Kalahari Manganese Field Research Articles

Features of the REE Geochemistry and Genesis of Rocks and Ores of the Nchwaning Manganese Deposit (Kalahari Manganese Field, South Africa)

Features of the REE Geochemistry and Genesis of Rocks and Ores of the Nchwaning Manganese Deposit (Kalahari Manganese Field, South Africa)

Boron isotopes of Manganese ores from the northern part of the Kalahari Manganese Deposit, South Africa

Abstract The world-class deposits of the Kalahari Manganese Field (KMF) in South Africa constitute a key resource of manganese (Mn) ore for the global steel industry. Many aspects of the origin of high metal-grade ores in the northernmost KMF remain unresolved, especially with respect to the complex hydrothermal history of these ores and the source/s of fluids responsible for epigenetic metal enrichment. In this study, the geochemistry of boron (B) is employed as a potential proxy for such processes, and the results are contextualised against an assumed low metal-grade precursor. Samples collected from the northern part of the Kalahari Manganese Deposit allow for the distinction of three Mn ore types, of which the precursor ore is the closest candidate, petrographically and geochemically, to primary/diagenetic Mn deposition. This precursor ore is dominated by Mn-carbonate and braunite, and records B concentrations in the order of a few 100s to 1 000s ppm and positive δ11B values at an average of 11 ± 6‰. Ferruginous Mn ores appear to have formed from decarbonation of precursor ore and metasomatic ferric iron addition, particularly in the stratigraphically upper Mn ore bed, which is closest to the overlying Olifantshoek and Kalahari unconformities. Ferruginous Mn ores appear depleted in B (ca. 500 ppm on average) and have lower boron isotope values (δ11B: 0 ± 3‰). Hydrothermally Mn-enriched ores, in contrast, are dominated by hausmannite, braunite-II and bixbyite and record highest B concentrations (up to 10 000s ppm) and δ11B values as high as 41‰, pointing to metasomatic introduction of B by circulating evaporitic brines. While further research is needed to comprehensively unravel the geochemical intricacies of B within the complex interplay of fluids and rocks in the Hotazel region, the findings of this study still strongly suggest that B holds promise as a tracer for alteration processes in the KMF.

Mineralogy and mineral paragenesis of the Palaeoproterozoic manganese ores of the Avontuur deposit of the Kalahari Manganese Field, South Africa

Abstract This study provides for the first time details of the mineralogy, petrography and mineral paragenetic relationships of manganese ores of the Avontuur deposit, a prominent northern outlier of the Kalahari Manganese Field in the Northern Cape Province of South Africa. Using a combination of light and electron microscopy and X-ray powder diffractometry on an extensive suite of exploration drill core samples, it is shown that the manganese ores comprise an exceptionally fine-grained assemblage of Mn2+-silicates (friedelite, tephroite, gageite), Mn2+/Mn3+-oxides (jacobsite, hausmannite) and Mn2+-carbonates (rhodochrosite, kutnahorite, Mn-dolomite and Mn-calcite). This mineral assemblage is a product of diagenesis and very low-grade regional metamorphism. Locally, this assemblage is overprinted by contact metamorphism or supergene alteration. Despite close geochemical and textural similarities, the manganese ores of the Avontuur deposit are surprisingly different in their mineralogy compared to the carbonate- and braunite-dominated mangano-lutites of the main Kalahari deposit. Distinctly higher concentrations of both SiO2and Fe2O3in the mangano-lutites of the Avontuur deposit as compared to the main Kalahari Deposit provide the reason for the markedly different mineralogy. Such marked differences in bulk chemistry are tentatively attributed to systematic lateral variations in the physicochemical conditions of mineral precipitation during the deposition of the Hotazel Formation.

Saccoite, Ca2Mn+32F(OH)8⋅0.5(SO4), a new, microporous mineral from the Kalahari Manganese Field, South Africa

AbstractSaccoite, Ca2Mn3+2F(OH)8⋅0.5(SO4), is a new mineral found at the N'Chwaning III mine, Kalahari Manganese Field, Northern Cape Province, Republic of South Africa. It occurs as fillings of voids in hydrothermally altered manganese ore (comprising mostly of bixbyite and baryte). Further associated minor minerals are braunite, gypsum, chlorite, sturmanite and ettringite. Saccoite forms small needles, felted crystal masses or crusts. The new mineral is olive green, transparent, with white streak and vitreous lustre. No luminescence is observed. Saccoite is uniaxial (–) with refractive indices at 589(1) nm of ω = 1.705(5) and ɛ = 1.684(2). Pleochroism is distinct, i.e. bluish green (ω) and yellowish green (ɛ). The chemical composition was studied by means of an electron probe micro-analyser (EPMA) using wavelength-dispersive X-ray spectrometry (WDS). The empirical mineral formula is Ca2.06Mn3+1.78Cu0.10Mg0.07F0.97(OH)8.02(SO4)0.39. The unit-cell dimensions of saccoite (space group P4/ncc) are a = 12.834(3) Å, c = 5.622(2) Å, V = 926.0(4) Å3), and the calculated mass density is 2.73 g⋅cm–3. Saccoite exhibits a heteropolyhedral framework structure that is composed of edge- and corner sharing CaF2(OH)6 and M(OH)6 polyhedra (M = Mn3+ and Cu2+) with large channels along [001], which host disordered and only partially occupied groups, especially SO42–. The hydrogen atoms of the OH groups point into the channel to form hydrogen bonds with the channel anions. Ca–F distances are ~2.3 Å, the Ca–OH distances in the range of 2.44–2.58 Ǻ, and the M(OH)6 octahedron is strongly 4+2 Jahn-Teller distorted (4 × ~1.92 Å, 2 × 2.27 Å). The F atom is tetrahedrally coordinated to calcium atoms. The strongest lines in the powder X-ray diffraction pattern [d in Å (relative intensity) (hkl)] are: 9.0735 (35) (110), 4.5370 (95) (220), 4.0644 (20) (310), 3.0105 (100) (321), 2.8117 (20) (002), 2.7242 (75) (411), 1.9755 (35) (611), and 1.8142 (20) (550).

Void filling and water sealing in a decline in the Kalahari Manganese Field

Investigations were conducted to determine the condition and stability of the existing decline at a mine in the Kalahari Manganese Field, Northern Cape Province, South Africa. During the inspection of the decline, voids were identified behind the concrete lining on the hangingwall and sidewalls over a total linear distance of 230 m. The voids did not provide confinement and, as a result, self-mining was occurring behind the lining. Water was flowing into the decline, over a total linear distance of 100 m, at areas where the decline intersected incompetent rock units, causing softening of the concrete lining and deterioration of the surrounding rock mass. Further damage to the concrete lining was caused by expansion and contraction of the wet red clay unit. Remedial work comprised void filling and water sealing to prevent further deterioration of the decline and ensure that it remained operable for the remainder of the life of mine. Void filling was accomplished by drilling rows of holes along the decline to access the voids and filling the voids with foam. This was followed by the sealing with polymer fluids. Telescopic pipes were also installed to allow water to drain off. A visual inspection was conducted and check-holes were drilled to assess the quality of the remedial work. The void filling material had penetrated cracks in the concrete lining, and areas where voids were intersected by check-holes were re-filled. Additional holes were drilled to re-seal areas that were still wet. The remedial work was completed successfully, as all voids were filled and stability achieved without compromising the concrete lining. The ingress of groundwater was also reduced to some residual dampness.

Hydroxymcglassonite-(K), KSr4Si8O20(OH)·8H2O, the first Sr-bearing member of the apophyllite group, from the Wessels mine, Kalahari Manganese Field, South Africa

Abstract A new mineral species, hydroxymcglassonite-(K), ideally KSr4Si8O20(OH)·8H2O, has been found in the Wessels mine, Kalahari Manganese Field, Northern Cape Province, South Africa. It is granular (<0.05 mm), associated with meieranite, sugilite, aegirine, pectolite, and yuzuxiangite. The mineral is colorless, transparent with a white streak and a vitreous luster. It is brittle and has a Mohs hardness of 4.5–5.0; cleavage is perfect on {001} and no parting or twinning was observed. The measured and calculated densities are 2.60(3) and 2.614 g/cm3, respectively. Optically, hydroxymcglassonite-(K) is uniaxial (+), with ω = 1.555(5), ε = 1.567(5) (white light), and absorption O > E. Hydroxymcglassonite-(K) is insoluble in water or hydrochloric acid. An electron microprobe analysis yielded an empirical formula (based on 13 non-H cations pfu) K1.01(Sr2.99Ca1.03)Σ4.02Si7.99O20(OH)·8H2O, which can be simplified to K(Sr,Ca)4Si8O20(OH)·8H2O. Hydroxymcglassonite-(K) is tetragonal with space group P4/mnc and unit-cell parameters a = 9.0792(2), c = 16.1551(9) Å, V = 1331.70(9) Å3, and Z = 2. It is isostructural with hydroxyapophyllite-(K), KCa4Si8O20(OH)·8H2O, with Sr substituting for Ca. The crystal structure of hydroxy-mcglassonite-(K) is characterized by SiO4 tetrahedra sharing corners to form (Si8O20)8– sheets parallel to (001), which are connected by the K and B (= Sr + Ca) cations, as well as hydrogen bonding. The K cation is coordinated by eight H2O groups, and the average K–O distance of 2.941(3) Å is shorter than that of 2.950(3)–2.975(3) Å in hydroxyapophyllite-(K) or fluorapophyllite-(K). The B cation is sevenfold-coordinated (4O + 2H2O + OH), and the average B-O distance of 2.522(3) Å is noticeably longer than that of 2.422–2.435 Å in hydroxyapophyllite-(K) or fluorapophyllite-(K). The Raman spectra of hydroxymcglassonite-(K) and hydroxyapophyllite-(K) are very comparable, especially in the O-H stretching region. The discovery of hydroxymcglassonite-(K), the first Sr-bearing mineral of the apophyllite group, implies that more Sr-bearing members of the group may be found in nature or synthesized in laboratories, but the possibility for an incomplete solid solution between hydroxyapophyllite-(K) and hydroxymcglassonite-(K), due to the size difference between Sr2+ and Ca2+, cannot be ruled out.

Taniajacoite and Strontioruizite, Two New Minerals Isostructural with Ruizite from the N'Chwaning III Mine, Kalahari Manganese Field, South Africa

ABSTRACT Two new mineral species, taniajacoite and strontioruizite, ideally SrCaMn3+2Si4O11(OH)4·2H2O and Sr2Mn3+2Si4O11(OH)4·2H2O, respectively, have been identified from the N'Chwaning III mine, Kalahari manganese field, South Africa. Both minerals occur as brown radiating groups or aggregates of acicular or prismatic crystals, with individual crystals up to 0.15 × 0.04 × 0.02 mm for taniajacoite and 1.3 × 0.2 × 0.2 mm for strontioruizite. Minerals associated with taniajacoite include sugilite, aegirine, pectolite, richterite, potassic-ferri-leakeite, and lipuite, whereas those associated with strontioruizite include sugilite, potassic-magnesio-arfvedsonite, and lipuite. Both taniajacoite and strontioruizite are brown in transmitted light, transparent with very light brown streak and vitreous luster. They are brittle and have a Mohs hardness of 5–5.5; cleavage is good on {010} and no parting or twinning is observed macroscopically. The measured and calculated densities are 3.05(2) and 3.09 g/cm3, respectively, for taniajacoite and 3.20(2) and 3.16 g/cm3 for strontioruizite. Optically, both taniajacoite and strontioruizite are biaxial (–), with α = 1.686(2), β = 1.729(2), γ = 1.746(2) (white light), 2V (meas.) = 63.7(5)°, 2V (calc.) = 62.5° for the former and α = 1.692(2), β = 1.734(2), γ = 1.747(2) (white light), 2V (meas.) = 59.1(5)°, 2V (calc.) = 56.6° for the latter. The calculated compatibility index based on the empirical formula is 0.008 for taniajacoite and 0.015 for strontioruizite. An electron microprobe analysis yielded an empirical formula (based on 17 O apfu) of Sr(Ca0.81Sr0.19)Σ1.00(Mn3+1.90Fe3+0.15Al0.01)Σ2.06Si3.96O11(OH)4·2H2O for taniajacoite and (Sr1.61Ca0.42)Σ2.03(Mn3+1.95Fe3+0.05)Σ2.00Si3.98O11(OH)4·2H2O for strontioruizite. Taniajacoite and strontioruizite are isostructural with ruizite. Strontioruizite, like ruizite, is monoclinic with space group C2 and unit-cell parameters a = 9.1575(4), b = 6.2857(4), c = 12.0431(6) Å, β = 91.744(4)°, and V = 692.90(6) Å3, whereas taniajacoite is triclinic, with space group C1 and a = 9.1386(5), b = 6.2566(3), c = 12.0043(6) Å, α = 90.019(4), β = 91.643(4), γ = 89.900(4)°, and V = 686.08(6) Å3. Their structures are characterized by chains of edge-sharing MnO6 octahedra extended along [010], which are linked together by corner-shared SiO4 tetrahedra in four-membered [Si4O11(OH)2] linear clusters, giving rise to a so-called “hetero-polyhedral framework”. The large cations Sr2+ and Ca2+ occupy the seven-coordinated interstices. Unlike monoclinic ruizite and strontioruizite, taniajacoite with Sr:Ca ≈ 1:1 is triclinic, owing to the ordering of Sr2+ and Ca2+ into two crystallographically distinct sites, indicating an incomplete solid solution between Ca and Sr endmembers. The unit-cell volumes for ruizite, taniajacoite, and strontioruizite appear to vary linearly with the Sr/(Ca + Sr) ratio.

The Effect of Manganese Ore Iron Content on Carbothermic Reduction Rates at Low Temperatures

Extensive studies on the carbothermic reduction of manganese ores from the Kalahari Manganese Field (KMF) in South Africa illustrated an increase in reduction rates with increased iron content in the ore (as oxides). This observation is most noticeable in stage two reduction, ranging from approximately 33% to 70% reduction at temperatures of 1200°C - 1350°C. These studies illustrated the complex mineralogy changes which occur as the ore reduction process proceeds. Manganese ore reduction is complex at intermediate reaction temperatures of 1100°C - 1400°C due to the formation of liquid oxide and/or alloy phases in varying phase proportions and distributions. The results prompt the question: how important is increased iron content in manganese ores in setting low temperature ore reduction rates, both for manganese ores of different mineralogy, and also within the same type of manganese ore? This important aspect is explored in this work by considering both literature evidence and reporting results from simplified experiments which simulate increased iron content in MnO-Fe-C mixtures. The MnO-Fe-C mixtures serve as a simplified reaction system because liquid oxide formation is excluded, allowing the work to be focused on alloy phase formation and its effect on MnO reduction. Furthermore, the results illustrate how the MnO reduction rate equation may be updated to incorporate the effect of manganese ore iron content.

The Where of Mineral Names: Wesselsite, Wessels Mine, Kalahari Manganese Field, South Africa

Wesselsite, SrCuSi4O10 (fig. 3), is a phyllosilicate member of the gillespite group of minerals found in, and named for, the Wessels mine, Kalahari manganese field, South Africa (Giester and Rieck ...

Origin of the Oligocene manganese deposit at Obrochishte (Bulgaria): Insights from C, O, Fe, Sr, Nd, and Pb isotopes

The large manganese (Mn) deposit at Obrochishte (NE Bulgaria) is part of a cluster of similar Early Oligocene deposits located around present-day Black Sea. They collectively constitute the Earth’s second largest endowment of Mn, after the Kalahari Manganese Field in Africa. We have employed a battery of isotopic techniques (C, O, Fe, Sr, Nd, Pb) to help understand the genesis of this deposit. Carbon isotope data indicates that some sections of the Mn-ore layer have diagenetic MnCO3 mineralization, formed by reaction of Mn oxides with organic carbon (Corg), whereas other sections have MnCO3 precipitated directly from the seawater column. Oxygen isotopes show that the high-grade Mn mineralization had seawater as the fluid source, whereas some lower-grade sections had a mix of ground water and seawater as fluid sources. Sr and Nd isotope values of ore leachates also indicate that the Mn deposition occurred in normal Early Oligocene seawater. Nd and Pb isotope values suggest that the clastic host sediments were sourced from continental bedrock rather than younger arc volcanic rocks to the west. Iron isotope composition of the Mn ore implies deposition in a redox-stratified basin, similar to the modern Black Sea, with much of the Fe sequestered in deep, anoxic-euxinic water as sulfides. Similar to the modern Black Sea, most of the detrital Fe was transferred from shallow oxic sediments into deep, anoxic-euxinic water by an “iron shuttle” and remobilized Mn sequestered in the upper suboxic water layer. However, during the Oligocene, the “iron shuttle” operated intermittently due to the chemocline falling mostly below the shelf break, thereby limiting the efficiency of the shuttle mechanism. We propose a model for the Lower Oligocene strata in which intense weathering during the Eocene weathering phase produced a thick lateritic crust on the southern European continent. The drastic sea-level drop at the end of the Eocene initiated downcutting of streams through this weathered material, transferring Fe- and Mn-oxides to the redox-stratified Western Black Sea. Here, these oxides were partly or entirely dissolved in the suboxic (Mn-oxides partly, Fe-oxyhydroxides entirely dissolved) and anoxic-euxinic (Mn-oxides entirely dissolved, dissolved Fe2+ re-precipitated) water layers. Eventually, Fe was re-precipitated as sulfide in the deep anoxic-euxinic water, while Mn accumulated in the suboxic water layer. Transgression in the Early Oligocene brought this Mn-rich water onto the shallow shelf where it precipitated as Mn-oxide, then converted to Mn-carbonates during early diagenesis. Some Mn was also contributed by submarine groundwater discharge. Further transgression brought lower-oxygen water onto the shelf and Mn-carbonate precipitated directly from the water column. The findings from this work provide insights about the unique Oligocene geochemical event in the region that lead to the formation of the 2nd largest cluster of Mn deposits in the world.

Geochemistry of Paleoproterozoic saprolite developed in diabase intruding the Hotazel Formation in the Avontuur deposit of the Kalahari Manganese Field, South Africa

Abstract A diabase sill intersected in drill core GHEX-59 from the Avontuur deposit of the Kalahari Manganese Field of South Africa displays an 8 m thick paleosaprolitic weathering profile developed below the regional unconformity at the base of the ~2.0 Ga red-bed succession of the Gamagara Formation of the Elim Group (Keis Supergroup). Tracking element mobility in the weathered diabase relative to unaltered parent material assists the reconstruction of surface conditions and the nature of pore waters associated with weathering in the Paleoproterozoic. The upper part of the regolith profile (i.e., “E/A and upper B horizon” equivalents of a modern soil profile) was removed in core GHEX-59 by erosion before deposition of the Gamagara Formation. The preserved red upper paleosaprolite (probably corresponding to the “B horizon” of a modern soil profile) grades into a veined light grey-green and eventually a minimally veined dark green paleosaprolite (“C horizon”) with depth, and into little-altered diabase (“R horizon”) deeper still. The weathering is characterized by minimal loss of Si, suggesting limited mass loss and compaction, and large decreases in alkali and alkali earth elements such as Mg, Ca, and Na due to the breakdown of plagioclase and primary mafic minerals. K increases dramatically upwards in the weathering profile towards the unconformity. Various indices of weathering attest to high degrees of chemical weathering, which, combined with paleogeographic constraints, support weathering in humid sub-tropical conditions with mean annual precipitation possibly in excess of 1100 mm/yr. The behavior of Fe (FeT, Fe(II) and Fe(III)), Mn, V, Ce and Cu suggest that the weathering occurred under the influence of oxygenated ground waters below an oxygenated atmosphere. The likely presence of a well-developed terrestrial biosphere during weathering is reflected by the behavior of Cu and P in the paleosaprolite, which is in support of earlier studies that have suggested the widespread bacterial colonization of land in the Paleoproterozoic.

A 1.25 Ga depositional age for the “Paleoproterozoic” Mapedi red beds, Kalahari manganese field, South Africa: New constraints on the timing of oxidative weathering and hematite mineralization

Abstract The Great Oxidation Event (GOE) is marked by the loss of readily oxidizable detrital minerals and the onset of oxidative weathering. One of the oldest post-GOE weathering surfaces, which extends for almost 350 km along strike, occurs in Griqualand West, South Africa. It is best preserved east of the Blackridge thrust, where oxidized paleoweathering profiles are developed below the unconformity at the base of Mapedi-Gamagara red beds. In the Maremane Dome, the red beds preserve pisolitic hematite laterites, which indicate a highly oxygenated atmosphere and suggest hot and humid climatic conditions. The Mapedi and Gamagara Formations are undated east of the Blackridge thrust but were thought to be lithological correlatives of the ≥1.91 Ga Mapedi red bed sequence to the west. Here, we report a U-Pb zircon age of 1.25 Ga for a felsic tuff in red beds of the Mapedi Formation in the Kalahari manganese field. The new tuff age shows that the Mapedi red beds east of the thrust were deposited >650 m.y. after the Mapedi Formation to the west, and therefore they are part of a distinct Mesoproterozoic sequence. Based on lithologic and sedimentological similarities, the Mapedi-east and Gamagara formations are likely to be correlatives that were deposited on an ancient weathering surface at ca. 1.25 Ga. Our findings suggest that key evidence for a highly oxygenated atmosphere during the early Paleoproterozoic actually formed at ca. 1.25 Ga during a major episode of Mesoproterozoic oxidative weathering.

Arsenic-bearing manganese ore of the Mukulu Enrichment in the Kalahari Manganese Field, South Africa: A new discrimination scheme for Kalahari manganese ore

The Thrusted manganese ore above the Blackridge thrust fault in the Kalahari Manganese Field, South Africa has undergone three significant alterations events, namely the Wessels alteration event, the newly identified Mukulu Enrichment and classic supergene alteration along the Kalahari unconformity. Alteration during the Mukulu Enrichment is manifested in the precipitation of fluorapatite within the thrusted manganese ore, resulting in a distinct supergene-related enrichment in arsenic. Using the low-grade, diagenetic Mamatwan-type manganese ore from Mamatwan mine in the south of the Kalahari Manganese Field as a reference protolith ore, a geochemical distinction has been established between the high vanadium-bearing classic supergene altered ore below the Kalahari unconformity, the arsenic-bearing ore of the Mukulu Enrichment, and the high nickel and copper-bearing, high-grade Wessels-type ore. Utilising these alteration-specific geochemical signatures unique to the area, a new method of ore discrimination has been established for the manganese ore types of the Kalahari Manganese Field.

Meieranite, Na2Sr3MgSi6O17, a New Mineral from the Wessels Mine, Kalahari Manganese Fields, South Africa

Abstract A new mineral species, meieranite, ideally Na2Sr3MgSi6O17, has been found in the Wessels mine, Kalahari Manganese Fields, Northern Cape Province, South Africa. It occurs in isolated aggregates embedded in a matrix mainly of sugilite, along with minor aegirine and pectolite. Crystals of meieranite are up to 0.5 × 0.5 × 0.4 mm in size. No twinning is observed. The mineral is light blue to blue in transmitted and under incident lights, transparent with white streak, and has vitreous luster. It is brittle and has a Mohs hardness of 5.5; cleavage is good on {010} and no parting was observed. The measured and calculated densities are 3.41(3) and 3.410 g/cm3, respectively. Optically, meieranite is biaxial (–), with α = 1.610(1), β = 1.623(1), γ = 1.630(1) (white light), 2V (meas.) = 70(1)°, 2V (calc.) = 72°. The calculated compatibility index based on the empirical formula is –0.007 (superior). An electron microprobe analysis yields an empirical formula (based on 17 O apfu) of Na1.96(Sr2.91Ba0.03Ca0.03Pb0.02)Σ2.99(Mg0.62Mn0.28Co0.07Fe0.01)Σ0.98Si6.03O17, which can be simplified to Na2Sr3MgSi6O17. Meieranite is orthorhombic, with space group P21nb and unit-cell parameters a 7.9380(2), b 10.4923(3), c 18.2560(6) Å, and V 1520.50(8) Å3. Its crystal structure is characterized by two kinds of layers that alternate along [010]: layers of corner-sharing SiO4 and M2+O4 tetrahedra (M2+ = Mg, Mn, Co, Fe) and layers of NaO6 and SrO8 polyhedra. The tetrahedral layers consist of eight-, five-, and four-membered rings and are composed of [Si6O17] ribbons (parallel to [101]) linked together by MO4 tetrahedra. Most remarkably, the structure of meieranite is topologically identical to that of the nordite group of minerals, which has the general chemical formula Na3SrR3+M2+Si6O17, where R = Ce and La and M = Zn, Fe, and Mn. Accordingly, chemically, meieranite may be obtained through the coupled substitution of 2Sr2+ for (Na+ + R3+) in nordite.

Rare elements — setting markers of the formation of the manganese and iron ore deposits of Kalahari and Postmasburg areas (South Africa). Communication 1. Kalahari manganese field

In manganese ores of the Hotazel Formation (Transvaal supergroup) of the Lower Proterozoic, associated with banded ferrous silicites, high concentrations of a number of rare elements (B, Ge, W, Mo, Cr, Ni, Zn, Cd, Pb, Ag, Bi, As, Sb, Te, Se) were determined. High boron contents in oxide-carbonate ores (manganese lutites) are considered as a consequence of the concentration by chemsorbtion of this element on Mn-carbonates. It is proposed that as a result of hydrothermal transformations, a wide range of ore-forming (mainly Fe, Mn) and rare elements (including REE) was removed from the underlying andesite-basaltic hyaloclastite Ongeluk Formation In manganese ores and ferruginous silicites, typical values of cerium (Ce/Ce* 0.28–1.72) and europium (Eu/Eu* 0.57–16.31) anomalies were established, which may indicate that the initial sediments accumulated in the marginal shallow sea basin with a pronounced oxide surface water layer and close to anoxide conditions near the bottom. Metalliferous (Mn, Fe) sediments of a shallow water basin at different stages of lithogenesis were enriched with europium (positive Eu/Eu*), subjected to metasomatosis (with redistribution of manganese and the formation of manganese carbonates) and, subsequently, regional metamorphism (up to the stage of sericitic green schists).

The Role of Hydrothermal Activity in the Formation of Karst-Hosted Manganese Deposits of the Postmasburg Mn Field, Northern Cape Province, South Africa

The Postmasburg Manganese Field (PMF), Northern Cape Province, South Africa, once represented one of the largest sources of manganese ore worldwide. Two belts of manganese ore deposits have been distinguished in the PMF, namely the Western Belt of ferruginous manganese ores and the Eastern Belt of siliceous manganese ores. Prevailing models of ore formation in these two belts invoke karstification of manganese-rich dolomites and residual accumulation of manganese wad which later underwent diagenetic and low-grade metamorphic processes. For the most part, the role of hydrothermal processes and metasomatic alteration towards ore formation has not been adequately discussed. Here we report an abundance of common and some rare Al-, Na-, K- and Ba-bearing minerals, particularly aegirine, albite, microcline, banalsite, sérandite-pectolite, paragonite and natrolite in Mn ores of the PMF, indicative of hydrothermal influence. Enrichments in Na, K and/or Ba in the ores are generally on a percentage level for most samples analysed through bulk-rock techniques. The presence of As-rich tokyoite also suggests the presence of As and V in the hydrothermal fluid. The fluid was likely oxidized and alkaline in nature, akin to a mature basinal brine. Various replacement textures, particularly of Na- and K- rich minerals by Ba-bearing phases, suggest sequential deposition of gangue as well as ore-minerals from the hydrothermal fluid, with Ba phases being deposited at a later stage. The stratigraphic variability of the studied ores and their deviation from the strict classification of ferruginous and siliceous ores in the literature, suggests that a re-evaluation of genetic models is warranted. New Ar-Ar ages for K-feldspars suggest a late Neoproterozoic timing for hydrothermal activity. This corroborates previous geochronological evidence for regional hydrothermal activity that affected Mn ores at the PMF but also, possibly, the high-grade Mn ores of the Kalahari Manganese Field to the north. A revised, all-encompassing model for the development of the manganese deposits of the PMF is then proposed, whereby the source of metals is attributed to underlying carbonate rocks beyond the Reivilo Formation of the Campbellrand Subgroup. The main process by which metals are primarily accumulated is attributed to karstification of the dolomitic substrate. The overlying Asbestos Hills Subgroup banded iron formation (BIF) is suggested as a potential source of alkali metals, which also provides a mechanism for leaching of these BIFs to form high-grade residual iron ore deposits.

Rare Elements—Markers of the Formation Setting of Manganese and Iron Ore Deposits in the Kalahari and Postmasburg Fields (South Africa): Communication 1. Kalahari Manganese Field

Manganese ores of the Lower Proterozoic Hotazel Formation (Transvaal Supergroup) associated with the banded Fe-silicites are marked by high concentrations of several rare elements (B, Ge, W, Mo, Cr, Ni, Zn, Cd, Pb, Ag, Bi, As, Sb, Te, Se). High boron contents in the oxide‒carbonate ores (Mn-lutites) are attributed to the chemosorptional concentration of this element on Mn-carbonates. Owing to hydrothermal transformations, a wide range of the ore-forming (mainly Fe and Mn) and rare elements (REE included) was removed from the underlying hyaloclastic basaltic andesites of the Ongeluk Formation. Manganese ores and Fe-silicites are characterized by the typical values of the cerium (Ce/Ce* 0.28–1.72) and europium (Eu/Eu* 0.57–16.31) anomalies that can suggest that primary sediments were deposited in a marginal shallow-marine basin with a prominent oxic surficial water layer and subanoxic conditions near the floor. At different stages of lithogenesis, metalliferous (Mn, Fe) sediments of the shallow-water basin were enriched in Eu (positive Eu/Eu*) and subjected to metasomatism (with the redistribution of Mn and the formation of manganese carbonates) and the consequent regional metamorphism (up to the stage of green sericite schists).

Structural Trends and Solid-Solutions Based on the Crystal Chemistry of Two Hausmannite (Mn3O4) Samples from the Kalahari Manganese Field

The crystal chemistry of two hausmannite samples from the Kalahari manganese field (KMF), South Africa, was studied using electron-probe microanalysis (EPMA), single-crystal X-ray diffraction (SCXRD) for sample-a, and high-resolution powder X-ray diffraction (HRPXRD) for sample-b, and a synthetic Mn3O4 (97% purity) sample-c as a reference point. Hausmannite samples from the KMF were reported to be either magnetic or non-magnetic with a general formula AB2O4. The EPMA composition for sample-a is [Mn2+0.88Mg2+0.11Fe2+0.01]Σ1.00Mn3+2.00O4 compared to Mn2+Mn3+2O4 obtained by refinement. The single-crystal structure refinement in the tetragonal space group I41/amd gave R1 = 0.0215 for 669 independently observed reflections. The unit-cell parameters are a = b = 5.7556(6), c = 9.443(1) Å, and V = 312.80(7) Å3. The Jahn–Teller elongated Mn3+O6 octahedron of the M site consists of M–O × 4 = 1.9272(5), M–O × 2 = 2.2843(7), and an average <M–O>[6] = 2.0462(2) Å, whereas the Mn2+O4 tetrahedron of the T site has T–O × 4 = 2.0367(8) Å. The site occupancy factors (sof) are M(sof) = 1.0 Mn (fixed, thereafter) and T(sof) = 1.0008(2) Mn. The EPMA composition for sample-b is [Mn0.99Mg0.01](Mn1.52Fe0.48)O4. The Rietveld refinement gave R (F2) = 0.0368. The unit-cell parameters are a = b = 5.78144(1), c = 9.38346(3) Å, and V = 313.642(1) Å3. The octahedron has M–O × 4 = 1.9364(3), M–O × 2 = 2.2595(6), and average <M–O>[6] = 2.0441(2) Å, whereas T–O × 4 = 2.0438(5) Å. The refinement gave T(sof) = 0.820(9) Mn2+ + 0.180(9) Fe2+ and M(sof) = 0.940(5) Mn3+ + 0.060(5) Fe3+. Samples-a and -b are normal spinels with different amounts of substitutions at the M and T sites. The Jahn–Teller elongation, Δ(M–O), is smaller in sample-b because atom substitutions relieve strain compared to pure Mn3O4.

An investigation into the 87Sr/86Sr radiogenic isotope geochemistry of the manganese ore of the Kalahari Manganese Field with a view on hydrothermal fluid flow and related rare earth element enrichments

Abstract The Paleoproterozoic Kalahari Manganese Field is the largest known land-based manganese (Mn) deposit on Earth and comprises five erosional relics of the iron- and manganese-rich Hotazel Formation. A total of 19 manganese ore samples from the lower manganese ore horizon of the Hotazel Formation were selected for analysis based on their relative metasomatic alteration states. These samples range from primary diagenetic, classic supergene enriched, hydrothermally enriched (Wessels-type ore) and thrusted manganese ore. When normalised to Post-Archaean Australian shale composites, rare earth elemental analyses on the selected samples indicate significant relative enrichments within the thrusted manganese ore, an ore type that hasn’t been studied from a geochemical point of view, so far. A comparison between these respective enrichments and 87Sr/86Sr ratios indicates a distinct link between REE enrichments and associated alteration events, and a progressive increase in 87Sr/86Sr isotope values. An isotopic relationship between fluid infiltration events and REE redistribution within the Hotazel Formation has been established, highlighting unique isotope signatures necessary in better defining and characterising metasomatism within the Paleoproterozoic Kalahari Manganese Field.

The role of manganese ore reduction morphology development in setting reduction mechanisms

Manganese ores differ extensively in their mineralogical and bulk chemical composition. Consequently these ores follow different mineralogical morphology development paths as the reduction reaction proceeds in the production furnace. Mineralogical factors such as composition and distribution of initial liquid silicate formed at specific temperatures, as well as iron and manganese metallisation patterns, are significant determining factors in the relative importance of different parallel reduction reaction mechanisms in each ore type. Applied mineralogy techniques were used to identify and analyse matrix liquid silicate phase formation in manganese ore reacted at 1300 °C with Carbon Black reductant. The study includes three South African ores from the Kalahari Manganese Field, the ores represent both the Wessels-type and Mamatwan-type mineralogy. FactSage computational thermodynamic calculations were made to explain liquid silicate phase formation and its evolution with increased reaction time. Matrix silicate phase liquidus temperatures and pseudo-ternary phase diagrams in the MnO-FeO-SiO2-CaO-MgO-Al2O3 composition system were calculated. Matrix liquid silicate formed at the relatively low reaction temperature of 1300 °C within all three ores, although different quantities of liquid silicate formed along differing composition paths set by ore mineralogy.