Fe-Mn Ores Research Articles

Mineralogical and radiological studies on some Paleozoic yellow ochre deposits in Southwestern Sinai, Egypt

Yellow ochre is the basic material used in the manufacture of yellow oxide (a commercial product). Yellow ochre samples were taken from three different formations in southwestern Sinai: Abu Hamata, Um Bogma, and Abu Zarab. Yellow ochre occasionally exists in Abu Hamata Formation particularly in El Ferah area, associated with Fe–Mn ore in Wadi El Sahu (Um Bogma Formation) and in Himayer area (Abu Zarab Formation). The XRD analysis of the raw material reveals that they are mainly composed of goethite, which is associated with quartz and kaolinite in El Ferah area, hematite, kaolinite and quartz in Himayer area, and kaolinite, gypsum and quartz in Wadi El Sahu. The commercial product is mainly composed of goethite, quartz, and calcite. The heavy mineral investigation shows that some yellow ochre samples contain zircon and rare earth sulfate which may be responsible for the radioactivity of ochre due to their thorium and uranium content. The average values of specific radio-activities of most radionuclides in the samples of Himayer area I and II, and El Sahu I are higher than the respective world averages, while their activities are lower in El Ferah and El Sahu II. Th/U and Ra/U ratios exhibit vigorous changes in physico-chemical conditions during uranium leaching and deposition. Most of the radiological parameters in the ferruginous sediment and commercial product samples from El Ferah, El Sahu II, and Himayer II are lower than the recommended international values but higher than those from Himayer I and El Sahu I samples. The plotted hierarchical cluster analysis (HCA) exhibits that the main contributors for the hazards of these sediments and their commercial product are 238U, 232Th and 226Ra in Himayer I &II, commercial products, and El Ferah area, 232Th and 226Ra in El Sahu II , 232Th, 40K and 226Ra in El Sahu I.

New insight into genesis of the Maojun laterite Fe–Mn deposit in the Lanshan area, Hunan Province, South China: Evidence from detailed mineralogical and geochemical studies

Laterite Fe–Mn deposits are widespread in South China, with the majority of Fe–Mn ore being present in residual quaternary clay beds. However, detailed geological data on the lateritization of low-iron-content carbonate rocks are rare. In this study, we present new results on the mineralogy and geochemistry, as well as a genetic model, of the Maojun laterite Fe–Mn deposit in the Lanshan area, Hunan Province, South China. The profile sequence of laterite consists of an eroded bedrock horizon at its base, an intermediate black–brown clay layer containing earthy Fe–Mn ore, and a reddish-brown clay layer with nodular ferromanganese ore in contact with reddish-brown or yellowish-brown clay on top. Field evidence and chemical analysis indicated that during lateritization, the Mn-Fe-containing carbonate rocks of the Huanggongtang (D2h) and Shetianqiao formations (D3s) saw a more significant removal of mobile elements (Mg, Ca, and Na) whilst insoluble elements (Fe, Mn, Si, Al, Pb, and Zn) exhibited persistent enrichment in situ. Discriminative diagrams of Fe–Mn mineralization, as well as the assemblage-related enrichment of Y, U, Mo, Pb, and Zn and depletion of high-field-strength elements Zr, Nb, and Th, imply that subsequent hydrothermal circulation overprinted on the previously formed hydrogenous deposit. Mineralogical studies conducted using XRD, EPMA, HR-TEM, and TIMA indicated the predominance of iron and manganese oxides; hematite, goethite, limonite, and hollandite were identified as major oxide phases and cryptomelane, pyrolusite, and coronadite were present in minute quantities. Similar minerals constitute the upper ferromanganese nodule horizons, although they possess distinct textures and concentrations. The mineralogy, geochemical associations, and Ti mass balance show a continuous vertical evolution from top to bottom in the lateritic profile. Ferromanganese concretions from the drenching zone with poorly crystallized Al–goethite, Al–hematite, limonite, Fe–kaolinite, Fe–Mn oxides and hollandite predominate in shallow parts, and microcrystalline hematite, goethite and hollandite were found in deeper layers. Mn2+ can be rapidly oxidized and precipitated on the surface of hematite and limonite as high-valence-state (Mn4+) manganese oxides and binds strongly with mobile elements (Ba, K, Pb, Zn, Ca, and Ni). Petrographical, mineralogical, and geochemical studies show that three stages comprised the formation of the Maojun laterite Fe–Mn deposit.

Magmatic–Hydrothermal Origin of Fe-Mn Deposits in the Lesser Khingan Range (Russian Far East): Petrographic, Mineralogical and Geochemical Evidence

Iron and iron–manganese deposits form three closely spaced clusters within the Lesser Khingan Range of the Russian Far East. Fe-Mn mineralization is hosted in Vendian–Cambrian carbonates and composed of magnetite, hematite, braunite, haussmanite, rhodochrosite and pyrolusite. The iron–manganese ores are closely associated with explosive intermediate–felsic breccias, magnetite-rich lavas, dolerites and mineralized lithocrystalloclastic tuffs. Magmatic rocks display both concordant and discordant relationships with Fe-Mn mineralization and contain abundant xenoliths of host carbonates. Both magmatic rocks (with the exception of Nb-enriched dolerites) and Fe-Mn ores are characterized by variable enrichments in large-ion lithophile and light rare earth elements and strong depletions in high-field strength elements compatible with the broad subduction setting for explosive volcanism and associated hydrothermal Fe-Mn ore mineralization. Nd-Sr isotope systematics suggest contamination by both ancient and juvenile continental crust and the involvement of recycled pelagic sediment in the formation of Fe-Mn deposits in the Lesser Khingan Range of the Russian Far East.

Electrochemical reactions driving Mn-enrichment in Fe[sbnd]Mn supergene ores: A mineralogical perspective

Iron and manganese oxides embody a geochemical system of great environmental, biological, and economical relevance. Chemical equilibria and the stability of FeMn phases under surface or near-surface conditions can influence the fate of contaminants in the environment, impact biological metabolic processes, or Fe and Mn phase distribution in weathered ores. In the present work, we focus on the textural, mineralogical, and chemical study of FeMn ores from the weathered zone of a vein-hosted deposit outcropping in the Iberian Pyrite Belt, SW Portugal, by means of micro-Raman spectroscopy coupled with electron microprobe microanalysis. The aims of our investigation are i) identifying the several Fe and Mn phases occurring in differently enriched ores samples, ii) relating their chemical composition with possible mineralization mechanisms, and iii) defining the mineral paragenetic pathway related to the observed textural features. Our approach enabled both the identification of the coexisting Fe and Mn phases, and unravelling paragenetic pathways leading to supergene enrichment mineralizations. Collected evidence demonstrates that changes in Eh/pH can lead to goethite dissolution under reductive conditions, promoting the release of Fe2+ into solution, whose electrochemical interaction with Mn4+ results in the formation of several types of Mn oxides, and secondary goethite. Our data shows a clear relationship between the type of Mn oxide crystallized and the ratio of aqueous Mn3+/Mn4+, alongside other prevalent cations, incorporated into tunnel or interlayer structural sites, which may be also desorbed/solubilized from primary goethite.

Investigating the capability of Sentinel-2 and Worldview-3 VNIR satellite data to detect mineralized zones at an igneous intrusion in the Koutala islet (Lavreotiki, Greece) using laboratory mineralogical analysis, reflectance spectroscopy and spectral indices

During the last decades, the rapid progress of remote sensing data processing for their utilization in detecting locations of possible sites linked to hydrothermal alteration and ores has gained increasing attention due to significant time and cost savings. In this study, we present the findings of a joint remote sensing and laboratory examination of a mineralization zone induced by a granitoid intrusion onshore the islet of “Koutala”, in Lavreotiki, central Greece. Our objective is to investigate the potential of Sentinel-2 and WorldView-3 VNIR satellite data to detect and map oxidized ore zones and alteration minerals that are detected from laboratory analysis of samples and could be linked to Fe-Mn mineralization. Two approaches are followed, namely reflectance spectroscopy and spectral indices. In reflectance spectroscopy, the spectral signatures of all minerals detected in the study area are retrieved from spectral libraries. The signatures are resampled to Sentinel-2 and to WorldView-3 VNIR spectral bands. Continuum-removal is then applied and the diagnostic absorption features of each mineral are detected for each spectral band configuration. The dataset with the best spectral configuration for mineral detection is then used for the production of mineral maps using the corresponding satellite image. The second approach involves the calculation of spectral indices, namely ferric, ferrous iron and hydroxyl-bearing alteration, on reflectance spectra. The ferric iron index is applied to both satellite datasets while the two other indices require the use of SWIR bands and therefore, they can be only calculated on Sentinel-2 data. All results show that laboratory and satellite data analyses results are consistent and complementary. WorldView-3 VNIR data seem to be sensitive only to the ferric and manganese phase. Sentinel-2 data seem to be capable to detect and map all alteration minerals that are potentially linked to Fe-Mn ore, including both ferric and ferrous phases. The mineral absorption and spectral indices maps show that in the investigated area, there is significant mineralization related to the granitoid intrusion. Hydrothermal alteration is observed on the entire surface of the islet but it seems to be stronger at the eastern part of the islet where the granitoid/schist contact is located. It is the first time that (i) minerals linked to a potential Fe-Mn ore are detected on the islet and (b) the corresponding alteration mineral maps are produced from satellite data, revealing their spatial distribution and providing indirect estimations of the degree of their presence.

Piccoliite, NaCaMn3+2(AsO4)2O(OH), a new arsenate from the manganese deposits of Montaldo di Mondovì and Valletta, Piedmont, Italy

AbstractPiccoliite, ideally NaCaMn3+2(AsO4)2O(OH), is a new mineral discovered in the Fe–Mn ore hosted in metaquartzites of the Montaldo di Mondovì mine, Corsaglia Valley, Cuneo Province, Piedmont, Italy. It occurs as small and rare black crystals and aggregates hosted by a matrix of quartz, associated with calcite and berzeliite/manganberzeliite. It has been also found in the Valletta mine near Canosio, Maira Valley, Cuneo Province, Piedmont, Italy, where it occurs embedded in quartz associated with grandaite, hematite, tilasite/adelite and rarely thorianite. The mineral is opaque (thin splinters may be very dark red), with brown streak and has a resinous to vitreous lustre. It is brittle with irregular fracture. No cleavage has been observed. The measured Mohs hardness is ~5–5.5. Piccoliite is non fluorescent. The calculated density is 4.08 g⋅cm–3. Chemical spot analyses by electron microprobe analysis using wavelength dispersive spectroscopy resulted in the empirical formula (based on 10 anions per formula unit) (Na0.64Ca0.35)Σ0.99(Ca0.75Na0.24)Σ0.99(Mn3+1.08Fe3+0.59Mg0.20Ca0.10)Σ1.97(As2.03V0.03Si0.01)Σ2.07O9(OH) and (Na0.53Ca0.47)Σ1.00(Ca0.76Na0.23Sr0.01)Σ1.00(Mn3+0.63Fe3+0.49Mg0.48Mn4+0.34Ca0.06)Σ2.00(As1.97P0.01Si0.01)Σ1.99O9(OH) for the Montaldo di Mondovì and Valletta samples, respectively. The mineral is orthorhombic, Pbcm, with single-crystal unit-cell parameters a = 8.8761(9), b = 7.5190(8), c = 11.689(1) Å and V = 780.1(1) Å3 (Montaldo di Mondovì sample) and a = 8.8889(2), b = 7.5269(1), c = 11.6795(2) Å, V = 781.43(2) Å3 (Valletta sample) with Z = 4. The seven strongest powder X-ray diffraction lines for the sample from Montaldo di Mondovì are [d Å (Irel; hkl)]: 4.85 (57; 102), 3.470 (59; 120, 113), 3.167 (100; 022), 2.742 (30; 310, 213), 2.683 (53; 311, 023), 2.580 (50; 222, 114) and 2.325 (19; 320, 214, 223). The crystal structure (R1 = 0.0250 for 1554 unique reflections for the Montaldo di Mondovì sample and 0.0260 for 3242 unique reflections for the Valletta sample) has MnO5(OH) octahedra forming edge-shared dimers; these dimers are connected through corner-sharing, forming two-up-two-down [[6]M2([4]TO4)4φ2] chains [M = Mn; T = As; φ = O(OH)] running along [001]. These chains are bonded in the a and b directions by sharing corners with AsO4 tetrahedra, giving rise to a framework of tetrahedra and octahedra hosting seven-coordinated Ca2+ and Na+ cations. The crystal structure of piccoliite is closely related to that of pilawite-(Y) as well as to carminite-group minerals that also show the same type of chains but with different linkage. The mineral is named after the mineral collectors Gian Paolo Piccoli and Gian Carlo Piccoli (father and son) (1926–1996 and b. 1953, respectively), the latter having discovered the type material at the Montaldo di Mondovì mine.

Comparative Study of Formation Conditions of Fe-Mn Ore Microbialites Based on Mineral Assemblages: A Critical Self-Overview

The role of biogenicity in the mineral world is larger than many might assume. Biological processes and physical and chemical processes interact both at the Earth’s surface and far underground, leading to the formation of banded iron and manganese deposits, among others. Microbial mats can form giant sedimentary ore deposits, which include enrichment of further elements. This article reviews the ways in which microbially-mediated processes contribute to mineralization, the importance of mineralized microbial textural features, and the methods that must be used to obtain high-resolution datasets. If the chosen methodology and/or the size dimension of investigation is not appropriate, then it is not possible to recognize that a system is microbially mediated, and the conclusion will be incomplete. We call attention to variable authigenic mineralization as the result of complex mineralization of cells and extracellular polymeric substances in the starving basins, which form giant ore deposits together with ore-forming minerals. Microbial mats and other biosignatures can serve as indicators of environmental reconstruction in ore formations. We suggest tests and analyses that will allow the potential role of biomineralization to be properly investigated for a more comprehensive view of formation processes and their implications.

Rare earth elements and origin of Fe[sbnd]Mn ores from the Lower Carboniferous Um Bogma Formation, Southwest Sinai, Egypt: A mixed source of metals and multiple formation processes

The economic FeMn ores of the Lower Carboniferous Um Bogma Formation, Southwest Sinai are an important mineral resource, and are also of interest because of their significant enrichment in Cu and U compared to other Phanerozoic Mn deposits. However, their origin remains controversial. Genetic theories range from sedimentary, to hydrothermal, to karst and to laterization origins. This study integrates geological, sedimentological, mineralogical, and geochemical data, particularly rare earth elements, to elucidate the origin of these deposits. Field relations showed the occurrence of FeMn deposits as lenses of Mn-rich material surrounded by Fe-rich clastic deposits, which then are overlain by dolostones, which, in the subsurface, are known to also contain MnFe lenses. The occurrence of the largest of these deposits at a major transgressive surface is consistent with syndepositional Mn mineralization, but not of ironstones. Geochemical proxies, based on modern hydrothermal, diagenetic and hydrogeneous Mn deposits, are mixed: some suggest a hydrogenous and some a hydrothermal source of Fe and Mn. The sweater (hydrogenous) source of Mn and Fe is indicated by the plotting of these ores in the hydrogenous field of the SiAl discrimination plot, by high ΣREE (42–327 ppm), low La/Ce ratios (0.261.5), relatively high Y/Ho ratios for Mn but not for Fe (averages of 35 and 28), and positive YSN anomalies (1–1.8). The ores plot in the sweater fields of the (La/Sm)SN-(La/Yb)SN and (Sm/Yb)SN-Y/Ho diagrams, which also supports this interpretation. However, the hydrothermal input to the source of these ores cannot be ignored and is indicated by high Ba, Cu, Zn, and by high LREE/HREE ratio as well as the plotting of the FeMn samples in the hydrothermal field of the Fe-Mn-(Ni + Co + Cu)*10, (Co + Ni)-(As+Cu + Mo + Pb + V + Zn), (Co + Ni + Cu)-Co/Zn, CeSN/CeSN*-YSN/HoSN and CeSN/CeSN*-NdSN diagrams. In addition, lower Er/Nd ratios than that of seawater and similarity of REE parameters such as ΣREY, Nd and CeSN/CeSN* between the diagenetic FeMn nodules and the FeMn ores of Um Bogma Formation suggest a post-depositional overprint on the REEs geochemistry of these ores. We propose, as most consistent with the evidence from tectonic subsidence history, sequence stratigraphy, and our geochemical-mineralogical data combined with that of others, an initial synsedimentary deposition of Mn, derived from a distally-located back-arc spreading center where modified seawater at relatively low temperature was the hydrothermal fluid released into the surrounding seawater. This plume of Mn-rich water, which can be far-travelled, deposited Mn on the unconformity surface during a rapid transgression. This accumulation of Mn was subsequently modified and significantly upgraded during karstification of the host dolostones soon after deposition of the dolostones. It is likely that the Fe was introduced at this stage via low-oxygen ground water flow along with As and possibly Ba. Finally, much later, there was a flow of warm, saline oxidizing water through the dolomitic aquifer that precipitated Cu, U and Zn in the weathered material accumulated in the karst cavities.

As-bearing new mineral species from Valletta mine, Maira Valley, Piedmont, Italy: IV. Lombardoite, Ba2Mn3+(AsO4)2(OH) and aldomarinoite, Sr2Mn3+(AsO4)2(OH), description and crystal structure

AbstractLombardoite, ideally Ba2Mn3+(AsO4)2(OH), and aldomarinoite, ideally Sr2Mn3+(AsO4)2(OH), are two new minerals of the arsenbrackebuschite group in the brackebuschite supergroup, discovered in Fe–Mn ore in metaquartzites of the abandoned mine of Valletta, Canosio, Val Maira, Cuneo Province, Piedmont, Italy. They occur as red–brown and orange brown, respectively, as subhedral crystals (< 0.5 mm) in thin masses, associated with quartz, aegirine, baryte, calcite, hematite, muscovite and Mn minerals such as cryptomelane, braunite and manganberzeliite. Both minerals are translucent, have yellow–orange streak and vitreous lustre. Both are brittle. Estimated Mohs hardness is 6–6½ for lombardoite (by analogy to canosioite), and 4½–5 for aldomarinoite (by analogy to tokyoite). Calculated densities are 5.124 g/cm3 for lombardoite and 4.679 g/cm3 for aldomarinoite. Both minerals are biaxial (+). Lombardoite shows 2Vz(meas.) = 78(4)° and is pleochroic with X = yellowish brown, Y = brown and Z = reddish brown (Z > Y > X). Aldomarinoite has 2Vz(meas.) = 67.1(1)°, and is pleochroic with X = brown, Y = brownish orange and Z = yellowish brown (Z > Y > X). Point analyses by electron microprobe using wavelength dispersive spectroscopy resulted in the empirical formula (based on 9 O anions): (Ba1.96Sr0.17Pb0.04Na0.02Ca0.02)Σ2.21(Mn3+0.62Fe3+0.13Al0.06Mg0.11)Σ0.92[(As0.87V0.12P0.01)Σ1.00O4]2(OH) for lombardoite, and (Sr1.93Ca0.21Ba0.04Pb0.01)Σ2.19(Mn3+0.48Al0.35Fe3+0.21Mg0.01)Σ1.05[(As0.92V0.03)Σ0.95O4]2(OH) for aldomarinoite. The absence of H2O was confirmed by Raman spectroscopy and infrared spectroscopy. Both minerals are monoclinic, P21/m, with unit-cell parameters a = 7.8636(1) Å, b = 6.13418(1) Å, c = 9.1197(1) Å, β = 112.660(2)° and V = 405.94(1) Å3, for lombardoite and a = 7.5577(4) Å, b = 5.9978(3) Å, c = 8.7387(4) Å, β = 111.938(6)° and V = 367.43(3) Å3, for aldomarinoite. The eight strongest powder X-ray diffraction lines are [d, Å (Irel) (hkl)]: 6.985 (39) (10$\bar{1}$), 3.727 (33) (111), 3.314 (100) (21$\bar{1}$), 3.073 (24) (020), 3.036 (33) (21$\bar{2}$, 10$\bar{3}$), 2.810 (87) (12$\bar{1}$, 112), 2.125 (20) (301, 11$\bar{4}$) and 1.748 (24) (321) for lombardoite and 3.191 (89) (21$\bar{1}$), 2.997 (45) (020), 2.914 (47) (21$\bar{2}$, 10$\bar{3}$), 2.715 (100) (112), 2.087 (39) (12$\bar{3}$, 1.833 (32) (31$\bar{4}$), 1.689 (36) (321), 1.664 (21) (132) for aldomarinoite. The minerals are isostructural with brackebuschite: infinite chains of edge sharing octahedra running parallel to the b axis and decorated with AsO4 groups are connected along the a and c axes through Ba and Sr atoms in lombardoite and aldomarinoite, respectively. The minerals are named after Bruno Lombardo (1944–2014), geologist and petrologist at C.N.R. (National Research Council of Italy), and Aldo Marino (b. 1942) the mineral collector and founding member of the AMI – Italian Micromineralogical Association.

Physicochemical Aspects of Oxidative Consolidation Behavior of Manganese Ore Powders with Various Mn/Fe Mass Ratios for Pellet Preparation.

With the depletion of rich manganese ore resources, plentiful manganese ore powders with various Mn/Fe mass ratios are produced. The physicochemical aspects of oxidative consolidation behavior of manganese ores with various Mn/Fe mass ratios were investigated in this work to determine whether manganese ore powders with high iron content (Fe-Mn ore) can be prepared as high-quality pellets. Physicochemical properties of the pellets were investigated, including cold compression strength (CCS), phase transformation, microstructural evolution, Vickers hardness (HV), porosity, and lattice parameter. CCS testing indicated that the strength of roasted Fe-Mn ore pellets was observably lower than that of pure hematite or manganese ore pellets. Phase and morphology results showed that in Fe-Mn ore pellets, an Mn ferrite phase was generated between hematite and pyrolusite particles. However, newborn Mn ferrites and hematite had an obvious crystal boundary in the crystallographic particles. Moreover, poorly crystallized Mn ferrite particles were evident, along with Mn and Fe element concentration gradients, due to the inadequate diffusion of metal ions. This resulted in poor mechanical properties of the Fe-Mn ore pellets. A temperature over 1275 °C and a roasting time of 15 min is required for the oxidative consolidation of Fe-Mn ores. In such optimized cases, Mn, Fe, O, and Al elements were uniformly distributed in the well-crystallized Mn ferrite grains, which provided favorable mineralogy for the consolidation of Fe-Mn ore powders.

Armellinoite-(Ce), Ca4Ce4+(AsO4)4⋅H2O, a new mineral species isostructural with pottsite, (Pb3Bi)Bi(VO4)4⋅H2O

AbstractArmellinoite-(Ce), ideally Ca4Ce4+(AsO4)4⋅H2O, is a new mineral discovered in Fe–Mn ore in metaquartzites of the Montaldo mine, Corsaglia Valley, Cuneo Province, Piedmont, Italy. It occurs as very small and rare, pale yellow to brown–yellow pseudo-octahedral translucent crystals hosted by a matrix of quartz, hematite, cryptomelane/hollandite, tilasite, muscovite, braunite and montmorillonite. The mineral is translucent, with white streak and has a resinous to vitreous lustre. It is brittle with irregular fracture and fair cleavage parallel to {110} and {100}. Estimated Mohs hardness is ~3–3.5. Calculated density is 4.29 g⋅cm–3. Armellinote-(Ce) is uniaxial (–), ω = 1.795(5), ɛ = 1.765(5) (white light), non-pleochroic and non-fluorescent. Chemical point analyses by WDS-EPMA yielded the empirical formula (based on 17 O+F anions): A(Ca3.89Th0.08Sr0.02La0.03)Σ4.02B(Ce4+0.76Nd0.13Y0.08Gd0.03Sm0.02Pr0.01Dy0.01Ho0.01)Σ1.05[(As4.00P0.01)Σ4.01O4]4⋅(H2O0.85F0.15)Σ2.00. The presence of H2O was confirmed by Raman spectroscopy. The mineral is tetragonal, I41/a, with single-crystal unit-cell parameters a = 10.749(2), c = 12.030(2) Å and V = 1390.0(6) Å3, with Z = 4. The eight strongest X-ray powder diffraction lines are [d Å (Irel; hkl)]: 7.983 (36; 101), 4.443 (23; 2̄11), 2.957 (100; 3̄12), 2.398 (14; 420), 1.875 (22; 424, 325), 1.728 (19; 3̄16), 1.612 (13; 613) and 1.475 (26; 712, 552). The crystal structure (R1 = 0.0284 for 1275 unique reflections) has isolated TO4 (T = As5+) tetrahedra that link Ca2+- or Ce4+-centred polyhedra via common oxygen ligands to form 2D blocks or double-layered (DL) structural units parallel to (001). Armellinoite-(Ce) is isostructural with pottsite, ideally (Pb3Bi)Bi(VO4)4⋅H2O, and closely related to a larger number of anhydrous synthetic compounds. The mineral is named after the mineral collector Gianluca Armellino (b. 1962), who collected the discovery sample.

Combined passivators regulate the heavy metal accumulation and antioxidant response of Brassica chinensis grown in multi-metal contaminated soils.

Passivation of heavy metals is one of the most efficient techniques to remediate soil pollution. However, passivators with single component are usually unsatisfactory in the case of multi-metal contaminated soils. To resolve this problem, a series of combined passivators containing different ratios of Fe-Mn ore, Fe powder, zeolite, bentonite, etc. were designed and used to study their effects on the growth, heavy metal accumulation, and the antioxidant response of Chinese cabbage (Brassica chinensis L.) as well as the soil available forms of heavy metals in a copper refinery's multi-metal (As, Cd, Pb, Cu) contaminated yellow-brown soil and an artificially contaminated (As, Cd, Pb, Cu) calcareous alluvial soil. The results showed that compared with the control, the addition of combined passivators significantly promoted cabbage growth, with the biomass increase up to 1.77 and 3.54 times in yellow-brown soil and calcareous alluvial soil, respectively. The activity of antioxidant enzymes (SOD, CAT, POD) and the content of malondialdehyde (MDA) and glutathione (GSH) decreased, while the chlorophyll content increased significantly, as compared with no passivators. In addition, passivator application decreased As, Cd, Pb, and Cu contents in shoots and roots by 34.8%, 45.6%, 34.9%, and 11.1% and 49.2%, 63.8%, 38.6%, and 46.4% in yellow-brown soil and by 29.8%, 27.3%, 26.8%, and 25.5% and 45.8%, 55.2%, 61.8%, and 5.7% in calcareous alluvial soil, respectively. Besides, the content of soil available heavy metals was reduced by 8.0-17.1% in yellow-brown soil and 3.3-19.1% in calcareous alluvial soil after the application of passivators. The results indicated that the combined passivators formulated in this experiment could efficiently reduce the content of the multi-metals in cabbage and relieve the oxidant stress and could be used as a way to remediate multi-metal polluted soils.

Re-Evaluation of Kombat-Style Mineralization and Implications for Exploration in the Otavi Mountainland, Namibia

This study re-evaluates the characteristics of Cu-Pb-Ag and Fe-Mn ore mineralization of the Kombat Mine and Gross Otavi Mine based on field geology, fluid inclusions, petrology, mineralogy, and geochemistry. This is to determine the genetic relationship between Fe-Mn and Cu-Pb-Ag mineralization. The study has established that the Cu-Pb-Ag ore at the Kombat Mine can be classified as a variant of MVT-type deposit, whereas the Fe-Mn ore can be classified as a stratiform-syn-sedimentary deposit. The formation of the MVT-type deposit is associated with a hydrothermal fluid system with a mean temperature of 183°C and mean salinity of 12.85 wt. % NaCl equivalent. The syn-sedimentary Fe-Mn ore, which is largely associated with calc-silicate lithologies, consists mainly of magnetite and hematite with minor pyrite, hausmannite and jacobsite, and was deposited by diagenetic and mixed diagenetic-hydrogenetic processes under changing oxic and anoxic conditions within the sedimentary basin. Acceptable geochemical exploration indicators of the existing mineralization include anomalous values above 0.5% Cu, 0.2% S; 0.05% Pb; 0.04% As; 0.01% Zn; V, W, Mo, and Ag are 0.002%. Mineralogical indicators include chalcopyrite, bornite, covellite and galena with minor chalcocite, sphalerite, and tennantite for the Cu-Pb MVT-type ores at Kombat Mine.

A study on separation of Mn and Fe from high-alumina ferruginous manganese ores by the carbothermal roasting reduction process

Carbothermal reduction followed by magnetic separation has been recognized as an effective recovery strategy to achieve separation of Mn and Fe from ferruginous manganese ores (Fe-Mn ores). However, it is difficult to improve the recovery of manganese more than 85% by changing carbothermic roasting reduction and magnetic separation. This work clarified the underlying reason for the poor separation with the magnetic separation process and proposed a promising process for the recovery of Fe and Mn from Fe-Mn ore. The effect of operating variables on recovery and separation of Mn and Fe from Fe-Mn ore is initially investigated during the carbothermic reduction roasting process followed by magnetic separation to reveal the underlying reason for the poor separation from Fe-Mn ores. Then, the stepwise reduction behaviors of the MnO-Fe2O3 and MnO-Fe2O3-Al2O3 systems were investigated to clarify that the formation of composite oxide Mn1−xFexO (0 < x < 0.497) and hercynite (FeO·Al2O3) directly caused the poor separation of Fe and Mn from high-alumina Fe-Mn ores. Then, the stepwise reduction roasting behaviors of Mn1−xFexO and FeO·Al2O3 were investigated by XRD, SEM-EDS and XPS analysis. After adjusting the experimental parameters, iron-rich products with a Fe recovery of 94.31% and a grade of 85.21% and manganese-rich product with a Mn recovery of 90.05% and a grade of 54.35% are obtained. The mass ratio of Mn/Fe increased to 8.5 in the manganese-rich product.

Systematic study on separation of Mn and Fe from ferruginous manganese ores by carbothermic reduction roasting process: Phase transformation and morphologies

Carbothermic roasting reduction followed by magnetic separation process is reported as an effective technological process to separation and recovery of Fe and Mn from low-grade ferruginous manganese ores (Fe–Mn ores) as an acceptable feed to meet the demands of the developing manganese industry. In this study, the effects of operating variables on the recovery and grade of Fe and Mn are initially investigated during the carbothermic roasting reduction process followed by magnetic separation. Then, the phase transformation and morphologies of spinel (FeyMn1−y)Al2O4, fayalite FeyMn2−ySiO4 and (FeO)x(MnO)1−x are investigated by SEM-EDS, XRD, TG/DTG and thermodynamic analyses. Finally, the stepwise reduction and interfacial reaction of three types of phases are investigated at 700–1100 °C for 10–120 min to clarify the reason for the poor separation of Mn and Fe from Fe–Mn ores. The effect of MnO on the stepwise reduction behavior of Fe2SiO4 and FeAl2O4 is analyzed in detail. Finally, the tight integration of the MnO phase with a metallic Fe–Mn alloy derived from the stepwise reduction of (FeO)x(MnO)1−x are closely associated with the stepwise reduction of the FeyMn2−ySiO4, (FeyMn1−y)Al2O4 and (Fe,Mn)2O3 phases. In addition, the formation mechanism and the interfacial reduction reaction of (FeO)x(MnO)1−x, (FeyMn1−y)Al2O4 and FeyMn2−ySiO4 are systematically analyzed to show the effect of the MnO phase on the stepwise reduction of the Fe2SiO4 and FeAl2O4 phases. Finally, some suggestions were recommended for the carbothermic reduction followed by magnetic separation for utilizing the Fe–Mn ores effectively. The manganese-rich product an acceptable feed containing 53.60 wt.% total Mn with the Mn recovery of 89.38% and mass fraction of Mn/Fe of 5.43 are obtained.

Synthesis and characterization of manganese ferrite MnxFe3-xO4 from ferruginous manganese ores by multi-step roasting and magnetic separation

Manganese ferrite spinel (MnxFe3-xO4) has been synthesized by multi-step roasting and magnetic separation from ferruginous manganese ore (FeMn ore). In the current work, during the carbothermic reduction process, the reduction behavior of FeMn ore at the high temperature was investigated. Then, the reduced FeMn ore was separated by two-step magnetic separation. The morphologies and properties of the obtained FexMn1-xO products with various x-values by two-step magnetic separation were characterized by XRD and SEM-EDS analysis to further understand the formation mechanism of FexMn1-xO from FeMn ore. In the end, the intermediates were magnetized in an oxidizing roasting step. Based on the experimental results and the thermodynamic calculations, the high temperature (above 950 °C) and long reduction time were conducted to promote the formation of MnxFe3-xO4. The formation mechanism of spinel-type MnxFe3-xO4 was also described in this paper. The morphology and the property evolution of manganese ferrite (MnxFe3-xO4) synthesized by multi-step roasting and magnetic separation were investigated in air atmosphere. The synthesized FexMn3-xO4 product with saturation magnetization was achieved when the intermediates were roasted at 1000 °C for 90 min in air. These findings can provide theoretical support for the reasonable utilization of FeMn ore by multi-step roasting and magnetic separation.

The connection between hydrothermal fluids, mineralization, tectonics and magmatism in a continental rift setting: Fluorite Sm-Nd and hematite and carbonates U-Pb geochronology from the Rhinegraben in SW Germany

Understanding the physical basics of tectonic events, related fluid flow and ore deposition represents one of the great challenges in modern geosciences. In this contribution, Sm-Nd ages of hydrothermal fluorites and U-Pb ages of carbonates and iron oxides from unconformity-related vein type deposits in the Schwarzwald next to the Upper Rhinegraben rift in SW Germany are used to distinguish different pulses of hydrothermal fluid activity and to understand their relation to large-scale tectonics and magmatism. While the fluorites are of Early Jurassic to Oligocene age, carbonate (calcite, dolomite, siderite) and hematite dated by U-Pb small-scale isochrons records formation from Permian to Quaternary with a clear culmination in the Neogene.These new age-data in combination with microthermometry data of primary fluid inclusions from growth zones in the fluorites and carbonates are used to constrain the timing of fluid signatures. This contribution shows that the ages are correlated with changes in fluid properties and/or tectonic events in the evolving continental crust. Comparison with published thermochronological data, apparent ages of URG-related volcanic rocks and the tectono-sedimentary evolution of the Upper Rhinegraben rift show clear correlations between the intensity of hydrothermal mineralization (and, hence, the intensity of fracture-bound fluid flow) with the U-Pb carbonate ages. This method accordingly provides an excellent tool to date rift-related processes like fluid flow, ore deposition and tectonic activation or reactivation of fractures.Fluid properties changed after the deposition of Middle Triassic Muschelkalk evaporites from low salinity, high temperature (1–6 wt.% NaCleq, 200–270 °C, cooling late-metamorphic basement fluids) to high salinity, moderate temperature (20–26 wt.% (NaCl + CaCl2), 50–170 °C, mixture of a modified bittern brine (“basement brine”) with halite dissolution brine). This change led to large scale ore deposition (fluorite-barite-quartz with Pb-Zn-Cu, Bi-Co-Ni-Ag-U, Fe-Mn ores). During the Paleogene and Neogene, previously separated aquifers from various sedimentary units were connected by juxtaposition of the fluid source rocks during Rhinegraben rifting, which resulted in variable salinity and temperature fluids (1–26 wt. % (NaCl + CaCl2), 50–350 °C) by a multi-component fluid mixing process. Typical mineralization related to this shows barren or Pb-Zn-Cu veins with large amounts of barite.

New understanding on separation of Mn and Fe from ferruginous manganese ores by the magnetic reduction roasting process

Magnetic reduction roasting followed by magnetic separation process is reported as a simple route to realize separation of Mn and Fe from ferruginous manganese ores (Fe-Mn ores). However, the separation and recovery of Mn and Fe oxides are not very effective. This work clarified the underlying reason for the poor separation and also proposed some suggestions for the magnetic reduction process. In this work, the effect of temperature on the magnetic reduction roasting – magnetic separation of Fe-Mn ore was investigated firstly. Then the reduction behaviors of MnO2-Fe2O3 system and MnO2-Fe2O3-10 wt.%SiO2 system under 10 vol.% CO-90 vol.% CO2 at 600–1000 °C were investigated by XRD, XPS, SEM-EDS, VSM, DSC and thermodynamics analyses. Reduction and separation tests showed that higher reduction temperature was beneficial to the recovery of iron while it’s not in favor of the recovery of manganese when the temperature was over 800 °C. The formation of composite oxide MnxFe3−xO4 with strong magnetism between the interface of the MnO2 and Fe2O3 particles leaded to the poor separation of iron and manganese. In addition, the formation mechanism of MnxFe3−xO4 from MnO2 and Fe2O3 as well as the interface reaction reduced under 10 vol.% CO was discussed in this study. Finally, some suggestions were recommended for the magnetic reduction roasting for utilizing the Fe-Mn ores effectively.

Textures and trace element composition of pyrite from the Bukit Botol volcanic-hosted massive sulphide deposit, Peninsular Malaysia

The Bukit Botol volcanic-hosted massive sulphide (VHMS) deposit is located in the Central Belt of Peninsular Malaysia. The deposit occurs in a package of Permian-aged coherent felsic volcanic and volcaniclastic rocks which have a geochemical signature indicative of a volcanic arc tectonic setting. Mineralisation shows distinct ore zonation, forming a stringer to massive sulphide zone at the footwall followed by barite lenses and exhalite layers (Fe-Mn ore) at the top. Mineralogy is characterised by pyrite as the major sulphide mineral, with minor chalcopyrite, sphalerite, and rare galena; traces of gold, silver- and tin-bearing minerals also occur in the massive sulphide and barite ores. Laser ablation inductively coupled plasma mass spectrometry (LA−ICP−MS) analysis combined with the textural characteristics of pyrite provides evidence for significant variations of trace elements in different pyrite types at Bukit Botol, having three types of pyrite in the paragenetic sequence. The concentrations of As, Se, Te, Cu, Zn and Pb decrease from the early pyrite 1 to the late stage pyrite 3, and the Co/Ni ratios vary for the three pyrite types. The combined textural and compositional data of pyrite suggest that the hydrothermal fluid responsible for mineralisation evolved from an early, high temperature, reduced, low pH and desulphurized fluid to more S-rich, oxidized, high pH and cooler fluid. Available sulphur isotope data from the Bukit Botol deposit point to reduced seawater, along with a possible magmatic contribution, as the most probable sources for the ore-forming fluids.

Mineralogy and Genesis of the Polymetallic and Polyphased Low Grade Fe-Mn-Cu Ore of Jbel Rhals Deposit (Eastern High Atlas, Morocco)

The Jbel Rhals deposit, located in the Oriental High Atlas of Morocco, hosts a polymetallic Fe-Mn-Cu ore. Large metric veins of goethite and pyrolusite cut through Paleozoic schists that are overlaid by Permian-Triassic basalts and Triassic conglomerates. The genesis of this deposit is clearly polyphased, resulting from supergene processes superimposed over hydrothermal phases. The flow of Permian-Triassic basalts probably generated the circulation of hydrothermal fluids through the sedimentary series, the alteration of basalts and schists, and the formation of hydrothermal primary ore composed of carbonates (siderite) and Cu-Fe sulfides. Several episodes of uplift triggered the exhumation of ores and host rocks, generating their weathering and the precipitation of a supergene ore assemblage (goethite, pyrolusite, malachite and calcite). In the Paleozoic basement, Fe-Mn oxihydroxides are mostly observed as rhombohedral crystals that correspond to the pseudomorphose of a primary mineral thought to be siderite; goethite precipitated first, rapidly followed by pyrolusite and other Mn oxides. Malachite formed later, with calcite, in fine millimetric veins cutting through host-rock schists, conglomerates and Fe-Mn ores.