MINERALOGICAL AND TEXTURAL EVOLUTION OF THE ECONOMIC MANGANESE MINERALIZATION IN WESTERN RHODOPE MASSIF, N GREECE

The western Rhodope massif contains a significant number of 'battery grade' Mn-oxide deposits which are best developed in the area near Kato Nevrokopi, Drama district, N. Greece. Economic Mn-oxide ore concentrations are confined to fault zones and related karsts in marbles. The mineralisation has formed by weathering of hydrothermal veins that were genetically related to Oligocene magmatism. At Kato Nevrokopi, progressive and continuous weathering of primary, hydrothermal veins of rhodochrosite, mixed sulphide, quartz and 'black calcite' (calcite and todorokite) has resulted in the formation of the assemblage MnO-gel-(amorphous Mn-oxide)-todorokite-azurite-goethite-cerussite in the veins and the assemblage MnO-gel-nsutite-chalcophanite-birnessite-cryptomelane-pyrolusite and malachite and amorphous Fe-oxides in karstic cavities. The f(S)2 and f(O)2 of the hydrothermal fluids increased with time. The breakdown of the hypogene Mn-carbonate was aided by the production of an acidic fluid due to the oxidation of sulphides. Precipitation of the supergene ores was caused by neutralisation of the fluids due to reaction with the host marble and to mixing of relatively reduced fluids with oxygenated surface water in a fluctuation water table regime. Zinc was also mobile during weathering and became concentrated in the intermediate Mn-oxides, effectively stabilising their structures. The mineral paragenesis records the progressive oxidation of the ore and the appearance of less hydrated Mn-oxides, low in alkalis and alkaline earths

Studi Xrd Mangan Oksida Birnessite yang Dipreparasi melalui Metode Sol-gel dan Keramik

Birnessite is a naturally occurring layered manganese oxide found as a manganese nodules in sea floor or soil deposit. In this study, birnessite was synthesized using two types of methods, solid state ceramic approach and sol-gel reaction both KMnO4 and maltose were used as reactants in these two methods. The products were then characterized using XRD for determination of phases, crystallinity and purity. The results showed the both techniques lead to the formation of birnessite with different crystallinity and purity. The ceramic method produced more crystalline and pure birnessite than that of sol-gel. The typical reaction parameters for the synthesis birnessite by the ceramic method were 3:1 mole ratio (KMnO4over maltose) calcination at 700o C for 7 hours with the 93,7% purity of birnessite. However, by the sol-gel method birnessite produced only 31,8% with the following condition 4:1 mole ratio (KMnO4 over maltose) and calcination temperature of 450o C for 2 hours

A New Method of Synthesizing Black Birnessite Nanoparticles: From Brown to Black Birnessite with Nanostructures

A new method for preparing black birnessite nanoparticles is introduced. The initial synthesis process resembles the classical McKenzie method of preparing brown birnessite except for slower cooling and closing the system from the ambient air. Subsequent process, including wet-aging at 7◦C for 48 hours, overnight freezing, and lyophilization, is shown to convert the brown birnessite into black birnessite with complex nanomorphology with folded sheets and spirals. Characterization of the product is performed by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA), and N2 adsorption (BET) techniques. Wet-aging and lyophilization times are shown to affect the architecture of the product. XRD patterns show a single phase corresponding to a semicrystalline birnessite-based manganese oxide. TEM studies suggest its fibrous and petal-like structures. The HRTEM images at 5 and 10 nm length scales reveal the fibrils in folding sheets and also show filamentary breaks. The BET surface area of this nanomaterial was found to be 10.6m2/g. The TGA measurement demonstrated that it possessed an excellent thermal stability up to 400◦C. Layerstructured black birnessite nanomaterial containing sheets, spirals, and filamentary breaks can be produced at low temperature (−49◦C) from brown birnessite without the use of cross-linking reagents

Arsenic(III) remediation from contaminated water by oxidation and Fe/Al co-precipitation

Battery grade γ-MnO2 powder was investigated as an oxidant and an adsorbent in combination with Fe/Al coagulants for removal of arsenic from contaminated water. Simultaneous oxidation of As(III) and removal by coprecipitation/adsorption (one step process) was compared with pre-oxidation and subsequent removal by coprecipitation/adsorption (two step process). The rate of As(III) oxidation with MnO2 is completed in two stages: rapid initially followed by a first order reaction. As(III) is oxidised to As(V) by the MnO2 with a release of approximately 1:1 molar Mn(II) into the solution. No significant pH effect on oxidation of As(III) was observed in the pH range 4 - 6. The rate showed a decreasing trend above pH 6. The removal of As(V) by adsorption on the MnO2 decreased significantly with increasing pH from 4 to 8. The adsorption capacity of the γ-MnO2 with particle size 90% passing 10 µm was determined to be 1.5 mg/g at pH 7. MnO2 was found to be more effective as an oxidant for As(III) in the two step process than in the one step process

Manganese Oxide Thin Films Prepared by Nonaqueous Sol-Gel Processing: Preferential Formation of Birnessite

High quality manganese oxide thin films with smooth surfaces and even thicknesses have been prepared with a nonaqueous sol–gel process involving reduction of tetraethylammonium permanganate in methanol. Spin-coated films have been cast onto soft glass, quartz, and Ni foil substrates, with two coats being applied for optimum crystallization. The addition of alkali metal cations as dopants results in exclusive formation of the layered birnessite phase. By contrast, analogous reactions in bulk sol–gel reactions yield birnessite, tunneled, and spinel phases depending on the dopant cation. XRD patterns confirm the formation of well-crystallized birnessite. SEM images of Li-, Na-, and K–birnessite reveal extremely smooth films having uniform thickness of less than 0.5 μm. Thin films of Rb– and Cs–birnessite have more fractured and uneven surfaces as a result of some precipitation during the sol–gel transformation. All films consist of densely packed particles of about 0.1 μm. When tetrabutylammonium permanganate is used instead of tetraethylammonium permanganate, the sol–gel reaction yields amorphous manganese oxide as the result of diluted Mn sites in the xerogel film. Bilayer films have been prepared by casting an overcoat of K–birnessite onto an Na–birnessite film. However, Auger depth profiling indicates considerable mixing between the adjacent layers

Synthesis of a new hollandite-type manganese oxide with framework and interstitial Cr(III)

Hollandite with Cr(III) in both tunnel and framework sites has been prepared hydrothermally from layered manganese oxide precursors

Structure of the Synthetic K-rich Phyllomanganate Birnessite Obtained by High-Temperature Decomposition of KMnO4. Substructures of K-rich Birnessite from 1000°C Experiment

International audienceThe structure of a synthetic potassium-rich birnessite prepared from the thermal decomposition of KMnO4 at 1000°C in air has been refined by Rietveld analysis of the powder X-ray diffraction (XRD) data, and the structure model shown to be consistent with extended X-ray absorption fine structure data. K-rich birnessite structure is a two-layer orthorhombic polytype (2O) with unit-cell parameters a = 5.1554(3) Ä, b = 2.8460(1) Ä, c = 14.088(1) Ä, α = β = γ = 90°, a/b = √3.281, and was refined in the Ccmm space group. The structure is characterized by the regular alternation of octahedral layers rotated with respect to each other by 180°. Octahedral layers are essentially devoid of vacant sites, the presence of 0.25 Mn 3+ layer cations within these layers being the main source of their deficit of charge, which is compensated for by interlayer K + cations. Mn3+ octahedra, which are distorted by the Jahn-Teller effect, are systematically elongated along the a axis (cooperative Jahn-Teller effect) to minimize steric strains, thus yielding an orthogonal layer symmetry. In addition, Mn 3+ octahedra are segregated in Mn3+-rich rows parallel to the b axis that alternate with two Mn 4+ rows according to the sequence ...-Mn3+-Mn4+-Mn4+-Mn3+-... along the a direction, thus leading to a A = 3a super-periodicity. At 350°C, the structure partially collapses due to the departure of interlayer H2O molecules and undergoes a reversible 2O-to-2H phase transition. This transition results from the relaxation of the cooperative Jahn-Teller effect, that is from the random orientation of elongated Mn 3+ octahedra

Analisis Sifat-sifat Permukaan Birnessiteyang Dipreparasi dari Dua Agen Pereduksi Berbeda

The layered manganese oxides having birnessite structure have been successfully synthesized using the two different types of reducing agents by solid-state ceramic method. The reducing agent used in this study was oxalic acid and glucose. Birnessite synthesized has been characterized using XRD, SEM and methylene blue adsorption. The XRD results indicated that the two types of reducing agents produced mainly birnessite phases with different crystallinity .Birnessites synthesized from two reducing agents have different surface properties as indicated from data of SEM and methylene blue adsorption