and compositionally distinct types of high-grade (>55 wt% Fe) iron ore that includes: (1) hypogene magnetite–talc veins, (2) hypogene specular hematite–quartz veins, (3) supergene goethite–hematite, and (4) supergene-modified, goethite–hematite-rich detrital ores. The spatial coincidence of these different ore types is a major factor controlling the overall size of the Madoonga ore body, but results in a compositionally heterogeneous ore deposit. Hypogene magnetite–talc veins that are up to 3 m thick and 50 m long formed within mylonite and shear zones located along the limbs of isoclinal, recumbent F₁ folds. Relative to least-altered BIF, the magnetite–talc veins are enriched in Fe₂O_3(total), P₂O₅, MgO, Sc, Ga, Al₂O₃, Cl, and Zr; and depleted in SiO₂ and MnO₂. Mafic igneous countryrocks located within 10 m of the northern contact of the mineralised BIF display the replacement of primary igneous amphibole and plagioclase, and metamorphic chlorite by hypogene ferroan chlorite, talc, and magnetite. Later-forming, hypogene specular hematite–quartz veins and their associated alteration halos partly replace magnetite–talc veins in BIF and formed during, to shortly after, the F₂-folding and tilting of the Weld Range tectono-stratigraphy. Supergene goethite–hematite ore zones that are up to 150 m wide, 400 m long, and extend to depths of 300 m replace least-altered BIF and existing hypogene alteration zones. The supergene ore zones formed as a result of the circulation of surface oxidised fluids through late NNW- to NNE-trending, subvertical brittle faults. Flat-lying, supergene goethite–hematite-altered, detrital sediments are concentrated in a paleo-topographic depression along the southern side of the main ENE-trending ridge at Madoonga. Iron ore deposits of the Weld Range greenstone belt record remarkably similar deformation histories, overprinting hypogene alteration events, and high-grade Fe ore types to other Fe ore deposits in the wider Yilgarn Craton (e.g. Koolyanobbing and Windarling deposits) despite these Fe camps being presently located more than 400 km apart and in different tectono-stratigraphic domains. Rather than the existence of a synchronous, Yilgarn-wide, Fe mineralisation event affecting BIF throughout the Yilgarn, it is more likely that these geographically isolated Fe ore districts experienced similar tectonic histories, whereby hypogene fluids were sourced from commonly available fluid reservoirs (e.g. metamorphic, magmatic, or both) and channelled along evolving structures during progressive deformation, resulting in several generations of Fe ore.     

The uptake of cobalt into ferromanganese nodules,soils, and synthetic manganese (IV) oxides

Strong enrichments of cobalt occur in marine manganese nodules, soils, wads, and natural and synthetic minerals such as hollandite, cryptomelane, psilomelane, lithiophorite, birnessite, and δ-MnO₂. Previously, it was suggested that Co³⁺ ions in these minerals replace either Mn³⁺ or substitute for Fe³⁺ in incipient goethite epitaxially intergrown with δ-MnO₂. Neither of these interpretations is now considered to be satisfactory on account of the large discrepancy of ionic radius between octahedrally coordinated low-spin Co³⁺ and high-spin Mn³⁺ or Fe³⁺ in oxide structures. The close agreement between the ionic radii of Co³⁺ and Mn⁴⁺ suggests that some cobalt substitutes for Mn⁴⁺ ions in edge-shared [MnO₆] octahedra in many manganese(IV) oxide mineral structures. It is proposed that hydrated cations, including Co²⁺ ions, are initially adsorbed on to the surfaces of certain Mn(IV) oxides in the vicinity of essential vacancies found in the chains or sheets of edge-shared [MnO₆] octahedra. Subsequently, fixation of cobalt takes place as a result of oxidation of adsorbed Co²⁺ ions by Mn⁴⁺ and replacement of the displaced manganese by low-spin Co³⁺ ions in the [MnO₆] octahedra or vacancies.     

西昆仑玛尔坎苏石炭纪大型锰矿带构造背景与成矿条件

西昆仑北段玛尔坎苏地区探明的大型碳酸锰成矿带,是我国近年最重要的找矿成果之一。该锰矿带构造上属北昆仑晚古生代弧后伸展盆地,其构造动力学背景为古特提斯洋向北俯冲于塔里木地块之下形成的弧盆体系。锰矿体主要发育于晚石炭世喀拉阿特河组含炭泥质灰岩夹薄层灰岩中。矿石中主要金属矿物为菱锰矿（75%~95%）,次为软锰矿、硫锰矿及少量黄铁矿等。含锰岩系岩性和岩相学研究表明,玛尔坎苏锰矿带属典型的海相沉积锰矿床,其矿床成因可能与晚古生代半局限盆地沉积和海底热液活动有关。海底热液活动可能为成矿提供了丰富的物质来源。含锰岩系元素和同位素地球化学特征表明,玛尔坎苏锰矿沉淀时的水体环境为常氧条件,而矿层下盘（部分）岩系的岩性及地球化学特征反映其沉积时的水体环境为低氧—贫氧条件。玛尔坎苏锰矿带锰矿石具有负的δ¹³C值（-23.3‰~-10.0‰）,推测有机质导致的还原作用是该锰矿由原生氧化锰在成岩期转化为菱锰矿和形成富锰矿的重要机制。     

The sorption of silver by poorly crystallized manganese oxides

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO₂. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnO_x at pH 7) while the γ-MnO₂ showed the least (0.3 moles silver/ mole MnO_x at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values.Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium.     

Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium Shewanella putrefaciens

The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO₂], bixbyite [Mn₂O₃] and K⁺-birnessite [K₄Mn₁₄O₂₇ · 8H₂O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO₂[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH]₃) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO₂(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.     

Molecular-scale mechanisms of distribution and isotopic fractionation of molybdenum between seawater and ferromanganese oxides

The distribution of Mo between seawater and marine ferromanganese oxides has great impacts on concentration and isotopic composition of Mo in modern oxic seawater. To reveal the adsorption chemistry of Mo to ferromanganese oxides, we performed (i) detailed structural analyses of Mo surface complexes on δ-MnO₂, ferrihydrite, and hydrogenetic ferromanganese oxides by L₃- and K-edge XAFS, and (ii) adsorption experiments of Mo to δ-MnO₂ and ferrihydrite over a wide range of pHs, ionic strengths, and Mo concentrations. XAFS analyses revealed that Mo forms distorted octahedral (Oh) inner-sphere complexes on δ-MnO₂ whereas it forms a tetrahedral (Td) outer-sphere complex on ferrihydrite. In the hydrogenetic ferromanganese oxides, the dominant host phase of Mo was revealed to be δ-MnO₂. These structural information are consistent with the macroscopic behaviors of Mo in adsorption experiments, and Mo concentration in modern oxic seawater can be explained by the equilibrium adsorption reaction on δ-MnO₂. In addition, the large isotopic fractionation of Mo between seawater and ferromanganese oxides detected in previous studies can be explained by the structural difference between and adsorbed species on the δ-MnO₂ phase in ferromanganese oxides. In contrast, smaller fractionation of Mo isotopes on ferrihydrite is due to little change in the Mo local structures during its adsorption to ferrihydrite.The structures of Mo species adsorbed on crystalline Fe (oxyhydr)oxides, goethite, and hematite were also investigated at pH 8 and I = 0.70 M (NaNO₃). Our XAFS analyses revealed that Mo forms inner-sphere complexes on both minerals: Td edge-sharing (46%) and Oh double corner-sharing (54%) for goethite, and Td double corner-sharing (14%) and Oh edge-sharing (86%) for hematite. These structural information, combined with those for amorphous ferrihydrite and δ-MnO₂, show the excellent correlation with the magnitude of adsorptive isotopic fractionation of Mo reported in previous studies: the proportion of Oh species or their magnitude of distortion in Mo surface complexes become larger in the order of ferrihydrite < goethite < hematite < δ-MnO₂, a trend identical to the magnitude of isotopic fractionation.Based on the comparison with previous reports for Mo surface species on various oxides, the chemical factors that affect Mo surface complex structures were also discussed. The hydrolysis constant of cation in oxides, log K_OH (or the acidity of the oxide surfaces, PZC) is well correlated with the mode of attachment (inner- or outer-sphere) of Mo surface complexes. Furthermore, the symmetric change in Mo species from Td to Oh is suggested to be driven by the formation of inner-sphere complexes on specific sites of the oxide surfaces.